JPH10148952A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrophotographic photoreceptor capable of sufficiently satisfying both requirements of repetition stability and resistance to offset at the same time without impairing electrophotographic characteristics by incorporating >=2 kinds of specified amine compounds as a charge transfer material in a photosensitive layer formed on a conductive substrate. SOLUTION: The photosensitive layer formed on the conductive substrate contains as the charge transfer material the >=2 kinds of amine compounds, each in a specified proportion, represented by the formula in which Ar1 is an optionally substituted aryl group; Ar2 is an optionally substituted phenylene, such naphthylene, such biphenylene, or such anthrylene group; R1 is an H atom or a lower alkyl or lower alkoxy group; M is an optionally substituted aryl group; and X is a tetramethylene or trimethylene group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive layer of an electrophotographic photosensitive member used in an electrophotographic copying machine, a printer, and the like, and more particularly, to a charge transport material of the photosensitive layer.

[0002]

2. Description of the Related Art Conventionally, selenium,
Inorganic photoconductive materials such as zinc oxide, cadmium sulfide, and silicon have been widely used. While these inorganic materials have many advantages, they also have various disadvantages. For example, selenium has the drawback that it is difficult to manufacture and is easily crystallized by heat and mechanical shock.Zinc oxide and cadmium sulfide have problems with moisture resistance and mechanical strength, and are charged by a dye added as a sensitizer. And exposure deterioration, and lacks durability. Silicon is also difficult to manufacture and uses highly irritating gas, so it is expensive and sensitive to humidity, so care must be taken during handling. In addition, selenium and cadmium sulfide have toxicity problems.

In recent years, organic photoreceptors using various organic compounds have been studied for the purpose of overcoming the disadvantages of these inorganic photoreceptors, and have been widely used. Organic photoreceptors include a single-layer photoreceptor in which a charge generating agent and a charge transporting agent are dispersed in a binder resin, and a laminated photoreceptor in which functions are separated into a charge generating layer and a charge transporting layer. The feature of such a photoreceptor, which is called a function-separated type, is that a material suitable for each function can be selected from a wide range. Has been advanced.

[0004] As described above, in order to satisfy the basic performance and high durability requirements of the electrophotographic photoreceptor, the development of new materials and the combination thereof are required.
Various improvements have been made. However, the characteristics of electrophotographic photoreceptors obtained by using only one kind of charge transport agent alone often have both advantages and disadvantages. For example, the solubility in a coating solvent is low, so that it may be difficult to dissolve a necessary amount of electrophotographic properties in a resin binder solution. Even if such a poorly soluble material is dissolved by stirring for a long time, microcrystals precipitate in the liquid or on the surface of the film during storage of the liquid or after preparation of the film. Further, when used in a copying machine, it is difficult to simultaneously satisfy repetition stability and transfer resistance. Therefore, even if the type of the main skeleton is the same, the types and positions of the substituents are changed, or the type of the main skeleton itself is changed, and by using two or more types of charge transport agents, the disadvantages are compensated for and the characteristics are improved. Attempts to improve have been made energetically, but it has been found that the charge traps are newly formed by the mixed materials, and the mobility and dark resistance may be lower than those of the individual charge transport agents. ing. Further, at present, an electrophotographic photoreceptor that sufficiently and simultaneously satisfies required characteristics such as repetition stability and transfer resistance has not yet been obtained.

[0005]

An object of the present invention is to provide an electrophotographic photosensitive member having a photoconductive layer containing a charge generating agent and a charge transporting agent on a conductive support.
An electrophotographic photoreceptor capable of sufficiently and simultaneously satisfying repetition stability and transfer resistance without impairing electrophotographic characteristics by including two or more types of charge transport agents in the photoconductive layer. Is to provide.

[0006]

According to the present invention, a photosensitive layer is provided on a conductive support, and the photosensitive layer comprises, as a charge transport agent, an amine compound represented by the following general formula. It is contained in.

