JPH05297613A - Photosensitive body - Google Patents

Abstract

PURPOSE:To provide a photosensitive body having high and good characteristics for repeated use and secular change in which deterioration of the surface due to oxidation of ozone, NOx, etc., is prevented. CONSTITUTION:This photosensitive body has a photosensitive layer on a conductive supporting body. The photosensitive layer contains an amino compd. expressed by formula I and a compd. containing hindered phenol structural units and/or hinderd amine structure units in the molecule. In formula I, Ar1, Ar2, Ar3 and Ar4 are alkyl groups, aralkyl groups, aryl groups, biphenyl groups or heterocyclic groups which may have substituents, R1, R2, R3 are independently hydrogen atoms, alkyl groups, alkoxy groups or halogen atoms, and X is expressed by formula II. In formula II, R4, R5, R6 are hydrogen atoms, alkyl groups, aralkyl groups or aryl groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreceptor having a photosensitive layer containing at least a charge generating material, a charge transporting material and a substance having an antioxidant function, and having improved sensitivity and repetitive characteristics.

[0002]

2. Description of the Related Art Conventionally, as a photoreceptor, one having a photosensitive layer containing an inorganic photoconductive substance as a main component and one having a photosensitive layer containing an organic photoconductive substance as a main component are known. Inorganic materials have drawbacks such as high toxicity, poor film-forming property, lack of flexibility, and high manufacturing cost.

On the other hand, research using organic photoconductive substances typified by polyvinylcarbazole compounds in the photosensitive layer of the photoconductor has progressed and has already been put to practical use. In general, an organic photoconductive substance is better in transparency, lighter in weight and excellent in film forming property than an inorganic photoconductive substance, but inferior in terms of sensitivity, durability and stability due to environmental changes. Therefore, the charge generation function and the charge transport function in the photoconductive function are separately assigned to different substances with high sensitivity and repeated stability,
A function-separated photoreceptor having excellent durability has been developed. The function-separated type photoreceptor has a photosensitive layer in which a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material are laminated, or a charge generating material and a charge transporting material. Some have a photosensitive layer contained in a binder resin.

[0004]

However, even in the above-described photoconductor, the residual potential gradually rises by repeating the image forming process such as charging, exposure, and charge elimination, which causes a problem that the image is fogged. Further ozone generated during corona discharge, causing the charge transport material degradation by NO _X, etc., decrease in charge potential, or there are problems such as image disturbance caused by an increase in residual potential. In order to prevent such a rise in residual potential,
For example, JP-A-57-122444 discloses an attempt to prevent composition deterioration by adding an antioxidant.
At present, a photoreceptor having satisfactory characteristics has not been obtained in long-term repetition.

It is therefore an object of the present invention, by containing a substance having a specific charge transporting material and the antioxidant function in the photosensitive layer, preventing in particular ozone, the oxidation of the charge transport material according to NO _X, etc., high An object is to provide a photoreceptor having excellent sensitivity and repeatability.

[0006]

In order to solve the above problems, the present invention provides a photosensitive member having a photosensitive layer containing a charge generating material and a charge transporting material on a conductive support,
At least an amino compound represented by the general formula [I] as a charge transport material,

[0007]

[Chemical 2]

[Wherein Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are alkyl groups such as methyl group and ethyl group; aryl groups such as phenyl group and naphthyl group; aralkyl groups such as benzyl group; heterocycle A formula group such as a biphenyl group, a thienyl group, a furyl group and a pyrrole group is shown. R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. Further, each of these groups may have a substituent such as an alkyl group, an aralkyl group, an aryl group, an alkoxy group or halogen. X is

[0009]

[Equation 2]

Represents However, R ₄ , R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. ] It is characterized by containing a compound having a hindered phenol structural unit and / or a hindered amine structural unit in the molecule.

The photoconductor of the present invention is a photoconductor in which a photoconductive layer containing a charge generating material and a charge transporting material is provided on a conductive support, and in the photoconductive layer, the above formula [I ] By containing an amino compound represented by the above formula and a compound having a hindered phenol structural unit and / or a hindered amine structural unit in the molecule, oxidative deterioration due to gases such as ozone is suppressed, and high image stability and repeated stability are achieved. It is possible to provide a photoconductor having less property and less change with time.

