JP2001051433A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior repetition stability without impairing electrophotographic characteristics such as potential by electrification and residual potential by disposing a photosensitive layer containing one or more specified benzotriazole-alkylenebisphenol compounds and one or more electric charge transferring agents each having an arylamino group in its molecule on an electrically conductive substrate. SOLUTION: The electrophotographic photoreceptor has a photosensitive layer containing one or more benzotriazole-alkylenebisphenol compounds of the formula and one or more electric charge transferring agents each having an arylamino group in its molecule on the electrically conductive substrate. In the formula, X is H, halogen, alkyl, cycloalkyl, alkoxy or alkylaryl, R1 is alkyl, cycloalkyl or the like, R2 is H, alkyl or aryl and R3 and R4 may be the same or different and are each alkyl, cycloalkyl or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member. More specifically, the present invention relates to an electrophotographic photoconductor having excellent stability and durability having excellent ozone resistance and light resistance.

[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, and a photoreceptor having an arbitrary performance can be easily manufactured. 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, but at present it has not yet been obtained.

[0005] One major problem is that when a photoreceptor is used in a copying machine, heat generated in the electrophotographic process,
It is possible that a strong oxidizing action is caused by light, ozone and the like. A photoreceptor made of an organic material is susceptible to this oxidizing action. For example, a decrease in sensitivity, a decrease in charging potential, an increase in residual potential, a decrease in surface resistance, etc. are observed, and as a result, a remarkable decrease in image and a short life of the photoreceptor are observed. Is occurring.

As a countermeasure, a number of studies have been made to prevent deterioration by adding a stabilizer such as an antioxidant or an ultraviolet absorber to the photoreceptor. Accordingly, there is a problem that these additives volatilize and their functions are not sufficiently exhibited. As a countermeasure, improvements have been made to increase the molecular weight by adding bulky side chains to stabilizers such as antioxidants and ultraviolet absorbers.
A mere measure to increase the molecular weight inevitably results in a decrease in the concentration of the functional structure portion exhibiting the performance, and further increasing the added amount causes a new problem that the abrasion resistance of the photoconductor is reduced. On the other hand, a benzotriazole-alkylenebisphenol compound having both functions of a light stabilizer and an antioxidant has been disclosed (Japanese Patent Application Laid-Open No. H10-175963). As a result of conducting a heat resistance test, it is reported that discoloration and coloring of those resins were prevented. However, there is no description of application examples in fields other than resins, for example, in the field of electrophotographic photoreceptors, and there is no specific description of addition to compounds such as low-molecular charge transport agents.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have investigated the possibility of adding a benzotriazole-alkylenebisphenol compound to an electrophotographic photoreceptor, and to prevent photodegradation and oxidative degradation of various charge transporting agents. As a result, it was found that the compound exhibited remarkable stabilization with respect to a charge transporting agent having an arylamino group in the molecule.

According to the present invention, when a charge transporting agent having an arylamino group in a molecule is used in a photoreceptor for electrophotography, the charge potential is prevented from lowering and the residual potential is prevented from rising. It is an object of the present invention to provide an electrophotographic photoconductor having excellent stability.

[0009]

According to the present invention, the following general formula [1] is provided on a conductive support.

[0010]

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[In the formula, X represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or an alkylaryl group, and R 1 represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or an aralkyl group. , R2 represents a hydrogen atom, an alkyl group or an aryl group, and R3 and R4 may be the same or different and each represents an alkyl group, a cycloalkyl group, an aryl group or an alkylaryl group]. One or two of bisphenol compounds
An electrophotographic photoreceptor comprising a photosensitive layer containing at least one kind and at least one kind of a charge transporting agent having an arylamino group in a molecule.

In the present invention, the charge transporting agent having an arylamino group in the molecule is represented by the following general formula [2], [3] or [4]:

[0013]

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[0014]

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[0015]