(1) On a conductive support, the following general formula [1]

[0008]

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(Wherein, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted biphenylene group; Represents an unsubstituted anthrylene group, R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom,
It represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, M represents a substituted or unsubstituted aryl group, and X represents a tetramethylene group or trimethylene group. A photosensitive member for electrophotography, comprising two or more of the amine compounds represented by the formula (1) in respective weight ratios.

(2) The amine compound represented by the general formula [1] is represented by the following general formula [2]

[0011]

(Wherein, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted biphenylene group; Represents an unsubstituted anthrylene group, R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom,
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a substituted or unsubstituted aryl group. The electrophotographic photoconductor according to the above (1), which is an amine compound represented by the formula (1):

(3) The amine compound represented by the general formula [1] is a compound represented by the following general formula [3]

[0014]

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(In the formula, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted biphenylene group; Represents an unsubstituted anthrylene group, R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom,
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a substituted or unsubstituted aryl group. The electrophotographic photoconductor according to the above (1), which is an amine compound represented by the formula (1):

(4) The amine compound represented by the general formula [2] is a compound represented by the following general formula [4]

[0017]

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(Wherein, Ar ₁ , Ar ₂ , R ₁ , L and M have the same meanings as in the above-mentioned general formula [2]) and the following general formula [5]

[0019]

(Where Ar ₁ , Ar ₂ , R ₁ , L and M have the same meanings as in the above formula [2]), which is a mixture of two kinds of amine compounds represented by the above formula (2). The photoconductor for electrophotography according to the above.

(5) The amine compound represented by the above general formula [3] is represented by the following general formula [6]

[0022]

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(Wherein, Ar ₁ , Ar ₂ , R ₁ , L and M have the same meanings as in the above-mentioned general formula [3]) and the following general formula [7]

[0024]

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(Where Ar ₁ , Ar ₂ , R ₁ , L and M have the same meanings as in the above-mentioned general formula [3]). The photoconductor for electrophotography according to the above.

(6) The amine compound represented by the general formula [1] is an amine compound represented by the following general formula [2].

[0027]

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And the following general formula [3]

[0029]

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The electrophotographic photosensitive member according to the above (1), which is a mixture of two kinds of amine compounds represented by the following formula (1): The mixing ratio of the two types of amine compounds (4), (5) and (6) is 5:95 to 95: 5, preferably 1: 9 to 9: 1.
It is.

In the present invention, when Ar ₁ is a substituted aryl group, the amine compound represented by the general formula [1] contained in the photosensitive layer has 1 to 4 carbon atoms as a substituent.
A lower alkyl group, a lower alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a benzyl group,
A phenyl group or a halogen atom can be selected, and when these substituents are a lower alkyl group or a lower alkoxy group, they may be further substituted with a lower alkoxy group having 1 to 4 carbon atoms or a halogen atom. Good, when the substituent is a benzyl group or a phenyl group, it has 1 to 1 carbon atoms.
It may be further substituted with 4 lower alkyl groups, lower alkoxy groups having 1 to 4 carbon atoms or halogen atoms.

Ar ₁ may be substituted or unsubstituted, and the aryl group may be selected from phenyl, naphthyl, biphenylyl, anthryl and pyrenyl.

When Ar ₂ is a substituted phenylene group, a substituted naphthylene group, a substituted biphenylene group or a substituted antrylene group, the substituent may be a lower alkyl group having 1 to 4 carbon atoms or a lower alkoxy group having 1 to 4 carbon atoms. Group or a halogen atom, etc., and when these substituents are a lower alkyl group or a lower alkoxy group, they may be further substituted with a lower alkoxy group having 1 to 4 carbon atoms or a halogen atom. .

When L and M are substituted aryl groups, the same substituents as those described above that Ar ₁ can have can be selected as the substituent. When L is a substituted alkyl group, a lower alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a halogen atom can be selected as the substituent. In both cases where L and M are substituted or unsubstituted, the aryl group can be selected from a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group and a pyrenyl group.