The charge transporting material used in the photoreceptor of the present invention contains at least one amino compound represented by the general formula [I].

All the amino compounds represented by the above formula [I] are asymmetrical with respect to X and have poor crystallinity, and exhibit good compatibility with the binder resin. From the viewpoint of sensitivity, it is desirable that at least one of Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ can have a biphenyl group.

The amino compound represented by the general formula [I] of the present invention can be synthesized, for example, by the following method.

For example, the following general formula [II]:

[0016]

[Chemical 3]

[Wherein R ₁ , R ₂ , R ₃ and X are general formulas
Same meaning as that of [I]. ] An iodine compound represented by
The following general formulas [III] and [IV]:

[0018]

[Chemical 4]

[In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ have the same meanings as those in formula [I]. ] The amino compound represented by the above can be synthesized by the Ullmann reaction in the presence of a basic compound or a transition metal compound catalyst and a solvent.

The reaction is generally 100 to 25 under normal pressure.
It is carried out at a temperature of 0 ° C., but 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.

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 synthesis of the amino compound of the present invention include Cu and F
Metals such as e, 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,
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, nitric acid Cupric, copper carbonate, cuprous acetate,
Cupric acetate and the like are preferred. Among them, especially CuCl, C
uCl ₂ , CuBr, CuBr ₂ , CuI, CuO, Cu ₂ O, Cu
SO 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 preferably 0.5 to 500 mol% of the halogenated diphenyl derivative 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 and N-methylpyrrolidone is preferable.

The general formulas used in the photoreceptor of the present invention are shown below.
Specific examples of the amino compound represented by [I] are shown below, but the invention is not limited thereto. The amino compound acts as a charge transport material and transports charge carriers generated by absorbing light very efficiently.

[0025]

[Chemical 5]

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

[0036]

[Chemical 16]

[0037]

[Chemical 17]

[0038]

[Chemical 18]

[0039]

[Chemical 19]

[0040]

[Chemical 20]

[0041]

[Chemical 21]

[0042]

[Chemical formula 22]

[0043]

[Chemical formula 23]

[0044]

[Chemical formula 24]

The hindered phenol compound used in the present invention is a compound represented by the following general formula [V], [VI] or [VII], or a compound containing these structural units in the molecule.

[0046]

[Chemical 25]

[Wherein X ₁ is independently a hydrogen atom, a hydroxyl group, an aryl group; for example, a phenyl group, a heterocyclic group; for example, a triazinylamino group, or a C1-C4 alkyl group or an alkoxy group. , The C1 to C4
The alkyl group of may have a hydroxyl group, a carboxyl group, an ester group, an amino group, a phenyl group or the like. When n ₁ is 2 or more, X ₁ may be the same or different. ]

[0048]

[Chemical formula 26]

[In the formula, X ₁ has the same meaning as X ₁ in formula [V].

N ₂ represents an integer of 0 to 3. When n ₂ is 2 or more, R ₇ may be the same or different.

R ₇ is hydrogen atom, hydroxyl group, C 1
It represents a C4 alkyl group, alkoxy group, carbonyloxy group, aralkyl group or heterocyclic group.

N ₃ represents an integer of 0 to 5, and when n ₃ is 2 or more, R ₇ may be the same or different.

Z is --O--, --S--, --NH--, --NR _{8
-, - CH 2 -, -} CHR 9 - (R 8 and R ₉ may have a substituent, an alkyl group or an aryl group), an alkylene group, an arylene group, aralkylene group, alkanecarboxylic acids A divalent residue and a divalent residue of an alkyl ether are shown. ]

[0054]

[Chemical 27]

[In the formula, X ₁ and R ₇ have the same meanings as those in the formula [V].

N ₄ is an integer of 0 to 3, n ₅ is an integer of 0 to _4, and when n ₄ and n ₅ are 2 or more, X ₁ and R ₇ may be the same or different. ..

