JPH1124300A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the wear resistance and cleaning characteristics of a photoreceptor surface layer by incorporating a binder resin having silicon atoms or fluorine atoms into the surface layer of a photoreceptor which is produced by applying a photosensitive liquid on a conductive substrate, and incorporating a specified amt. of dioxolane. SOLUTION: The surface layer of a photoreceptor produced by applying a photosensitive liquid on a conductive substrate contains a binder resin having silicon atoms or fluorine atoms and contains 0.001 to 10 wt.% dioxolane or dioxolane deriv. The binder resin containing silicon atoms or fluorine atoms incorporated into the surface layer of the photoreceptor is, for example, a siloxane carbonate block copolymer and a carbonate fluorine-substd. paraffin block copolymer. The amt. of the binder resin containing silicon atoms or fluorine atoms in the photoreceptor layer is preferably >=0.1 wt.% of the binder resin in the surface layer, more preferably >=1 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly durable electrophotographic photosensitive member which is free from fatigue deterioration due to abrasion, damage and poor cleaning of a surface layer in the process of repeated image formation.

[0002]

2. Description of the Related Art Generally, in order to form an image by electrophotography, a toner image is formed by charging, exposing and developing an image on the surface of an electrophotographic photosensitive member (hereinafter, also simply referred to as a photosensitive member), and the toner image is transferred. While transferring and fixing on the material to form an image,
After the transfer, the photosensitive member is cleaned for residual toner and neutralized, and is used repeatedly for a long period of time.

Accordingly, the photosensitive member has a charging potential,
Electrophotographic performance such as sensitivity and residual potential, as well as good physical properties such as printing durability, abrasion resistance, and moisture resistance during repeated use, and resistance to ozone generated during corona discharge and image exposure. Requested.

The fatigue deterioration of the electrophotographic performance due to the repeated use of the photoreceptor is caused by transferring and separating a toner image formed on the photoreceptor onto a transfer material and cleaning residual toner on the photoreceptor after the transfer. This is considered to be due to abrasion and damage of the photoconductor surface layer in each step and filming of a hygroscopic substance such as toner and paper powder.

Conventionally, inorganic photoconductors containing an inorganic photoconductive substance have been widely used as the above photoconductor. The inorganic photoconductor, for example, an inorganic photoconductive substance such as cadmium sulfide or a photoconductor obtained by depositing an inorganic photoconductive substance such as selenium or amorphous silicon on a conductive support by vapor deposition or glow discharge or the like, There is a photoreceptor obtained by coating a photosensitive liquid containing a binder resin on a conductive support, but the contained inorganic photoconductive substance generally has high toxicity, and has problems such as poor processability. . Therefore, an organic photoreceptor that is low in cost, has no toxicity, is excellent in processability, and has a high degree of freedom for selection according to the purpose has attracted attention.

The above-mentioned organic photoreceptor comprises an organic photoconductive substance,
A photosensitive member obtained by applying a photosensitive solution obtained by dissolving or dispersing in a solvent together with a binder resin as necessary onto a conductive support, and in particular, sharing a charge generation function and a charge transport function with different substances. A function-separated type photoconductor is important. As the function-separated type photoreceptor, specifically, a photoreceptor obtained by laminating a charge generation layer containing a charge generation substance and a charge transport layer containing a charge transport substance on a conductive support is often used. .

Here, the photoreceptor obtained by applying the above-mentioned organic or inorganic photoconductive substance using a solvent is coated with an inorganic photoconductive substance such as selenium or amorphous silicon without using a solvent. The surface is softer than the photoreceptor deposited by discharge or the like, and the photoreceptor surface layer has a drawback in that it is liable to cause filming of the hygroscopic substance due to abrasion, damage and poor cleaning of the photoreceptor surface layer during repeated use. Improvement of physical properties of the photoconductor surface layer has become more important.

Therefore, for example, Japanese Patent Application Laid-Open No. Hei 5-113670 (Publication 1) discloses that a siloxane copolymerized polycarbonate is contained in a surface layer of a photoreceptor as a binder resin. A method of incorporating fine particles of a fluororesin in the photoreceptor surface layer to impart lubricity to the photoreceptor surface layer to improve cleaning properties and prevent filming of a hygroscopic substance such as toner and paper powder. Proposed.

Japanese Patent Application Laid-Open No. 3-155558 (Patent Publication 3) proposes a method in which inorganic fine particles such as silica and tin oxide are contained in a photoconductor surface layer to improve the abrasion resistance of the photoconductor surface layer. Have been.

On the other hand, as a solvent for an inorganic photoreceptor obtained by coating and processing a photosensitive liquid containing the above-mentioned inorganic photoconductive substance,
Toluene, tetrahydrofuran, dioxane, methyl ethyl ketone, cyclohexane, etc. have been used, but these solvents have poor solubility of the binder resin of the organic photoconductor containing an organic photoconductive substance, and instead, methylene chloride, ethylene chloride, chloroform Halogen solvents such as monochlorobenzene are mainly used. The halogen-based solvent is excellent in solubility in a binder resin of an organic photoreceptor, for example, a resin such as polycarbonate and polyarylate, and is excellent in coating processability.