When R ₁ is a lower alkyl group or a lower alkoxy group, the lower alkyl group has 1 to 1 carbon atoms.
As the lower alkoxy group, a linear or branched alkoxy group having 1 to 4 carbon atoms can be selected.

The electrophotographic photoreceptor of the present invention has a photosensitive layer containing two types of isomers at different weight ratios depending on the substitution position of the amine compound. There are various forms of the photosensitive layer, and any of the photosensitive layers of the electrophotographic photosensitive member of the present invention may be used. As representative examples, FIGS. 1 to 5 show such photoconductors.

The photoreceptor shown in FIG. 1 has a conductive support 1 on which a photosensitive layer 2 comprising an amine compound, a binder resin and a sensitizing dye is provided.

The photoreceptor shown in FIG. 2 comprises a conductive support 1 and a photosensitive layer 21 in which a charge generating agent 4 is dispersed in a charge transporting medium 3 comprising an amine compound and a binder resin. In the present photoreceptor, the charge generating agent absorbs light to generate charge carriers, which are transported by the charge transport medium.
In this case, it is desirable that the charge transport agent is transparent to light that generates charge carriers. Since the amine compound hardly absorbs in the visible wavelength range, it satisfies the condition that the charge generating agent and the absorption wavelength range do not overlap.

In the photoreceptor shown in FIG. 3, a photosensitive layer 22 composed of a laminate of a charge generation layer 5 mainly composed of a charge generation agent 4 and a charge transport layer 3 made of an amine compound and a binder resin is formed on a conductive support 1. It is provided. In the present photoreceptor, light transmitted through the charge transport layer 3 reaches the charge generation layer 5 and is absorbed by the charge generation agent 4 to generate charge carriers. The charge carriers are injected into the charge transport layer 3 and transported.

The photoreceptor shown in FIG. 4 has the photoreceptor shown in FIG. 3 provided with a photosensitive layer 23 in which the charge generation layer 5 and the charge transport layer 3 are stacked in the reverse order. Generation and transport of charge carriers can be explained by a mechanism similar to that described above.

The photoreceptor shown in FIG. 5 is obtained by providing a photosensitive layer 24 in which a protective layer 6 is further laminated on the charge generation layer 5 of the photoreceptor of FIG. 4 for the purpose of improving mechanical strength.

[0042]

BEST MODE FOR CARRYING OUT THE INVENTION The photoreceptor of the present invention can be manufactured according to a conventional method as follows. For example, two kinds of amine compounds having different substitution positions represented by the above general formula [1] and a binder resin are dissolved in an appropriate solvent, and a charge generating substance, a sensitizing dye, A coating solution is prepared by adding a compound or an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, a pigment, and other additives. The coating solution is coated on a conductive support and dried to form a photosensitive layer having a thickness of several μm to several tens μm, whereby a photosensitive member can be manufactured. In the case of a photosensitive layer comprising a charge generation layer and a charge transport layer, the above-mentioned coating solution is applied on the charge generation layer, or the charge generation layer is placed on the charge transport layer obtained by applying the above coating solution. Can be produced. The photoreceptor thus manufactured may be provided with an undercoat layer, an intermediate layer, and a barrier layer, if necessary.