W is a divalent residue of an alkylcarboxylic acid ester, a divalent residue of an alkylcarboxylic acid ester alkyl ether (including thioether), a divalent residue of an aryloxycarbonyl ester, or a heterocyclic ether. Two
A divalent residue, an aralkylene group, a di- (alkylcarbamoylalkyl), an arylcarboxylic acid ester divalent residue, and a carboxylic acid hydrazide divalent residue are shown. p, q
Are integers of 1 or more, and the sum of p and q is 2 to 4. The hindered amine compound used in the present invention is a compound represented by the following general formula [VIII] or a compound containing a structural unit represented by the following formula in the molecule.

[0058]

[Chemical 28]

[Wherein R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R
₁₄ represents a hydrogen atom, an alkyl group or an aryl group, and Z represents an atomic group necessary for forming a nitrogen-containing alicyclic ring.

One of R ₁₀ and R ₁₁ , and one of R ₁₃ and R ₁₄ may form a ring structure together with Z. The hindered phenol compound and hindered amine compound used in the photoconductor of the present invention are specifically shown below, but the invention is not limited thereto.

[0061]

[Chemical 29]

[0062]

[Chemical 30]

[0063]

[Chemical 31]

[0064]

[Chemical 32]

[0065]

[Chemical 33]

[0066]

[Chemical 34]

[0067]

[Chemical 35]

[0068]

[Chemical 36]

[0069]

[Chemical 37]

[0070]

[Chemical 38]

[0071]

[Chemical Formula 39]

[0072]

[Chemical 40]

[0073]

[Chemical 41]

[0074]

[Chemical 42]

The charge transporting material represented by the general formula [I] and the compound having a hindered phenol structural unit and / or a hindered amine structural unit in the molecule will be described in detail below. a the incorporation can be obtained photoreceptor of the present invention which is excellent in ozone resistance and NO _X resistance with high sensitivity.

Examples of the form of the photoreceptor of the present invention include those shown in FIGS.

For example, a conductive support 1 as shown in FIG.
A function-separated type laminated photoreceptor in which a charge generation layer 5 containing a charge generation material 2 and a charge transport layer 6 containing a charge transport material 3 are laminated in this order, or a conductive material as shown in FIG. A functionally separated photoreceptor in which a charge transporting layer 6 containing a charge transporting material 3 and a charge generating layer 5 containing a charge generating material 2 are laminated in this order on a conductive support 1. A single-layer type photoreceptor in which the photosensitive layer formed on the conductive support 1 as shown in FIG. 3 is formed by mixing the charge generating material 2 and the charge transporting material 3 together with a binder resin to form the photosensitive layer 4. Further, as shown in FIG. 4, a surface protective layer 7 is provided on the surface of the photosensitive member of FIG. 1, and an intermediate layer 8 is provided between the conductive support 1 and the photosensitive layer 4 as shown in FIG. It may be one.

The photoreceptor of the present invention is most preferably a photoreceptor having a structure in which a charge generation layer and a charge transport layer are laminated in this order on a conductive support.

First, the case of producing a laminated photoreceptor as shown in FIG. 1 as the photoreceptor of the present invention will be described. In this case, the charge generation material is vacuum-deposited on the conductive support, or is dissolved in a suitable solvent and applied,
The charge generation material is dispersed in a suitable solvent or, if necessary, a solution in which a binder resin is dissolved, and a coating solution prepared is applied and dried to form a charge generation layer. The thickness of the charge generation layer is 4 μm or less, preferably 2 μm or less. Furthermore, a binder resin, a charge transport material represented by the general formula [I], a hindered phenol compound represented by the general formulas [V], [VI] and [VII], and a general formula [VIII]. The hindered amine compound represented by the formula (1) is combined and dissolved in a suitable solvent, and this solution is applied and dried to form a charge transport layer. As the charge transport material, the compound represented by the general formula [I] of the present invention can be used.
These amino compounds are used alone or in combination of two or more. Further, other charge transport materials may be mixed within the range that does not impair the effects of the present invention. When the proportion of the amino compound in the charge transport layer is small, sufficient sensitivity cannot be obtained, and when the proportion is large, problems such as poor charging and weak mechanical strength of the photosensitive layer occur. 0.02 for the division
To 2 parts by weight, preferably 0.3 to 1.3 parts by weight. The thickness of the charge transport layer is 3 to 50 μm, preferably 5 to 30 μm.
It is desirable to set m. Further, if the addition amount of the hindered phenol compound or the hindered amine compound is small, the effect for preventing the rise of the residual potential cannot be obtained, and if it is too large, the sensitivity may be lowered, or the charge transport material may be crystallized during coating. Therefore, the amount is 1 to 30 wt%, preferably 5 to 25 wt%, and more preferably 10 to 20 wt% with respect to the charge transport material in the charge transport layer.