[0011]

However, in a photoreceptor obtained by applying a photosensitive solution containing the above-mentioned inorganic or organic photoconductive substance, a part of the solvent is inevitably generated in a drying step after the application. It remains in the photoconductor surface layer. This residual solvent reduces or loses the effect of improving the abrasion resistance and cleaning properties of the photoreceptor surface layer described in, for example, the above publications 1 to 3, when image formation is repeatedly performed using the photoreceptor. In addition, the photoreceptor deteriorates due to fatigue due to abrasion, damage and poor cleaning of the surface layer of the photoreceptor.

The above-mentioned halogen-based solvent is disclosed in the aforementioned publication 1.
In addition to reducing or losing the effect of improving the abrasion resistance and cleaning properties of the photoreceptor surface layer described in Nos. 1 to 3, there is a problem of environmental pollution and carcinogenicity.

As a result of extensive studies by the present inventors, dioxane or a derivative thereof is used in place of the above-mentioned halogen-based solvent as a solvent for the photosensitive solution when the photosensitive solution is formed by coating the photosensitive solution. In addition to being excellent in solubility or dispersibility in a photoconductive substance and a binder resin, there is no problem of environmental pollution, carcinogenicity, ozone hole, etc., and by allowing the dioxolane or a derivative thereof to remain in an appropriate amount in the photosensitive layer. The present inventors have found that the effects of improving the abrasion resistance and cleaning properties of the photoreceptor surface layer described in the above publications 1 to 3 can be further improved, and the present invention has been completed.

The present invention has been proposed in view of the above circumstances, and an object thereof is to provide a specific amount of dioxolane or dioxolane on a photosensitive member surface layer obtained by applying a photosensitive solution on a conductive support. By leaving the derivative,
A binder resin containing silicon atoms or fluorine atoms in the photoreceptor surface layer, or organic fine particles, or inorganic fine particles, etc., to further improve the effect of improving the abrasion resistance and cleaning properties of the photoreceptor surface layer, An object of the present invention is to provide a photoreceptor which does not suffer from fatigue deterioration in the process of repeated image formation of the photoreceptor, has no fog for a long period of time, and can stably obtain a high-density and clear image.

[0015]

The above object of the present invention is achieved by the following constitution.

1. A photosensitive layer formed by applying a photosensitive solution on a conductive support contains a binder resin having a silicon atom or a fluorine atom, and 0.001 to 10% by weight.
An electrophotographic photoreceptor comprising: a dioxolane or a dioxolane derivative.

2. 2. The electrophotographic photosensitive member according to the item 1, wherein the binder resin having a silicon atom or a fluorine atom is polycarbonate and a copolymer thereof.

3. An organic fine particle is contained in a photoreceptor surface layer obtained by applying and processing a photosensitizing solution on a conductive support, and 0.0
An electrophotographic photoreceptor containing from 0.01 to 10% by weight of dioxolane or a dioxolane derivative.

4. 4. The electrophotographic photoconductor according to the above item 3, wherein the organic fine particles have a fluorine atom.

[5] 5. The electrophotographic photoconductor according to the above item 3 or 4, wherein the photoconductor surface layer contains a binder resin having a silicon atom or a fluorine atom.

6. A photosensitive surface layer formed by applying a photosensitive solution on a conductive support contains inorganic fine particles,
An electrophotographic photoreceptor containing from 0.01 to 10% by weight of dioxolane or a dioxolane derivative.

7. 7. The electrophotographic photosensitive member according to the item 6, wherein the inorganic fine particles are oxides of silicon atoms or tin atoms.

8. 8. The electrophotographic photoconductor according to the above item 6 or 7, wherein the photoconductor surface layer contains a binder resin having a silicon atom or a fluorine atom.

9. A photoconductor surface layer formed by applying a photosensitizing solution onto a conductive support, containing inorganic fine particles and organic fine particles, and containing 0.001 to 10% by weight of dioxolane or a dioxolane derivative. Photoreceptor.

10. 10. The electrophotographic photoreceptor according to the item 9, wherein the organic fine particles have a fluorine atom, and the inorganic fine particles are an oxide of a silicon atom or a tin atom.

11. The electrophotographic photoconductor according to the above item 9 or 10, wherein the photoconductor surface layer contains a binder resin having a silicon atom or a fluorine atom.

Hereinafter, the present invention will be described in detail.

In the photoreceptor of the present invention, the photoreceptor surface layer has
Dioxolane or dioxolane is used as a solvent in a coating solution for forming a photoreceptor surface layer while containing a binder resin containing silicon or fluorine atoms for imparting lubricity, organic fine particles and / or inorganic fine particles for imparting wear resistance. Using a derivative, and drying the dioxolane or dioxolane derivative in the photoreceptor surface layer after drying.
By containing 0% by weight, the abrasion resistance and cleaning properties of the photoreceptor are further improved, and there is no fatigue deterioration of the photoreceptor in the process of repeated image formation, and a high density clear image can be stably obtained. The feature is that it is made possible.