As the charge generating agent, α-type, β-type, τ-type,
Phthalocyanine pigments such as metal-free phthalocyanine, copper phthalocyanine, aluminum phthalocyanine, zinc phthalocyanine, α-type titanyl phthalocyanine, Y-type titanyl phthalocyanine, Y-type titanyl phthalocyanine and cobalt phthalocyanine of various crystal types such as X type; Azo pigments having a triphenylamine skeleton, azo pigments having a diphenylamine skeleton, azo pigments having a carbazole skeleton, azo pigments having a fluorene skeleton, azo pigments having an oxadiazole skeleton,
Azo pigments having a bisstilbene skeleton, azo pigments having a dibenzothiophene skeleton, azo pigments having a stilbene skeleton, azo pigments having a distyrylbenzene skeleton,
An azo pigment such as a trisazo pigment having a carbazole skeleton. Perylene pigments such as perylene anhydride and perylene imide. Polycyclic quinone pigments such as anthraquinone derivatives, anthuanthrone derivatives, dibenzpyrene quinone derivatives, pyranthrone derivatives, biolanthrone derivatives and isobiolanthrone derivatives. Diphenylmethane and triphenylmethane pigments. Cyanine and azomethine pigments. There are indigoid pigments, bisbenzimidazole pigments, azurenium salts, pyrylium salts, thiapyrylium salts, benzopyrylium salts, squarylium salts and the like. These may be used alone or as a mixture of two or more as necessary.

As the antioxidant, 2,6-di-ter
t-butyl-p-cresol, 2,6-di-tert-
4-methoxyphenol, 2-tert-butyl-4-
Methoxyphenol, 2,4-di-methyl-6-ter
t-butylphenol, 2,6-di-tert-butyl-4-methylphenol, butylated hydroxyanisole, stearyl-propionate-β- (3,5-di-te
rt-butyl-4-hydroxyphenyl, α-tocopherol, β-tocopherol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t
tert-butylanilino) -1,3,5-triazine,
Octadecyl-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate, 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 2,4-bis [(octylthio) methyl] -o-cresol, isooctyl-
Monophenolic compounds such as 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. Triethylene glycol-bis [3- (3-ter
t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2 -Thio-
Diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N,
N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,
3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl)- Isocyanurate, 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (6-tert-butyl-4-methylphenol), 4,4′-butylidene-bis- (3 -Methyl-6-tert-butylphenol), 4,4′-thiobis (6-tert-butyl-3)
-Methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl)
And polyphenol compounds such as butane. These monophenolic compounds and polyphenolic compounds may be used alone or in combination of two or more. Moreover, you may mix and use with an ultraviolet absorber and a light stabilizer.

As the ultraviolet absorber, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole,
[2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -benzotriazole, 2- (3
5-di-tert-butyl-2-hydroxyphenyl)
Benzotriazole, 2- (3-tert-butyl-5)
-Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert) -Amyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,
5,6-tetra-hydrophthalimido-methyl) -5
Benzotriazole-based compounds such as methylphenyl]. 2
-Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,
2 ′, 4,4′-tetrahydroxybenzophenone,
2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,
2'-dihydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-octadecyloxybenzophenone,
Benzophenone compounds such as 4-dodecyloxy-2-hydroxybenzophenone. Benzoate compounds,
Cyanoacrylate compound, oxalic acid anilide compound,
Commercially available triazine compounds are also preferably used. These ultraviolet absorbers may be used alone or in combination of two or more. Further, they may be used as a mixture with a light stabilizer and an antioxidant.

As a light stabilizer, dimethyl succinate / 1
-(2-hydroxyethyl) -4-hydroxy-2,
2,6,6-tetramethylpiperidine polycondensate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, N, N′-bis (3-aminopropyl) ethylenediamine · 2,4-bis [N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,
3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,
2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2- (3,5-ditert-butyl-4-)
Hindered amine compounds such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) hydroxybenzyl) -2-n-butylmalonate and the like. These light stabilizers may be used alone or in combination of two or more. Further, it may be used as a mixture with an ultraviolet absorber and an antioxidant.

Examples of the solvent for preparing the coating solution include tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, cyclohexanone, acetonitrile, N, N-
Polar organic solvents such as dimethylformamide and ethyl acetate,
Aromatic organic solvents such as toluene and xylene, and chlorinated hydrocarbon solvents such as dichloromethane and 1,2-dichloroethane can be used. A solvent having high solubility for the amine compound and the polycarbonate resin is preferably used.