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[In the formulas [2], [3] and [4], Z represents a divalent group -O-, -S- or -N (R10)-. R5 and R6 may be the same or different and each is unsubstituted or has 1 to 1 carbon atoms having a substituent.
A straight-chain or branched alkyl group having 2 to 20 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, or an unsubstituted or substituted aralkyl group having 1 to 4 carbon atoms; Represents an aryl group. R7,
R8, R9 and R11 are each a hydrogen atom, an unsubstituted or substituted straight-chain or branched alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted C7-C20 straight-chain alkyl group; Or branched aralkyl group, linear or branched alkoxy group having 1 to 4 carbon atoms, aryloxy group, acyl group, alkoxycarbonyl group having 2 to 5 carbon atoms, halogen atom, nitro group, carbon atom A monoalkyl group substituted with an alkyl group having 1 to 4 atoms, a dialkylamino group substituted with an alkyl group having 1 to 4 carbon atoms, or an amide group. R10 is an unsubstituted or substituted straight-chain or branched alkyl group having 1 to 12 carbon atoms, or an unsubstituted or substituted straight-chain or branched aralkyl group having 1 to 12 carbon atoms. Represents When R5 to R11 have a substituent, the substituent represents a halogen atom, an alkoxy group, an aryloxy group, a dialkylamino group or an alkylthio group;
Only when R5 or R6 is an aryl group, further represents an alkyl group. And a photosensitive layer containing one or more of the hydrazone compounds.

In the present invention, a charge transporting agent having an arylamino group in the molecule is represented by the following general formula [5]:

[0018]

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[In the formula [5], R12 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a substituted amino group. m is an integer of 1 or 2, and when m = 2, both groups may be the same or different, and both groups may combine with each other to form a tetramethylene ring or a trimethylene ring. R13 represents an unsubstituted or substituted phenyl group. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, and a phenyl group. R14 represents hydrogen, a halogen atom, an alkyl group, an alkoxy group or an alkylamino group. R15
And R16 may be the same or different and each is an unsubstituted or substituted phenyl group, an unsubstituted or substituted naphthyl group, an unsubstituted or substituted anthryl group, an unsubstituted or substituted fluorenyl group. Alternatively, it represents an unsubstituted or substituted heterocyclic group, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, and a phenyl group. And a photosensitive layer containing one or more of the styryl compounds.

In the present invention, a charge transporting agent having an arylamino group in the molecule is represented by the following general formula [6]:

[0021]

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[In the formula [6], R17 represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom;
18, R'18, R19 and R'19 may be the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a substituted amino group. n is 1 or 2
When n = 2, the two groups substituted by the same phenyl group may be the same or different. p is an integer of 1 or 2, and when p = 2, two groups substituted by the same phenyl group may be the same or different. And a photosensitive layer containing one or more of the benzidine compounds.

The present invention also relates to a benzotriazole-alkylenebisphenol compound represented by the following general formula [7]:

[0024]

Embedded image [Wherein, R 1 represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or an aralkyl group, R 2 represents a hydrogen atom, an alkyl group or an aryl group, and R 3 and R 4 may be the same or different; Group, a cycloalkyl group, an aryl group or an alkylaryl group].

Specific examples of the benzotriazole-alkylenebisphenol compound represented by the general formula [1] are shown below. The compounds used in the present invention are not limited to these compounds.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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The electrophotographic photoreceptor of the present invention has a photosensitive layer containing one or more kinds of charge transporting agents having an arylamino group in the molecule, and further comprises the benzotriazole-alkylenebisphenol described above. It contains one or more compounds. The diffusion of the benzotriazole-alkylenebisphenol compound used in the present invention is suppressed even by drying at a high temperature during the preparation of a photoreceptor, and the photodeterioration and antioxidant effects of a charge transport agent having an arylamino group in the molecule are also suppressed. Is remarkable, so there is no need for additional preparation at the time of initial addition,
It is possible to prevent a decrease in physical properties of the photoreceptor, particularly a decrease in surface resistance, due to an increase in the amount of the additive. In addition, since it acts on a charge transporting agent having an arylamino group in the molecule to surely suppress light degradation and prevent oxidation, it is possible to prevent deterioration of the image of the photoconductor and shortening of life.

[0039]

DESCRIPTION OF THE PREFERRED EMBODIMENTS There are various forms of the photosensitive layer, and any of them can be employed as the photosensitive layer of the electrophotographic photosensitive member of the present invention. As representative examples, FIGS. 1 to 5 show such photoconductors.

The photoreceptor of FIG. 1 has a charge transporting agent having an arylamino group in a molecule on a conductive support 1-these are represented by the general formulas [2], [3], [4], [5], A photosensitive layer 2 comprising a sensitizing dye and a benzotriazole-alkylenebisphenol compound, which may be a specific amine compound represented by [6].