The photoreceptor of the present invention includes an inorganic photoreceptor containing an inorganic photoconductive substance in a binder resin and an organic photoreceptor containing an organic photoconductive substance in a binder resin. This will be mainly described.

Examples of the binder resin containing a silicon atom or a fluorine atom contained in the photoreceptor surface layer of the present invention include the following.

<Binder Resin Containing Silicon Atom> For example, siloxane-carbonate block copolymers and siloxane-ester block copolymers described in pages 5 and 6 of JP-A-3-171506,
Siloxane-carbonate block copolymer described in JP-A-113670, pp. 5-7, JP-A-8-871
No. 19, pp. 11-14, 16-20, 23
-Siloxanes described on pages 32 to 35 and pages 35 to 37
Carbonate block copolymers and the like.

<Binder Resin Containing Fluorine Atom> For example, carbonate-fluorine-substituted paraffin block copolymer described in page 3 of JP-A-3-45958 and JP-A-5-188628 And the like. Polycarbonate having a fluorine substituent described on page.

The amount of the binder resin containing a silicon atom or the binder resin containing a fluorine atom in the surface layer of the photoreceptor is preferably about 0.1% of the binder resin of the surface layer.
1 wt% or more, more preferably 1 wt% or more;
If the amount is less than 0.1 wt%, sufficient lubricity cannot be imparted to the surface layer of the photoreceptor, and cleaning failure tends to occur during image formation.

Next, examples of the organic fine particles and inorganic fine particles contained in the photoreceptor surface layer of the present invention include the following.

<Organic Fine Particles> In the above-mentioned organic fine particles, for example, polytetrafluoroethylene, polyvinylidene fluoride, poly (trifluorochloroethylene), polyvinyl fluoride, polytetrafluoroethylene-perfluoroalkylvinyl ether copolymer, polytetrafluoroethylene Ethylene-propylene hexafluoride copolymer, polyethylene-ethylene trifluoride copolymer, polytetrafluoroethylene-propylene hexafluoride-perfluoroalkyl vinyl ether copolymer, polyethylene, polyvinyl chloride, metal stearate , Polymethyl methacrylate or melamine, and the volume average particle diameter is preferably 0.05 to 10 μm. The amount of the organic fine particles contained in the photoconductor surface layer is preferably 0.1 to 100 wt.
%, More preferably 1 to 50% by weight, and if it is less than 0.1%, sufficient lubricity cannot be imparted to the photosensitive layer, and cleaning failure tends to occur during image formation.
If the amount exceeds wt%, the photosensitivity of the photoreceptor decreases, and fogging easily occurs.

<Inorganic fine particles> In the above inorganic fine particles,
Examples of the metal oxide include magnesium oxide, calcium oxide, titanium oxide, zirconium oxide, tin oxide,
Examples include aluminum oxide, silicon oxide (silica), indium oxide, beryllium oxide, lead oxide, bismuth oxide, and the like. Examples of nitrides include boron nitride, aluminum nitride, and silicon nitride. For example, silicon carbide, boron carbide and the like can be mentioned. The inorganic fine particles are preferably subjected to a hydrophobizing treatment with a hydrophobizing agent such as a titanium coupling agent, a silane coupling agent, an aluminum coupling agent, or a high-molecular fatty acid.

The inorganic fine particles preferably have a volume average particle diameter of 0.05 to 2 μm. The amount of the inorganic fine particles contained in the surface layer of the photoreceptor is preferably from 0.1 to 100 wt%, more preferably from 1 to 50 wt%, and preferably less than 0.1%, based on the binder resin of the surface layer. In the case of (1), sufficient mechanical strength cannot be imparted to the photoreceptor surface layer, and the photoreceptor surface layer is liable to be worn and damaged during image formation.
If it exceeds 00% by weight, the surface roughness of the photoconductor surface layer becomes large, and the cleaning member is damaged, resulting in poor cleaning.

The volume average particle diameter of the organic fine particles and the inorganic fine particles is measured by a laser diffraction / scattering type particle size distribution analyzer “LA-700” (manufactured by Horiba, Ltd.).

Hereinafter, dioxolan or a dioxolane derivative used as a solvent of a coating solution for forming a photoreceptor surface layer (particularly, a charge transport layer) of the present invention will be described.

<Dioxolane or dioxolane derivative>
The dioxolane or the dioxolane derivative is a cyclic five-membered ether compound having a dioxolane nucleus containing two non-adjacent oxygen atoms in the molecule, and specifically, represented by the following general formula (1). Those represented are preferably used.

[0041]

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[0042] (wherein, R ₁ to R ₆ are substituted C1-4 hydrogen atom or a carbon atom, an unsubstituted alkyl group. Further, R ₅
And at least two groups of R ₆ or R _{1 to} R ₄ may combine to form a ring. The substituent of the alkyl group may be any,
Preferably, an alkoxy group, an acyl group, an acyloxy group, or a hydroxyl group having 1 to 4 carbon atoms is used. The ring formed by combining at least two of R ₅ and R ₆ or R _{1 to} R ₄ may be any, but is preferably a 5- to 6-membered aromatic ring (for example, a benzene ring) or ,
Non-aromatic rings (for example, cyclohexane ring) are mentioned.