Examples of the binder resin include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylate, methacrylate, and butadiene, polyvinyl acetal, polycarbonate, polyester, polyphenylene oxide, polyurethane, and the like. Various resins that are compatible with the amine compound, such as cellulose ester, phenoxy resin, silicon resin, epoxy resin, and the like. The amount of the binder resin used is usually in the range of 0.4 to 10 times, preferably 0.5 to 5 times the weight of the amine compound.

As sensitizing dyes, methyl violet,
Brilliant green, crystal violet, triarylmethane dyes such as acid violet, rhodamine B, eosin S, xanthene dyes such as rose bengal, thiazine dyes such as methylene blue, pyrylium dyes and thiapyrylium dyes such as benzopyrylium salts, Alternatively, a cyanine dye or the like can be used.

The electron-withdrawing compound forming a charge transfer complex with an amine compound includes chloranil, 2,3-
Quinones such as dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 2-chloroanthraquinone and phenanthrenequinone; aldehydes such as 4-nitrobenzaldehyde; 9-benzoylanthracene; indandione; 3,5-dinitrobenzophenone; , 4,7-
Ketones such as trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, acid anhydrides such as phthalic anhydride and 4-chloronaphthalic anhydride, tetracyanoethylene, terephthalalmalenonitrile, 9-anthryl Cyano compounds such as methylidene malenonitrile, 3-benzalphthalide, 3- (α-cyano-p-nitrobenzal)-
And phthalides such as 4,5,6,7-tetrachlorophthalide.

The photosensitive layer of the present invention may contain a well-known plasticizer for the purpose of improving film formability, flexibility, and mechanical strength. As the plasticizer, for example, phthalate, phosphate, chlorinated paraffin, methylnaphthalene, epoxy compound, chlorinated fatty acid ester and the like can be used.

As the conductive support on which the photosensitive layer of the present invention is formed, well-known materials used for electrophotographic photosensitive members can be used. Aluminum, stainless steel, copper and other metal drums, sheets or laminates of these metals,
Deposits, metal powders, carbon black, copper iodide,
A plastic film, plastic drum, paper, paper tube, or a plastic film or plastic drum that has been rendered conductive by containing a conductive material by applying a conductive material of a polymer electrolyte together with a suitable binder and conducting the conductive treatment. Can be used.

[0053]

The present invention will be described below in detail with reference to examples. Parts in the examples represent parts by weight, and the concentration represents Wt%.

[Example 1] The following bisazo pigment (charge generator No. 1) was used as a charge generator.

[0055]

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1.0 part and 8.6 parts of a 5% tetrahydrofuran solution of a polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) were added to 83 parts of tetrahydrofuran, and the resulting mixture was placed in an agate pot containing agate balls. (Fritsch) for 1 hour to disperse. The obtained dispersion is applied to the aluminum surface of an aluminum-deposited PET film as a conductive support using a wire bar,
Dried at ℃ for 2 hours and further under reduced pressure for 2 hours.
m of the charge generation layer was formed. On the other hand, the following amine compound (amine compound No. 1) as a charge transporting agent

[0057]

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And the following amine compound (amine compound No.
2)

[0059]

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[0060] 1.5 parts of a 1: 1 mixture by weight of 18.7% of an 8% 1,2-dichloroethane solution of a polycarbonate resin (Iupilon Z, manufactured by Mitsubishi Engineering-Plastics Corporation).
Ultrasonic waves were added to 5 parts of the solution to completely dissolve the amine compound. This solution was applied on the above-mentioned charge generating layer with a wire bar, and dried at 60 ° C. under normal pressure for 2 hours and further under reduced pressure for 2 hours to form a charge transport layer having a thickness of 20 μm, thereby producing a photoreceptor. .

Example 2 In Example 1, the amine compound No. 1 and amine compound No. 1 The following amine compound (amine compound No. 3) instead of using

[0062]

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[0063] And the following amine compound (amine compound No. 4)

[0064]

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A photoreceptor was prepared in the same manner as in Example 1, except that a mixture having a weight ratio of 1: 1 was used.