The photoreceptor of FIG. 2 comprises a charge transporting agent having an arylamino group in the molecule on the conductive support 1-these are represented by the general formulas [2], [3], [4], [5], [5] 6], and a photosensitive layer 21 in which a charge generator 4 is dispersed in a charge transport medium 3 made of a benzotriazole-alkylenebisphenol compound. . 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.

The photoreceptor shown in FIG. 3 has a charge generating layer 5 mainly composed of a charge generating agent 4 on a conductive support 1 and a charge transporting agent having an arylamino group.
Specific amine compounds represented by [3], [4], [5], [6] may be used, and benzotriazole-
Charge transport layer 3 composed of alkylene bisphenol compound
The photosensitive layer 22 is formed by stacking the following. 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 has a structure 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.

The photoreceptor of the present invention can be manufactured according to a conventional method as follows. For example, the benzotriazole-alkylene bisphenol compound represented by the general formula [1] and the general formulas [2], [3], [4],
The specific amine compound represented by [5] or [6] is dissolved in a suitable solvent together with a binder resin, and if necessary, a charge generating substance, a sensitizing dye, an electron-withdrawing compound, or a plasticizer, A coating liquid is prepared by adding 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 solvent for preparing the coating liquid, 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 binder resin is preferably used.

Examples of the binder resin include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylate and methacrylate butadiene, polyvinyl acetal, polycarbonate, polyester, polyphenylene oxide, and polyurethane cellulose ester. And various resins compatible with a benzotriazole-alkylenebisphenol compound and a specific amine compound, such as phenoxy resin, silicon resin and epoxy resin. 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.

Charge transporting agents having an arylamino group in the molecule-these are represented by the general formulas [2], [3], [4],
The specific amine compound represented by [5] or [6] may be used, whereas one or more of the benzotriazole-alkylenebisphenol compounds represented by the general formula [1] may be replaced by It is effective to add up to 40% by weight, preferably 3 to 30% by weight.

As the charge generator, α-type, β-type, τ-type,
Metal-free phthalocyanine, copper phthalocyanine, aluminum phthalocyanine, zinc phthalocyanine, α-type, β-type, Y-type oxotitanyl phthalocyanine, cobalt phthalocyanine, hydroxygallium phthalocyanine, chloroaluminum phthalocyanine, chlorindium phthalocyanine, Cu- 9.6 of black angle 2θ with respect to Kα ray (wavelength 1.541)
Phthalocyanine pigments such as titanyl phthalocyanine having large peaks at ° and 27.2 °. Azo pigments having a triphenylamine skeleton, azo pigments having a diphenylamine skeleton, azo pigments having a carbazole skeleton,
Azo pigment having fluorene skeleton, azo pigment having oxadiazole skeleton, azo pigment having bisstilbene skeleton, azo pigment having dibenzothiophene skeleton, azo pigment having stilbene skeleton, azo pigment having distyrylbenzene skeleton, carbazole skeleton And azo pigments such as trisazo pigments. 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. Indigo pigments, bisbenzimidazole pigments, azurenium salts, pyrylium salts, thiapyrylium salts, benzopyrylium salts, squarylium salts and the like. These can be used alone or as necessary.
You may mix and use more than one kind.

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.

As electron-withdrawing compounds which form a charge transfer complex with an amine compound, 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.

[0054]

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%.

[Example 1] X-type metal-free phthalocyanine (charge generator No. 1) as charge generator

[0056]

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1.5 parts of the solution was added to 50 parts of a 3% cyclohexanone solution of polyvinyl butyral resin (Eslec BL-S, manufactured by Sekisui Chemical Co., Ltd.), and the mixture was dispersed with an ultrasonic disperser for 1 hour. The obtained dispersion was applied on an aluminum surface of an aluminum-deposited PET film as a conductive support using a wire bar, and dried at 110 ° C. under normal pressure for 1 hour to obtain a film thickness of 0.4.
A μm charge generation layer was formed. On the other hand, the following benzotriazole-alkylenebisphenol compound (additive No. 1) 16 parts as an additive

[0058]

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The following hydrazone compound (charge transport agent No. 1) was used as the charge transport agent.

[0060]

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144 parts of polycarbonate resin (Iupilon Z, manufactured by Mitsubishi Engineering-Plastics Corporation)
Was added to 2000 parts of a 9.0% 1,2-dichloroethane solution, and ultrasonic waves were applied thereto to completely dissolve the benzotriazole-alkylenebisphenol compound and the hydrazone compound. This solution was applied on the above-mentioned charge generating layer with a wire bar, and dried at 120 ° C. under normal pressure for 1 hour to form a film having a thickness of 20 μm.
m was formed to form a photoreceptor.