Of these, those in which any of R _{1 to} R ₆ are hydrogen atoms are preferred, and those in which all of R _{1 to} R ₆ are hydrogen atoms are particularly preferred.

The dioxolane or dioxolane derivative used in the present invention has a boiling point of 70 to 20 at normal pressure.
The temperature is preferably 0 ° C, more preferably 150 ° C or lower, and particularly preferably 70 to 130 ° C.

Here, if the boiling point exceeds 200 ° C., the drying step becomes longer, which is disadvantageous in terms of cost. If the drying step is carried out in the usual way, the amount of the residual solvent becomes large. Potential stability decreases. Further, if the boiling point is less than 70 ° C., the drying speed is increased during drying,
It is easily affected by air currents and it is difficult to obtain a uniform coating film.

Next, specific examples of the compound which can be preferably used in the present invention are shown below.

[0047]

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[0048]

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[0049]

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[0050]

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Incidentally, the photoreceptor of the present invention is usually formed by providing an undercoat layer on a conductive support as necessary, and providing a charge generation layer and a charge transport layer on the undercoat layer in this order. The charge transport layer is obtained by applying and drying a coating solution obtained by dissolving a charge transport material and a binder resin in a solvent containing dioxolane or a dioxolane derivative on the charge generation layer, and forming the charge transport layer. When the liquid is applied and dried, a solvent containing dioxolane or a dioxolane derivative inevitably remains in the charge transport layer.

In the present invention, it is essential that the amount of dioxolane or dioxolane derivative remaining in the charge transporting layer is in the range of 0.001 to 10% by weight based on the charge transporting layer. If the amount is less than 10% by weight, the effect of improving the cleaning properties and abrasion resistance of the photoreceptor surface layer by a physical property improver (a binder resin having a silicon atom or a fluorine atom, organic fine particles and / or inorganic fine particles) in the charge transport layer is obtained. When the content exceeds 10% by weight, abrasion resistance is reduced, and fog tends to occur due to an increase in residual potential during image formation.

When a solvent for the charge transport layer is used in combination with the dioxolane or the dioxolane derivative, another solvent is not particularly limited, but generally has excellent compatibility with dioxolane or a derivative thereof, and dissolves the binder resin. Those having excellent properties are used.

<Structure of Photoreceptor><< Photosensitive Layer >> The photoreceptor of the present invention is preferably provided with a photosensitive layer comprising an organic photoconductive layer on a conductive support, and in particular, a charge containing a charge generating substance. A function-separated organic photoreceptor having a generating layer and a charge transporting layer containing a charge transporting substance in this order is preferred.

The charge generation layer is formed by dispersing a charge generation material in a binder resin as required. As the charge generating substance, a metal or metal-free phthalocyanine compound, a bisazo compound, an azo compound such as a trisazo compound, a squarium compound, an azurenium compound, a perylene compound, an indico compound, a quinacridone compound,
Polycyclic quinone compounds, cyanine dyes, xanthene dyes,
Examples of the charge transfer complex include poly-N-vinylcarbazole and trinitrofluorenone, and the like.In particular, imidazole perylene compounds, which are a kind of perylene compounds excellent in photoconductive properties, and titanyl phthalocyanine, gallium phthalocyanine, and hydroxygallium phthalocyanine. Metal phthalocyanine compounds are preferred.

Examples of the binder resin usable for the charge generation layer include polystyrene resin, polyethylene resin, polypropylene resin, polyacryl resin, polymethacryl resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, and poly (vinyl butyral) resin. Epoxy resins, polyurethane resins, polyphenol resins, polyester resins, polyalkyd resins, polycarbonate resins, polysilicone resins, polymelamine resins, and copolymer resins containing two or more of the repeating units of these resins, for example, vinyl chloride-acetic acid Examples include, but are not limited to, vinyl copolymer resins, vinyl chloride-vinyl acetate-maleic anhydride copolymer resins, and high molecular organic semiconductors such as poly-N-vinyl carbazole.

The charge transport layer provided on the charge generation layer comprises a charge transport substance alone or usually together with a binder resin. Examples of the charge transport material include carbazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, and pyrazoline. Derivative, oxazolone derivative, benzimidazole derivative, quinazoline derivative, benzofuran derivative, acridine derivative, phenazine derivative, aminostilbene derivative, triarylamine derivative, phenylenediamine derivative, stilbene derivative, benzidine derivative, poly-N-vinylcarbazole, poly-1 -Vinyl pyrene,
Examples include, but are not limited to, poly-9-vinyl anthracene. These charge transporting substances may be used alone or in combination of two or more.

Since the charge transport layer usually forms the surface layer of the photoreceptor of the present invention, it may be used as a binder resin described in JP-A-3-171506, JP-A-5-113670 or JP-A-8-87119. A silicon atom-containing resin such as a siloxane-ester block copolymer or a siloxane-carbonate block copolymer described in the publication is mainly used, and further, each of the above-mentioned JP-A-3-45958 or JP-A-5-188628 The polycarbonate resin having a fluorine atom described in the publication is mainly used, but the following other resins can be contained in an amount of 50% by weight or less as necessary.