Example 3 In Example 1, the amine compound No. 1 and amine compound No. 1 The following amine compound (amine compound No. 5) instead of using 2

[0067]

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And the following amine compound (amine compound no.
6)

[0069]

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A photoreceptor was prepared in the same manner as in Example 1, except that a mixture of 1: 1 by weight was used.

Example 4 In Example 1, the amine compound No. 1 and amine compound No. 1 The following amine compound (amine compound No. 7) instead of using 2

[0072]

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And the following amine compound (amine compound no.
8)

[0074]

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A photoconductor was prepared in the same manner as in Example 1, except that the mixture of 7: 3 by weight was used.

Example 5 In Example 1, the amine compound No. 1 and amine compound No. 1 Instead of using amine compound No. 2, 1 and the following amine compound (amine compound No. 9)

[0077]

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A photoreceptor was prepared in the same manner as in Example 1, except that a mixture having a weight ratio of 9: 1 was used.

Example 6 In Example 1, the amine compound No. 1 and amine compound No. 1 Instead of using amine compound No. 2, 5 and amine compound no. 7 of 9:
A photoconductor was prepared in the same manner as in Example 1, except that the mixture was used in a weight ratio of 1%.

Example 7 In Example 1, the amine compound No. 1 and amine compound No. 1 The following amine compound (amine compound No. 10) instead of using 2

[0081]

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And the following amine compound (amine compound no.
11)

[0083]

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A photoreceptor was prepared in the same manner as in Example 1, except that a mixture having a weight ratio of 1: 9 was used.

Example 8 In Example 3, the charge generating agent No. Bisazo pigment (charge generator No. 2)

[0086]

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A photoreceptor was prepared in the same manner as in Example 3 except that the photoreceptor was used.

Example 9 The charge generating agent No. 1 instead of perylene pigment (charge generator No. 3)

[0089]

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A photoreceptor was produced in the same manner as in Example 4 except that the above was used.

Example 10 In Example 1, the charge generating agent No. Anthuanthrone pigment (charge generator No. 4) instead of using 1

[0092]

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A photoreceptor was prepared in the same manner as in Example 1 except that the above was used.

Example 11 In Example 1, the charge generating agent No. Instead of using 1, squarylium compound (charge generator No. 5)

[0095]

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A photoreceptor was prepared in the same manner as in Example 1 except that

[Examples 1 to 11] The photoreceptors prepared in Examples 1 to 11 were subjected to an electrostatic copying paper test apparatus (trade name "EPA-8").
100 "manufactured by Kawaguchi Electric Works, Ltd.) to evaluate the electrophotographic characteristics. First, the photosensitive member was subjected to a corona discharge of -6 kV in a dark place, and the charging potential V0 at this time was measured. Then, the substrate was exposed to 5.0 lux of white light, and the half-life exposure amount E1 /
2 (lux · sec) was determined. Further, the appearance of the photoreceptor after repeated measurement was visually observed. The results are shown in [Table 1].

[0098]

[Table 1]

Example 12 7 parts by weight of an alcohol-soluble polyamide resin (CM-8000, manufactured by Toray) were dissolved in 93 parts by weight of methanol, and then aluminum-deposited PE of a conductive support was used.
It is applied on an aluminum surface of a T film using a wire bar, dried at 110 ° C. under normal pressure for 10 minutes, and has a thickness of 1.0 μm.
Was formed. Next, 1.5 parts of α-titanyl phthalocyanine (charge generating agent No. 6) as a charge generating agent was added to 50 parts of a 3% cyclohexanone solution of polyvinyl butyral resin (Eslec BM-2, manufactured by Sekisui Chemical Co., Ltd.) The dispersion was performed for 1 hour with an ultrasonic disperser. The resulting dispersion was applied on the undercoat layer with a wire bar, and dried at 60 ° C. under normal pressure for 2 hours and further under reduced pressure for 2 hours to form a film having a thickness of 0.1 μm.
A 4 μm charge generation layer was formed. On the other hand, the amine compound No. 10 and the following amine compounds (amine compound No. 12)