Further, it is preferable to add a plasticizer, a leveling agent, an electron-withdrawing compound and the like to the charge transport layer. In the photoconductor of the present invention, benzyldiphenyl and O-terphenyl are preferably used as the plasticizer, and the addition amount thereof is about 1 to 30 wt% with respect to the charge transport material.
Silicone oil is suitable as the leveling agent, and it is effective to add 0.01 to 1 wt% of the charge transport material. The electron-withdrawing compound acts very effectively with respect to the rise in residual potential due to repeated use of the photoconductor, and the malodinitrile compound is particularly preferable in the photoconductor of the present invention. In addition, a sensitizer, a thickener, a surfactant, an anti-curl agent, an ultraviolet absorber and the like which are known per se may be added.

A case of producing a single-layer type photoconductor as shown in FIG. 3 as the photoconductor in the present invention will be described.
In this case, the charge generating material, the charge transporting material, the hindered phenol compound, and the hindered amine compound are dispersed in a solution in which the binder resin is dissolved, and this is coated and dried on a conductive support to form a photosensitive layer. A photoconductor is prepared. As the charge transport material, the above amino compounds are used alone or in combination of two or more. In addition, a leveling agent, a plasticizer, etc. are added as appropriate. The mixing ratio of the amino compound in the photosensitive layer is 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, based on 1 part by weight of the binder resin in the photosensitive layer. When the amount of the charge generating material is small, sufficient sensitivity cannot be obtained, and when it is large, problems such as poor charging and weak mechanical strength of the photosensitive layer occur. It is preferable to add 0.01 to 2 parts by weight, preferably 0.2 to 1.2 parts by weight to the parts by weight. The amount of hindered phenol compound and hindered amine compound added is
1 to 30 wt% of charge transport material, preferably 5 to 2
5 wt% is desirable. The thickness of the photosensitive layer is usually 3 to 30 μm, preferably 5 to 20 μm.

The photoreceptor of the present invention may be provided with an intermediate layer as shown in FIG. 5, whereby the adhesion is improved, the coatability is improved, the support is protected, and the photosensitive material is exposed from the support side. The charge injection property to the layer can be improved.

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.

Further, the photoreceptor of the present invention may be provided with a surface protective layer. As a material used for the surface protective layer, a polymer such as an acrylic resin, a polyaryl resin, a polycarbonate resin, or a urethane resin is directly used,
Alternatively, a material in which a low resistance compound such as tin oxide or indium oxide is dispersed is suitable.

Further, an organic plasma polymerized film can be used. The organic plasma polymerized film is appropriately oxygen,
It may contain nitrogen, halogen, and atoms of Group 3 and Group 5 of the periodic table.

As the conductive support used in the photoconductor of the present invention, a sheet or drum of copper, aluminum, iron, nickel or the like is used. In addition, these metals are attached to a plastic film by vacuum deposition, electroless plating, etc.,
Alternatively, a layer of a conductive compound such as a conductive polymer, indium oxide, tin oxide or the like, which is similarly provided by coating or vapor deposition on a support such as paper or a plastic film, can be used.

Examples of the charge generating material used in the photoreceptor of the present invention include bisazo pigments, triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, cyanine dyes, styryl dyes, pyrylium dyes. Organic substances such as dyes, azo dyes, quiacdrine dyes, indigo dyes, perylene dyes, polycyclic quinone pigments, bisbenzimidazole pigments, indathlon pigments, squarylium pigments, phthalocyanine pigments, and pyrrolopyrrole pigments Inorganic substances such as selenium, selenium / tellurium, selenium / arsenic, cadmium sulfide, and amorphous silicon can be used. In addition, any material can be used as long as it absorbs light and generates charge carriers with an extremely high probability.