In the case where the organic fine particles and / or the inorganic fine particles of the present invention are contained in the photoreceptor surface layer, the following other resin may be used as a main component as a binder resin. A polycarbonate resin is used.

Examples of the other resins include polycarbonate (bisphenol A-type polycarbonate, bisphenol Z-type polycarbonate), polycarbonate copolymer, polyester, polyurethane, polystyrene, polystyrene copolymer, polysiloxane, polyacrylate, and polyacrylate. Copolymers, phenoxy resins, ABS resins, polyvinyl chloride, polyvinyl chloride-based copolymers, polyvinyl acetate-based copolymers, polyvinyl ormal, polyvinyl butyral, and the like are included.

As particularly preferable conditions of the present invention, the binder resin having a silicon atom or a fluorine atom is used in the surface layer of the photoreceptor, and a physical property improving agent such as organic fine particles and / or inorganic fine particles is further contained. In this case, 0.001 to 10% by weight of dioxolane or a dioxolane derivative remains, and a photoreceptor excellent in cleaning properties and abrasion resistance can be obtained by a synergistic effect of these.

Further, it is preferable that the photosensitive layer of the photoreceptor of the present invention, particularly the charge transporting layer, contain a silicone oil.
No. 643, JP-A-57-5050, JP-A-57-21
No. 2453, JP-A-59-208556, JP-A-63
-80262, JP-A-1-234854, JP-A-4
And silicone oils described in JP-A-199154 and JP-A-5-27456. In particular, methylphenyl silicone oil and dimethyl silicone oil are preferable, and the content of the contained layer in the solid content is preferably 10 to 1000 ppm.

In order to reduce fatigue deterioration upon repeated use or to improve durability, any of the layers constituting the photosensitive layer of the photosensitive member may be provided with a conventionally known antioxidant, electron-accepting agent, etc. An appropriate amount of a substance, a surface modifier, an environment-dependent reducing agent such as a plasticizer, etc. can be added as necessary.

Further, in order to improve the durability, a non-photosensitive layer such as a protective layer may be provided in addition to the photosensitive layer, if necessary. It may be a photoreceptor having a charge transport layer of the type.

The charge transport layer above the protective layer or the multilayer charge transport layer constitutes a photoreceptor surface layer, and therefore has a two-layered photoreceptor comprising a charge transport layer laminated on the charge generation layer. As in the case of the charge transport layer in the case of (1), physical property improvers (a binder resin having a silicon atom or a fluorine atom, organic fine particles and / or
Or inorganic fine particles) and leaving 0.001 to 10% by weight of dioxolane or a dioxolane derivative, whereby the photoreceptor can similarly exhibit excellent cleaning properties and abrasion resistance.

In addition, a dye for correcting color sensitivity may be added to the photoreceptor of the present invention. Further, an additive such as an antioxidant may be used in combination.

There are various methods for applying the photosensitive liquid for forming the photosensitive member, and it is particularly preferable to apply the photosensitive liquid by using a circular amount-regulating type coating apparatus, particularly a slide hopper type coating apparatus. These techniques are disclosed in
JP-A-189061, JP-A-8-318209, and JP-A-9-10654.

<< Undercoat Layer, Support >> When an undercoat layer is provided, a so-called resin undercoat layer using a polyamide compound such as nylon or a so-called undercoat layer using an organometallic compound and a silane coupling agent. A ceramic-based underlayer (also referred to as a curable underlayer) is preferably used.

Next, as the conductive support for supporting the photosensitive layer, a metal plate or a metal drum of aluminum, nickel or the like, a plastic film or a plastic drum on which aluminum, tin oxide, indium oxide or the like is deposited, or a conductive material Paper, a plastic film, a plastic drum, or the like, to which is coated.

Hereinafter, the present invention will be described in more detail with reference to examples, but embodiments of the present invention are not limited thereto.

[0071]

【Example】

Example 1 <Preparation of Photoconductor 1> An aluminum support having a diameter of 80 mm and a height of 355 mm, which had been mirror-finished, was used as a conductive support.

The undercoat layer coating solution UC shown below was coated on the support.
L-1 was applied to form an undercoat layer having a dry film thickness of 0.8 μm.

In the following application of each photoreceptor,
In each case, coating was performed using a slide hopper type coating apparatus, which is a kind of a circular quantity control type coating apparatus.

<< Undercoat Layer Coating Solution UCL-1 >> Copolymer Nylon “CM8000” (manufactured by Toray Industries, Inc.) 2 g Methanol / 1-butanol = 10/1 1000 ml Then, the following charge generation occurs on the undercoat layer. Layer coating liquid CG
L-1 was applied to form a charge generation layer having a dry film thickness of 1.5 μm.

<< Charge Generating Layer Coating Solution CGL-1 >> Fluorenone-type disazo pigment (CGM-1) having the following structure 25 g Butyral “ESLEC BX-L” (manufactured by Sekisui Chemical Co., Ltd.) 10 g 2-butanone 1430 ml The above composition Was dispersed for 20 hours using a sand mill and used as a coating liquid.