[0100]

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1.5 parts of the 8: 2 weight ratio mixture was added to 18.75 parts of an 8% 1,2-dichloroethane solution of a polycarbonate resin (Iupilon Z, manufactured by Mitsubishi Engineering-Plastics Co., Ltd.), and ultrasonic waves were applied. The amine compound was completely dissolved. This solution was applied on the above-mentioned charge generating layer with a wire bar, and dried at 60 ° C. under normal pressure for 2 hours and further under reduced pressure for 2 hours to form a charge transport layer having a thickness of 20 μm, thereby producing a photoreceptor. .

Example 13 In Example 12, the charge generating agent No. A photoconductor was prepared by the same way as that of Example 12 except that X-type metal-free phthalocyanine (charge generating agent No. 7) was used instead of using 6.

[Example 14] The following trisazo pigment (charge generator No. 8) was used as a charge generator.

[0104]

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1.0 part and 5% of polyvinyl butyral resin (Eslec BM-2, manufactured by Sekisui Chemical Co., Ltd.)
8.6 parts of cyclohexanone solution is added to cyclohexanone 83
In addition, the mixture was placed in an agate pot containing agate balls, and rotated and dispersed for 1 hour with a planetary type fine particle grinder (manufactured by Fritsch). The resulting dispersion is deposited on an aluminum deposited P as a conductive support.
It was applied on an aluminum surface of the ET film using a wire bar and dried at 60 ° C. under normal pressure for 2 hours and further under reduced pressure for 2 hours to form a charge generation layer having a thickness of 0.3 μm. On the other hand, an amine compound (amine compound No. 13) was used as a charge transport agent.

[0106]

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And the following amine compound (amine compound no.
14)

[0108]

1.5 parts of a 7: 3 weight ratio mixture was added to 18.75 parts of an 8% 1,2-dichloroethane solution of a polycarbonate resin (Iupilon Z, manufactured by Mitsubishi Engineering-Plastics Corporation), and ultrasonic waves were applied. The amine compound was completely dissolved. This solution was applied on the above-mentioned charge generating layer with a wire bar, and dried at 60 ° C. under normal pressure for 2 hours and further under reduced pressure for 2 hours to form a charge transport layer having a thickness of 20 μm, thereby producing a photoreceptor. .

[Example 15] In Example 14, the charge generating agent No. Azurenium compound (charge generator No. 9)

[0111]

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A photoreceptor was produced in the same manner as in Example 14 except that the photoreceptor was used.

[Example 16] In Example 14, the charge generating agent No. Azurenium compound (charge generator No. 10)

[0114]

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A photoreceptor was prepared in the same manner as in Example 14 except for using.

[Examples 12 to 16] The photoreceptors prepared in Examples 12 to 16 were subjected to an electrostatic copying paper test apparatus (trade name “EPA”).
-8100 ") to evaluate the electrophotographic properties. First, a corona discharge of -7.0 kV is performed on the photoreceptor in a dark place,
The charging potential V0 at this time was measured. Then 5μW / c
Exposure with 790 nm monochromatic light of m ²
2 (μJ / cm ² ) was determined. Further, the appearance of the photoreceptor after repeated measurement was visually observed. The results are shown in [Table 2].

[0117]

[Table 2]

[Example 17] The following thiapyrylium salt (charge generator No. 11) was used as a charge generator.