The binder resin used in the present invention is preferably electrically insulating and has a volume resistance of 1 × 10 ¹² Ω · cm or more when measured alone. For example, known thermoplastic resins, thermosetting resins, photocurable resins,
A binder such as a photoconductive resin can be used. Specifically, saturated polyester resin, polyamide resin, acrylic resin, ethylene-vinyl acetate resin, ion-crosslinked olefin copolymer (ionomer), styrene-butadiene block copolymer, polycarbonate, vinyl chloride-
Thermoplastic resins such as vinyl acetate copolymer, cellulose ester, polyimide, styrene resin; epoxy resin,
Thermosetting resin such as urethane resin, silicone resin, phenol resin, melamine resin, xylene resin, alkyd resin, and thermosetting acrylic resin; photocurable resin; photoconductivity such as polyvinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylpyrrole Resins and the like can be used, and these binder resins can be used alone or in combination of two or more kinds.

The photoreceptor of the present invention includes a binder resin and a plasticizer such as halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, dibutylphthalate, O-terphenyl, and benzyldiphenyl, chloranil, tetracyanoethylene, 2,4,7. -Trinitrofluorenone, 5,6-
Electron withdrawing sensitizers such as dicyanobenzoquinone, tetracyanoquinodimethane, tetrachlorophthalic anhydride, 3,5-dinitrobenzoic acid, sensitizers such as methyl violet, rhodamine B, cyanine dyes, pyrylium salts, thiapyrylium salts, etc. May be used.

The solvent for dissolving these resins varies depending on the kind of the resin, but for example, alcohols such as methanol, ethanol and iso-propyl alcohol,
Ketones such as acetone, methyl ethyl ketone and cyclohexane, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, tetrahydrofuran, dioxane,
Ethers such as ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, chloroform, methylene chloride, dichloroethylene, carbon tetrachloride,
Aliphatic halogenated hydrocarbons such as trichlorethylene,
Or benzene, toluene, xylene, ligroin,
Aromatic compounds such as monochlorobenzene and dichlorobenzene can be used.

[0091]

[Synthesis Example] The synthesis method of the amino compound represented by the above-mentioned amino compound example [4] is shown below. 4-iododiphenyl-
50 g (0.10 mol) of 4'-p-iodobenzyl, 3-
44 g (0.24 mol) of methyldiphenylamine, 35 g (0.3 mol) of potassium carbonate, 10 g (0.16 mol) of copper powder and 400 g of nitrobenzene were charged into a 4-liter flask equipped with a reflux condenser and charged with nitrogen. 1 at 200 ° C under air flow
The reaction was stirred for 8 hours. After the reaction was completed, 200 g of tetrahydrofuran was added to the reaction solution, and then the solid matter was filtered.
The filtrate was separated by silica gel column chromatography, and the separated product was recrystallized in a toluene-ethanol mixed solvent for purification to obtain white crystals having a melting point of 75 to 76 ° C.

The results of elemental analysis are as follows.

[0093]

[0094]

EXAMPLES The present invention will be described below with reference to specific examples.

The amino compounds of the present invention used in the following examples were synthesized by the above-mentioned synthetic examples or a method similar thereto.

Example 1 As the conductive support, an aluminum drum having an outer diameter of 80 mm and a length of 350 mm was used.

The following structural formula:

[0098]

[Chemical 43]

0.45 parts by weight of a bisazo pigment represented by and polyvinyl butyral resin (BX-1, manufactured by Sekisui Chemical Co., Ltd.)
0.45 parts by weight and 50 parts by weight of cyclohexanone were dispersed by a sand mill. The bisazo compound dispersion thus obtained was placed on an aluminum drum to give an impression film thickness of 0.3 g / m ²
And then dried to form a charge generation layer. On top of this, 50 parts by weight of amino compound [12], polycarbonate resin (Panlite K-1300, Teijin Chemicals Ltd.)
50 parts by weight, hindered phenol [P-5] 5 parts by weight, the following formula:

[0100]

[Chemical 44]

1 part by weight of a malodinitrile compound represented by and fluorosilicone oil (X-22-8-19,
Shin-Etsu Chemical Co., Ltd.) with 0.05 part by weight of dichloromethane 40
A solution dissolved in 0 part by weight was applied so as to have a dry film thickness of 20 μm, and dried to form a charge transport layer, thereby preparing a photoreceptor having a photosensitive layer composed of two layers.