[0076]

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Next, after applying the following charge transport layer coating solution CTL-1 on the charge generation layer, drying was carried out at 100 ° C. for 1 hour, and a charge transport layer having a dry film thickness of 23 μm was laminated and provided. Photoconductor 1 for the present invention was obtained. At this time, Compound Example No. The residual content in the photosensitive layer of No. 1 was 1.0% by weight.

<< Charge Transport Layer Coating Solution CTL-1 >> Charge Transport Material CTM-1 having the following structure 420 g Siloxane copolymerized polycarbonate B-1 having the following structure (viscosity average molecular weight Mv = 40,000) 560 g Compound Example No. 1 2800ml

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[0080]

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<Preparation of Photoconductor 2> Photoconductor 2 of the present invention was obtained in the same manner as photoconductor 1, except that the drying temperature of the charge transport layer was changed from 100 ° C. to 120 ° C. .
At this time, the compound No. No. The quantity of 1 is
It was 0.01% by weight of the photosensitive layer.

<Preparation of Photoconductor 3> Photoconductor 3 of the present invention was obtained in the same manner as photoconductor 1, except that the drying temperature of the charge transport layer was changed from 100 ° C. to 90 ° C. . At this time, the compound No. No. The amount of 1 was 3.5% by weight of the photosensitive layer.

<Preparation of Photoconductor 4> In Photoconductor 1, the binder resin for the charge transport layer was changed from siloxane copolymer polycarbonate B-1 to siloxane copolymer polycarbonate B-2 having the following structure (viscosity average molecular weight Mv = 20,000,
Photoconductor 4 of the present invention was obtained in the same manner as photoconductor 1, except that 0) was used. Example of compound N remaining in photosensitive layer at this time
o. The amount of 1 was 1.2% by weight of the photosensitive layer.

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<Preparation of Photoconductor 5> In Photoconductor 1, the binder resin of the charge transport layer was changed from siloxane copolymerized polycarbonate B-1 to fluorine atom-containing polycarbonate B-3 having the following structure (viscosity average molecular weight Mv = 30,000).
Compound No. remaining in photoreceptor 1 except for changing to The amount of 1 was 1.2% by weight of the photosensitive layer.

[0086]

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<Preparation of Photoconductor 6> As a conductive support, a mirror-finished aluminum support having a diameter of 80 mm and a height of 355 mm was used.

The following undercoat layer coating solution UCL was coated on the support.
-2 was applied to form an undercoat layer having a dry film thickness of 1.0 μm.

<< Undercoat Layer Coating Solution UCL-2 >> Titanium chelate compound “TC-750” (manufactured by Matsumoto Pharmaceutical Co., Ltd.) 30 g Silane coupling agent “KBM-503” (manufactured by Shin-Etsu Chemical Co., Ltd.) 17 g 2-propanol 150 ml Then, the following charge generation layer coating solution CG was formed on the undercoat layer.
L-2 was dispersed and prepared, and applied to a film thickness of 0.5 μm.

<< Charge Generating Layer Coating Solution CGL-2 >> Y-type titanyl phthalocyanine 10 g Silicone resin "KR-5240" (manufactured by Shin-Etsu Chemical Co., Ltd.) 10 g t-butyl-acetate 1000 ml The above composition was prepared using a sand mill. What was dispersed over time was used as a coating solution. Next, the following charge transport layer coating solution CTL-2 was applied on the charge generation layer,
After drying for 1 hour, a charge transport layer having a dry film thickness of 23 μm was laminated to obtain a photoreceptor 6 for the present invention. At this time, the compound No. No. 1 and Compound Example No. The total amount of 2 was 1.5% by weight of the photosensitive layer.

<< Charge Transport Layer Coating Solution CTL-2 >> Charge Transport Material CTM-1 420 g Siloxane copolymerized polycarbonate B-1 660 g Compound Example No. 1 2600 ml Compound Example No. 2 200 ml <Preparation of Photoreceptor 7> An undercoat layer and a charge generation layer were sequentially provided on a conductive support in the same manner as for Photoreceptor 6, and the following charge transport layer coating solution CTL-3 was coated on the charge generation layer. , 100 ° C, 3
After drying for 0 minutes, a charge transport layer having a dry film thickness of 23 μm was laminated thereon to obtain a photoreceptor 7 for the present invention. At this time, the compound No. No. 1 and Compound Example No. The total amount of 2 was 1.5% by weight of the photosensitive layer.

<< Charge Transport Layer Coating Solution CTL-3 >> Charge transport material CTM-1 420 g Siloxane copolymerized polycarbonate B-1 660 g Dichloromethane 2500 ml 1 270 ml Compound Example No. 230 ml <Preparation of Photoconductor 8> In Photoconductor 6, the binder resin of the charge transport layer was changed to siloxane copolymerized polycarbonate B-1.
The photoreceptor 8 for use in the present invention was obtained in the same manner as the photoreceptor 6 except that siloxane copolymer polycarbonate B-2 was used. At this time, the compound No. No. 1 and Compound Example No. The total amount of 2 is 1.2% by weight of the photosensitive layer
Met.