[0119]

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0.1 part and the amine compound No. 5 to 9
Part and the amine compound No. 6 was added to 125 parts of an 8% 1,2-dichloroethane solution of a polycarbonate resin (Iupilon Z, manufactured by Mitsubishi Engineering-Plastics Co., Ltd.), and ultrasonic waves were used to completely dissolve the charge generating agent and the amine compound. . This solution was applied on an aluminum surface of an aluminum-deposited PET film as a conductive support using a wire bar, and was then applied under normal pressure at 60 ° C. for 2 hours and further under reduced pressure.
After drying for a time to form a photosensitive layer having a thickness of 20 μm, a photosensitive member was prepared. This photoreceptor was evaluated for electrophotographic characteristics using an electrostatic copying paper test apparatus (trade name "EPA-8100"). First, the photoreceptor was subjected to a corona discharge of +8 kV in a dark place, and the charging potential V0 at this time was measured. Then, 5.
Exposure with white light of 0 lux, half-exposure amount E1 / 2 (lu
x · sec). As a result, V0 is + 901V,
E1 / 2 was 1.11 (lux · sec). When the appearance of the photoreceptor after repeated measurement was visually observed, the photoreceptor was found to be excellent without crystal precipitation.

As described above, according to the present invention, by including two or more kinds of charge transporting agents in the photoconductive layer, a photosensitive material for electrophotography having excellent repetition stability without deteriorating the basic performance of electrophotography. A body is provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a single-layer photoconductor for electrophotography.

FIG. 2 is a cross-sectional view of a single-layer photoconductor for electrophotography in which a charge generating substance is dispersed.

FIG. 3 is a cross-sectional view of an electrophotographic photoconductor in which a charge generation layer and a charge transport layer are laminated on a conductive support in this order.

FIG. 4 is a cross-sectional view of an electrophotographic photoconductor in which a charge transport layer and a charge generation layer are laminated in this order on a conductive support.

FIG. 5 is a cross-sectional view of an electrophotographic photoconductor provided with a protective layer.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Conductive support 2, 21, 22, 23, 24 Photosensitive layer 3 Charge transport medium, charge transport layer 4 Charge generating substance 5 Charge generating layer 6 Protective layer

Claims (7)

[Claims] 1. A conductive support having the following general formula [1] (Wherein, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted group; R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a substituted or unsubstituted group. Wherein X represents a tetramethylene group or a trimethylene group.) A photosensitive member for electrophotography, comprising a photosensitive layer containing at least two kinds of amine compounds represented by the following formula: 2. The amine compound represented by the general formula [1] is a compound represented by the following general formula [2]: (Wherein, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted group; R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a substituted or unsubstituted group. The electrophotographic photoreceptor according to claim 1, which is an amine compound represented by the following formula: 3. The amine compound represented by the general formula [1] is a compound represented by the following general formula [3]: (Wherein, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted group; R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a substituted or unsubstituted group. The electrophotographic photoreceptor according to claim 1, which is an amine compound represented by the following formula: 4. The amine compound represented by the general formula [2] is a compound represented by the following general formula [4]: (Wherein, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted group; R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a substituted or unsubstituted group. And an amine compound represented by the following general formula [5]: (Wherein, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted group; R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a substituted or unsubstituted group. 3. The electrophotographic photoconductor according to claim 2, wherein the mixture is two kinds of amine compounds represented by the following formula: 5. The amine compound represented by the general formula [3] is a compound represented by the following general formula [6]: (Wherein, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted group; R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a substituted or unsubstituted group. And an amine compound represented by the following general formula [7]: (Wherein, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted group; R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a substituted or unsubstituted group. The electrophotographic photoreceptor according to claim 3, which is a mixture of two kinds of amine compounds represented by the following formula: 6. The two types of amine compounds represented by the general formula [1] are represented by the following general formula [2]: (Wherein, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted group; R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a substituted or unsubstituted group. And an amine compound represented by the following general formula [3]: (Wherein, Ar ₁ represents a substituted or unsubstituted aryl group; Ar ₂ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted group; R ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, L represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a substituted or unsubstituted group. The electrophotographic photoreceptor according to claim 1, which is a mixture of two kinds of amine compounds represented by the following formula: 7. The mixing ratio of two kinds of amine compounds is 5:
7. The electrophotographic photoconductor according to claim 4, wherein the ratio is 95 to 95: 5.