Examples 2-5 Hindered phenol compounds added to the charge transport layer
The amount of [P-5] added was 2.5 parts by weight, 7.5 parts by weight, and 1 part by weight, respectively.
Four types of laminated photoconductors were produced in the same manner as in Example 1 except that the amount was 0 parts by weight and 15 parts by weight.

Example 6

[0104]

[Chemical 45]

The bisazo pigment represented by the above general formula 0.4
5 parts by weight and 0.45 part by weight of a polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) were dispersed in a sand mill together with 50 parts by weight of cyclohexanone. The resulting dispersion of the bisazo compound was dried on an aluminum drum to give a dry film thickness of 0.1.
The charge generation layer was formed by applying 3 g / m ² and then drying. On top of this, 50 parts by weight of amino compound [16], 50 parts by weight of polycarbonate resin, 5 parts by weight of hindered phenol compound [p-15], 10 parts by weight of benzyldiphenyl, 1 part by weight of malodinitrile compound and fluorosilicone oil (FL- 100, manufactured by Shin-Etsu Chemical Co., Ltd.)
A solution having 0.1 part by weight dissolved in 400 parts by weight of tetrahydrofuran is applied so as to have a dry film thickness of 20 μm and dried to form a charge transport layer to prepare a photoreceptor having a photosensitive layer composed of two layers. did.

Examples 7 to 10 Similar to Example 6 except that the amounts of the amino compound, hindered phenol compound, benzyldiphenyl and fluorosilicone oil used in the charge transport layer were changed as shown in Table 2 below. Then, each photoconductor was prepared.

[0107]

[Table 2]

Example 11 0.45 part by weight of τ-type phthalocyanine and 0.45 part by weight of butyral resin (BH-3, manufactured by Sekisui Chemical Co., Ltd.) were dispersed in a sand mill together with 50 parts by weight of dichloroethane. The resulting dispersion of the phthalocyanine pigment was applied on an aluminum drum so that the film thickness after application was 0.2 g / m ^2, and then dried to form a charge generation layer. Further on this, 50 parts by weight of the amino compound [51], 50 parts by weight of a polycarbonate resin (PC-Z, manufactured by Mitsubishi Gas Chemical Co., Inc.), 7.5 parts by weight of the hindered amine compound [A-5], 4 parts by weight of O-terphenyl. Parts, 0.6 parts by weight of malononitrile compound and 0.03 parts by weight of dimethyl silicone oil (KF-69, manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 400 parts by weight of dichloroethane so that the dry film thickness was 25 μm. Was applied and dried to form a charge-transporting layer to prepare a photoreceptor having a two-layered photosensitive layer.

Examples 12 to 15 Example 1 except that the amounts of the amino compound, hindered phenol compound, silicone oil and O-terphenyl used in the charge transport layer were changed as shown in Table 3 below.
Each photoconductor was prepared in the same manner as in 1.

[0110]

[Table 3]

Example 16 In Example 11, the hindered amine compound [A-5]
Instead of using 7.5 parts by weight of hindered phenol compound [P-5] 5 parts by weight and hindered amine compound
A photoconductor was produced in the same manner as in Example 11 except that 5 parts by weight of [A-17] was used.

Comparative Examples 1 to 3 Hindered Phenolic Compounds Added to Charge Transport Layer
Three types of laminated photoconductors were prepared in the same manner as in Example 1 except that the addition amount of [p-5] was 0 parts by weight, 0.2 parts by weight, and 20 parts by weight.

Comparative Examples 4 to 5 Example 1 except that the amount of the fluorosilicone oil added to the charge transport layer was set to 0 parts by weight and 0.7 parts by weight.
A laminated photoreceptor was prepared in the same manner as in.

Comparative Examples 6 to 9 In Example 1, the hindered phenol compound [P-
A photosensitive member was prepared in the same manner as in Example 1 except that the following compound was added instead of [5].