<Preparation of Photoreceptor 9> An undercoat layer and a charge generation layer are sequentially provided on a conductive support in the same manner as for Photoreceptor 6, and the following charge transport layer coating solution CTL-4 is coated on the charge generation layer. And
After drying at 100 ° C. for 1 hour, a charge transport layer having a dry film thickness of 23 μm was laminated to obtain a photoreceptor 9 for the present invention. At this time, the compound No. No. The amount of 1 was 1.0% by weight of the photosensitive layer.

<< Charge Transport Layer Coating Solution CTL-4 >> Charge Transport Material CTM-1 420 g Polycarbonate “Z200” (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 660 g Polytetrafluoroethylene PTFE “Rubron L2” (Daikin Co., Ltd.) 132g Dispersing aid “GF-300 (purified product)” (manufactured by Toagosei Co., Ltd.) 13.2 g Compound Example No. 1 2800 ml The above composition was dispersed in a sand mill for 3 hours and used as a coating liquid.

<Preparation of Photoreceptor 10> In the photoreceptor 9, the binder resin of the charge transport layer was changed to polycarbonate "Z20".
Photoconductor 1 for use in the present invention in the same manner as photoconductor 9 except that siloxane copolymer polycarbonate B-1 was used instead of "0".
0 was obtained. At this time, Compound Example No. The residual content in the photosensitive layer No. 1 was 1.0% by weight of the photosensitive layer.

<Preparation of Photoreceptor 11> An undercoat layer and a charge generation layer were sequentially provided on an aluminum support in the same manner as for Photoreceptor 6, and the following charge transport layer coating solution CTL-5 was formed on the charge generation layer.
And dried at 100 ° C. for 1 hour to obtain a dry film thickness of 23 μm.
m of the charge transport layers were laminated to obtain a photoreceptor 11 for the present invention. At this time, the compound No. No. The amount of 1 was 1.0% by weight of the photosensitive layer.

<< Charge Transport Layer Coating Solution CTL-5 >> Charge Transport Material CTM-1 420 g Polycarbonate “Z200” 660 g Tin oxide fine particles (average particle size 0.5 μm) 66 g Compound Example No. 1 2800 ml A composition obtained by dispersing the above composition for 3 hours was used as a coating liquid.

<Preparation of Photoreceptor 12> An undercoat layer and a charge generation layer were sequentially provided on an aluminum support in the same manner as for the photoreceptor 11, and the following charge transport layer coating solution CTL-6 was formed on the charge generation layer.
And dried at 100 ° C. for 1 hour to obtain a dry film thickness of 23 μm.
m of the charge transport layers were laminated to obtain a photoreceptor 12 for the present invention. At this time, the compound No. No. The amount of 1 was 1.0% by weight of the photosensitive layer.

<< Charge Transport Layer Coating Solution CTL-6 >> Charge Transport Material CTM-1 20 g Siloxane copolymerized polycarbonate B-1 660 g Tin oxide fine particles (average particle diameter 0.5 μm) 66 g Compound Example No. 1 2800 ml A composition obtained by dispersing the above composition for 3 hours was used as a coating liquid.

<Preparation of Photoreceptor 13> An undercoat layer and a charge generation layer were sequentially provided on an aluminum support in the same manner as for the photoreceptor 11, and the following charge transport layer coating solution CTL-7 was formed on the charge generation layer.
And dried at 100 ° C. for 1 hour to obtain a dry film thickness of 23 μm.
m of the charge transport layers were laminated to obtain a photoreceptor 13 for the present invention. At this time, the compound No. No. The amount of 1 was 1.0% by weight of the photosensitive layer.

<< Charge Transport Layer Coating Solution CTL-7 >> Charge transport substance CTM-1 420 g Siloxane copolymerized polycarbonate B-1 660 g Silica "Admafine SO-C1" (manufactured by Admatechs Co., Ltd.) 66 g 1 2800 ml A composition obtained by stirring the above composition for 3 hours was used as a coating liquid.

<Preparation of Photoreceptor 14> An undercoat layer and a charge generation layer were sequentially provided on an aluminum support in the same manner as for Photoreceptor 11, and the following charge transport layer coating solution CTL-8 was formed on the charge generation layer.
And dried at 100 ° C. for 1 hour to obtain a dry film thickness of 23 μm.
m of the charge transport layers were laminated to obtain a photoreceptor 14 for the present invention. Compound No. No. remaining in the photosensitive layer at this time. The amount of 1 was 1.0% by weight of the photosensitive layer.

<< Charge Transport Layer Coating Solution CTL-8 >> Charge transport material CTM-1 420 g Siloxane copolymerized polycarbonate B-1 660 g Tin oxide fine particles (average particle size 0.5 μm) 66 g PTFE “Rubron L2” 132 g Compound Example No. 1 2800 ml A composition obtained by stirring the above composition for 3 hours was used as a coating liquid.