Example 2 The charge transporting agent No. The following hydrazone compound (charge transporting agent No. 2) instead of using 1

[0063]

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

Example 3 In Example 1, the charge transporting agent No. Instead of using 1, the following benzidine compound (charge transporting agent No. 3)

[0066]

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

Example 4 The charge transporting agent No. Instead of using 1, the following benzidine compound (charge transporting agent No. 4)

[0069]

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

[Comparative Example 1]
o. Instead of using 1, the following benzotriazole compound (additive No. 2)

[0072]

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And the following phenolic compounds (additive no.
3)

[0074]

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A comparative photoreceptor was prepared in the same manner as in Example 2 except that a 1: 1 weight ratio mixture was used. [Example 5] In Example 2, the charge generation agent No. A photoconductor was prepared by the same way as that of Example 2 except that τ-type metal-free phthalocyanine (charge generating agent No. 2) was used instead of using photoreceptor 1.

Example 6 In Example 5, the charge transporting agent No. Instead of using styryl compound (charge transporting agent No. 5)

[0077]

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And the following styryl compound (charge transporting agent No.
6)

[0079]

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A photoreceptor was prepared in the same manner as in Example 5, except that a 1: 1 weight ratio mixture was used.

Example 7 In Example 5, the charge transporting agent No. A photoconductor was prepared by the same way as that of Example 5 except that instead of using Benzidine 2, a benzidine compound (charge transporting agent No. 4) was used.

Example 8 In Example 5, the charge transporting agent No. Instead of using 2, the following benzidine compound (charge transporting agent No. 7)

[0083]

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A photoreceptor was produced in the same manner as in Example 5 except that the photoreceptor was used.

Comparative Example 2 Additive N in Example 6
o. Instead of using 1, a benzotriazole compound (additive No. 2) and a phenol compound (additive No. 3)
A comparative photoconductor was prepared in the same manner as in Example 6, except that a 1: 1 weight ratio mixture was used.

Example 9 In Example 2, the charge generating agent No. Y-type oxotitanyl phthalocyanine (charge generator No. 3)

[0087]

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A photoconductor was prepared in the same manner as in Example 2 except that

Example 10 In Example 6, the charge generating agent No. A photoconductor was prepared by the same way as that of Example 6 except that α-type oxotitanyl phthalocyanine (charge generating agent No. 4) was used instead of the photoreceptor 2.

Comparative Example 3 Additive N in Example 10
o. Instead of using 1, a benzotriazole compound (additive No. 2) and a phenol compound (additive No. 3)
A photoconductor for comparison was prepared in the same manner as in Example 10, except that a 1: 1 weight ratio mixture was used.

[Examples 1 to 10 and Comparative Examples 1 to 3] The photosensitive drums manufactured in Examples 1 to 10 and Comparative Examples 1 to 3 were used as photosensitive drum characteristics measuring devices (trade name "ELYSIA-II", Trek Japan (trade name)). (Manufactured by Co., Ltd.). First, a corona discharge of -5.0 kV was performed on the photoreceptor in a dark place, and subsequently, a charging potential V0 when a 50 lux erase lamp was turned on was measured. Then 780 nm-4
Exposure was performed with 0 μW monochromatic light, and the residual potential Vr was determined. Next, after exposing this photoreceptor to 20 ppm ozone gas for 5 days in a room under fluorescent lamp illumination, in the same manner as before exposure,
The charging potential V0 and the residual potential Vr were measured. The results are shown in [Table 1].

[0092]

[Table 1]

Example 11 The following bisazo pigment (charge generator No. 5) was used as a charge generator.

[0094]

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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,
Drying was performed at 2 ° C. for 2 hours to form a charge generation layer having a thickness of 0.3 μm. On the other hand, 16 parts of a benzotriazole-alkylenebisphenol compound (additive No. 1) as an additive and a hydrazone compound (charge transport agent No. 1) as a charge transport agent.
1) 144 parts of a polycarbonate resin (Iupilon Z,
9.0 of Mitsubishi Engineering-Plastics Corporation)
The benzotriazole-alkylenebisphenol compound and the hydrazone compound were completely dissolved by adding ultrasonic waves to 2000 parts of a 1,2-dichloroethane solution.
This solution was applied on the above-mentioned charge generation layer with a wire bar, and dried at 120 ° C. under normal pressure for 1 hour to form a charge transport layer having a thickness of 20 μm, thereby producing a photoreceptor.