Comparative Example 6 N-phenyl-β-naphthylamine Comparative Example 7 6-Ethoxy-2,2,4-trimethyl-1,
2-Dihydroquinoline Comparative Example 8 Tri-Nolylphenyl-phosphite Comparative Example 9 2-Hydroxy-n-octoxybenzophenone Comparative Examples 10-12 In Example 1, the following were used as charge transport materials instead of the amino compound [12]. A photoconductor was prepared in the same manner as in Example 1 except that the compound was used.

[0116]

[Chemical 46]

The photoconductors of Examples and Comparative Examples produced as described above were used as commercially available electrophotographic copying machines (Minolta Camera Co., Ltd.).
EP-5400) manufactured by the same company and charged by corona discharge of -6 Kv to obtain an initial surface potential V ₀ (V) and an exposure amount necessary to reduce the surface potential to half of the initial surface potential (hereinafter referred to as a half exposure amount). ) E _1/2 (Lux · sec) The decay rate DDR ₁ (%) of the initial potential when left in the dark for 1 second was measured. The results are shown in Tables 4-5.

After the electrophotographic process was repeated 5000 times with the developing device removed, V ₀ '(V), E _1/2 ' (L
ux · sec) and DDR ₁ '(%) were measured. The results are shown in Table 6. At this time, the discharges from the charging charger and the transfer charger are in a continuous state.

Next, the photoconductors obtained in Examples 1, 6 and 11 and Comparative Examples 4 to 5 were negatively charged by a commercially available electrophotographic copying machine (EP-5400 manufactured by Minolta Camera Co., Ltd.). Repeated live action shots were taken. Initial surface potential V ₀ (V) of each photoconductor before and after actual copying of 10,000 sheets
And the potential V _i (V) after exposure was measured, and the results are shown in the table. The image quality after the actual copying of 10,000 sheets was evaluated in three grades of ◯ Δ ×. However, in the table, ◯ means good, Δ means that there is some problem, and × means that there is a very problem.

In the photoconductors of Examples 1, 6 and 11,
It was confirmed that in the final image as well as in the initial stage, the gradation was excellent, there was no change in sensitivity, and a clear image was obtained, and the photoreceptor of the present invention was stable in repeatability.
The coating liquid prepared in Example 1 was good even after 6 months, but the coating liquid prepared in Comparative Example 13 had a thickened and slightly yellowish color.

[0121]

[Table 4]

[0122]

[Table 5]

[0123]

[Table 6]

[0124]

By combining a specific charge transporting material with a hindered phenol compound and / or a hindered amine compound, oxidation due to ozone, NO _x, etc. is prevented, high image stability and repeated stability are excellent, and there is no change over time. We were able to provide fewer photoreceptors.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a photoreceptor according to the present invention in which a charge generation layer and a charge transport layer are laminated on a conductive support.

FIG. 2 is a schematic cross-sectional view of a photoreceptor according to the present invention in which a charge transport layer and a charge generation layer are laminated on a conductive support.

FIG. 3 is a schematic sectional view of a photosensitive member according to the present invention having a photosensitive layer on a conductive support.

FIG. 4 is a schematic cross-sectional view of a photoreceptor according to the present invention in which a surface protective layer is provided on the surface of a single-layer type photoreceptor.

FIG. 5 is a schematic cross-sectional view of a photoreceptor according to the present invention in which an intermediate layer is provided between a conductive support and a photosensitive layer.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Conductive support 2 Charge generating material 3 Charge transporting material 4 Photosensitive layer 5 Charge generating layer 6 Charge transporting layer 7 Surface protective layer 8 Intermediate layer

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yuki Shimada 2-3-13 Azuchi-cho, Chuo-ku, Osaka Osaka International Building Minolta Camera Co., Ltd.

Claims (1)

[Claims] 1. A photoreceptor having a photosensitive layer containing a charge generating material and a charge transporting material provided on a conductive support, wherein at least an amino compound represented by the general formula [I] is used as the charge transporting material, and a hinder. A photoreceptor containing a compound having a dephenol structural unit and / or a hindered amine structural unit in its molecule. [Chemical 1] [In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ 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 and R ₃ each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. X is the following Represents. However, R ₄ , R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. ]