[Example 12] In Example 11, the charge transporting agent No. A photoconductor was prepared by the same way as that of Example 11 except that a styryl compound (charge transport agent No. 6) was used instead of the photoreceptor 1.

Example 13 In Example 11, the charge transporting agent No. Instead of using styryl compound (charge transport agent No. 5) and styryl compound (charge transport agent No. 5).
Example 11 except that the mixture of 6) in a 1: 1 weight ratio was used.
A photoreceptor was produced in the same manner as described above.

Comparative Example 4 Additive N in Example 12
o. Instead of using 1, a benzotriazole compound (additive No. 2) and a phenol compound (additive No. 3)
A comparative photoconductor was prepared in the same manner as in Example 12, except that a 1: 1 weight ratio mixture was used.

Example 14 The following trisazo pigment (charge generator No. 6) was used as a charge generator.

[0100]

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1.0 part and 5% of polyvinyl butyral resin (Eslec BL-S, manufactured by Sekisui Chemical Co., Ltd.)
8.6 parts of a tetrahydrofuran solution was added to 83 parts of tetrahydrofuran, put into an agate pot containing agate spheres, and dispersed by rotating for 1 hour with a planetary-type fine-mill (Fritsch). The obtained dispersion was applied on an aluminum surface of an aluminum-deposited PET film as a conductive support using a wire bar, and dried at 60 ° C. under normal pressure for 2 hours to obtain a film thickness of 0.3 μm.
Was formed. On the other hand, the following benzotriazole-alkylenebisphenol compound (additive No. 4) as an additive

[0102]

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16 parts and the following styryl compound as a charge transport agent (charge transport agent No. 8)

[0104]

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144 parts of polycarbonate resin (Iupilon Z, manufactured by Mitsubishi Engineering-Plastics Corporation)
Was added to 2000 parts of a 9.0% 1,2-dichloroethane solution, and ultrasonic waves were applied thereto to completely dissolve the benzotriazole-alkylenebisphenol compound and the styryl compound. This solution was applied on the charge generation layer with a wire bar and dried at 120 ° C. under normal pressure for 1 hour to form a film having a thickness of 20 μm
To form a photoreceptor.

[Example 15] In Example 14, the charge transporting agent No. Instead of using 8, the following benzidine compound (charge transporting agent No. 9)

[0107]

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

Comparative Example 5 Additive N in Example 15
o. Instead of using benzotriazole compound (additive No. 2) and phenol compound (additive No. 3)
A comparative photoconductor was prepared in the same manner as in Example 15, except that a mixture having a weight ratio of 1: 1 was used.

[Examples 11 to 15 and Comparative Examples 4 and 5] The photosensitive drums manufactured in Examples 11 to 15 and Comparative Examples 4 and 5 were subjected to a photosensitive drum characteristic measuring apparatus (trade name “ELYSIA-II”, Trek Japan, Inc.). (Manufactured by Co., Ltd.). First, a corona discharge of -5.0 kV was performed on the photoreceptor in a dark place, and subsequently, a charging potential V0 when a 50 lux erase lamp was turned on was measured. Next, the resultant was exposed with an image exposure of 70 lux to determine a residual potential Vr. next,
After exposing this photoreceptor to 20 ppm ozone gas for 5 days in a room under fluorescent lamp illumination, the charged potential V0 and the residual potential Vr were measured in the same manner as before the exposure. The results are shown in [Table 2].

[0111]

[Table 2]

As is apparent from the results of Table 1 and Table 2, in the examples using the benzotriazole-alkylenebisphenol compound of the present invention as an additive, the charge potential V0 of the photoreceptor decreases even after exposure to ozone gas. It can be seen that the rise in the residual potential (Vr) of the photoconductor is also suppressed. On the other hand, in the comparative example, it can be seen that the charging potential V0 of the photoconductor decreases after exposure to the ozone gas, and the residual potential (Vr) of the photoconductor increases.

[0113]

According to the electrophotographic photoreceptor of the present invention using a charge transporting agent having an arylamino group in the molecule and adding a benzotriazole-alkylenebisphenol compound, the charge potential is prevented from lowering even after exposure to ozone gas. , The rise of the residual potential is suppressed. Furthermore, since the addition amount of the additive is small, it exhibits properties excellent in repetition stability without deteriorating the basic performance of electrophotography.

[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]

 REFERENCE SIGNS LIST 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

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2H068 AA16 AA17 AA20 AA21 BA12 BA13 BA16 BA22 BA24 FA01 FA02

Claims (6)

[Claims] 1. A conductive support having the following general formula [1] [In the formula, X represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or an alkylaryl group, R1 represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or an aralkyl group;
Represents a hydrogen atom, an alkyl group or an aryl group;
And R4 may be the same or different and each represents an alkyl group, a cycloalkyl group, an aryl group or an alkylaryl group], and one or more benzotriazole-alkylenebisphenol compounds represented by the formula:
An electrophotographic photoreceptor comprising a photosensitive layer containing one or more charge transporting agents having an arylamino group in the molecule. 2. A charge transporting agent having an arylamino group in a molecule represented by the following general formula [2], [3] or [4]: Embedded image Embedded image [In the formulas [2], [3] and [4], Z represents a divalent group -O-, -S- or -N (R10)-. R5 and R6 may be the same or different and each is an unsubstituted or substituted straight-chain or branched alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted C7-C20 alkyl group. Represents a linear or branched aralkyl group, or an unsubstituted or substituted aryl group having 1 to 4 rings. R7, R8, R9 and R11 are each a hydrogen atom, an unsubstituted or substituted linear or branched alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted carbon atom having 7 carbon atoms.
To 20 linear or branched aralkyl groups, linear or branched alkoxy groups having 1 to 4 carbon atoms, aryloxy groups, acyl groups, alkoxycarbonyl groups having 2 to 5 carbon atoms, halogen atoms , A nitro group, a monoalkyl group substituted with an alkyl group having 1 to 4 carbon atoms, a dialkylamino group substituted with an alkyl group having 1 to 4 carbon atoms, or an amide group.
R10 is an unsubstituted or substituted straight-chain or branched alkyl group having 1 to 12 carbon atoms, or an unsubstituted or substituted straight-chain or branched aralkyl group having 1 to 12 carbon atoms. Represents When R5 to R11 have a substituent, the substituent represents a halogen atom, an alkoxy group, an aryloxy group, a dialkylamino group or an alkylthio group, and also represents an alkyl group only when R5 or R6 is an aryl group. 2. The electrophotographic photoconductor according to claim 1, further comprising a photosensitive layer containing one or more of the hydrazone compounds represented by the formula (1). 3. The charge transporting agent having an arylamino group in the molecule is represented by the following general formula [5]: [In the formula [5], R12 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a substituted amino group.
m is an integer of 1 or 2, and when m = 2, both groups may be the same or different, and both groups may combine with each other to form a tetramethylene ring or a trimethylene ring. R13 represents an unsubstituted or substituted phenyl group. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, and a phenyl group. R14 represents hydrogen, a halogen atom, an alkyl group, an alkoxy group or an alkylamino group. R15 and R16 may be the same or different and each is an unsubstituted or substituted phenyl group, an unsubstituted or substituted naphthyl group, an unsubstituted or substituted anthryl group, an unsubstituted or substituted fluorenyl. Represents an unsubstituted or substituted heterocyclic group, and in this case, the substituent includes an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, and a phenyl group. 2. The electrophotographic photoreceptor according to claim 1, further comprising a photosensitive layer containing one or more styryl compounds represented by the following formula: 4. A charge transporting agent having an arylamino group in a molecule is represented by the following general formula [6]: [In the formula [6], R17 represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R18, R'18,
R19 and R'19 may be the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a substituted amino group. n is an integer of 1 or 2, and when n = 2, two groups substituted by the same phenyl group may be the same or different. p is an integer of 1 or 2, and when p = 2, two groups substituted by the same phenyl group may be the same or different. 2. The electrophotographic photoreceptor according to claim 1, further comprising a photosensitive layer containing one or more of the benzidine compounds. 5. A benzotriazole-alkylene bisphenol compound represented by the following general formula [7]: Wherein R 1 represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or an aralkyl group; R 2 represents a hydrogen atom, an alkyl group or an aryl group; R 3 and R 4 may be the same or different; Or a cycloalkyl group, an aryl group or an alkylaryl group]. 6. An amount of 1 to 40% by weight of one or more benzotriazole-alkylenebisphenol compounds represented by the general formula [1] to a charge transporting agent having an arylamino group in a molecule. The electrophotographic photoconductor according to claim 1, wherein the photoconductor is used.