<Preparation of Photoreceptor 15>
A photoconductor 15 for comparison was obtained in the same manner as the photoconductor 1 except that the drying temperature of the charge transport layer was changed to 100 ° C. and set to 130 ° C. At this time, the compound No. No. The amount of 1 was 0.0001% by weight of the photosensitive layer.

<Preparation of Photoconductor 16>
A photoreceptor 16 for comparison was obtained in the same manner as the photoreceptor 1, except that the drying temperature of the charge transport layer was changed to 100 ° C. and set to 60 ° C. At this time, the compound No. No. The amount of 1 was 12.5% by weight of the photosensitive layer.

<Preparation of Photoreceptor 17> An undercoat layer and a charge generation layer were sequentially provided on an aluminum support in the same manner as in Photoreceptor 1, and the following charge transport layer coating solution CTL-9 was formed on the charge generation layer.
And dried at 100 ° C. for 1 hour to obtain a dry film thickness of 23 μm.
m of the charge transporting layers were laminated to obtain a photosensitive member 17 for comparison. At this time, the amount of 1,2-dichloroethane remaining in the photosensitive layer was 1.0% by weight of the photosensitive layer.

<< Coating Solution for Charge Transport Layer CTL-9 >> 420 g of charge transport material CTM-1 560 g of siloxane copolymerized polycarbonate B-1 2800 ml of 1,2-dichloroethane <Preparation of Photoreceptor 18> Aluminum support similar to Photoreceptor 1 An undercoat layer and a charge generation layer are sequentially provided thereon, and the following charge transport layer coating solution CTL-10 is coated on the charge generation layer.
After drying at 00 ° C. for 1 hour, a charge transport layer having a dry film thickness of 23 μm was laminated to obtain a photoreceptor 18 for comparison. Compound No. No. remaining in the photosensitive layer at this time. The amount of 1 was 1.0% by weight of the photosensitive layer.

<< Charge Transport Layer Coating Solution CTL-10 >> Charge Transport Material CTM-1 420 g Polycarbonate “Z200” 560 g Compound Example No. 1 2800 ml <Preparation of Photoreceptor 19> In Photoreceptor 9, the solvent of the coating solution for the charge transport layer was changed to Compound Example No. Photoconductor 19 for comparison was obtained in the same manner as photoconductor 9 except that 1,2-dichloroethane was used instead of 1. At this time, the amount of 1,2-dichloroethane remaining in the photosensitive layer was 1.1% by weight of the photosensitive layer.

<Preparation of Photoreceptor 20> In the photoreceptor 10, the solvent of the coating solution for the charge transport layer was changed to Compound Example No. 1 to 1,
A photoconductor 20 for comparison was obtained in the same manner as the photoconductor 10 except that 2-dichloroethane was used. At this time, the amount of 1,2-dichloroethane remaining in the photosensitive layer is 1.1% of the photosensitive layer.
% By weight.

<Preparation of Photoreceptor 21> In Photoreceptor 11, the solvent of the coating solution for the charge transport layer was changed to Compound Example No. 1 to 1,
A photoconductor 21 for comparison was obtained in the same manner as the photoconductor 11 except that 2-dichloroethane was used. At this time, the amount of 1,2-dichloroethane remaining in the photosensitive layer is 1.1% of the photosensitive layer.
% By weight.

<Preparation of Photoreceptor 22> In Photoreceptor 12, the solvent of the coating solution for the charge transport layer was changed to Compound Example No. 1 to 1,
A photoconductor 22 for comparison was obtained in the same manner as the photoconductor 12 except that 2-dichloroethane was used. At this time, the amount of 1,2-dichloroethane remaining in the photosensitive layer is 1.1% of the photosensitive layer.
% By weight.

<Preparation of Photoreceptor 23> In Photoreceptor 14, the solvent of the coating solution for the charge transport layer was changed to Compound Example No. 1 to 1,
A photoconductor 23 for comparison was obtained in the same manner as the photoconductor 14 except that 2-dichloroethane was used. At this time, the amount of 1,2-dichloroethane remaining in the photosensitive layer is 1.1% of the photosensitive layer.
% By weight.

[0113]

[Table 1]

The binder resin of the charge transport layer (surface layer) of each of the photoconductors 1 to 23, the type of solvent (amount ml), the type of organic fine particles and inorganic fine particles, the drying conditions, the dioxolane solvent in the photosensitive layer (comparative) Table 1 shows the residual amounts (wt%) of the photoconductors 17 and 19 to 23 (1,2-dichloroethane).

[Evaluation of Performance] The electrophotographic performances of the photoconductors 1 to 14 for the present invention and the photoconductors 15 to 23 for comparison obtained as described above were evaluated using an electronic copying machine U-BIX4045.

<Repeated Potential Characteristics> The photoconductors 1 to 14 of the present invention and the photoconductors 15 to 23 for comparison are sequentially mounted on a modified machine in which a surface electrometer is arranged in the developing section of the electronic copying machine. The black paper potential (Vb), white paper potential (Vw), and residual potential (Vr) were measured at the 10th and 50,000 times when the process of charging → exposure → removal was repeated 50,000 times. Are shown in Table 2.

<Evaluation of Image> The photoreceptors 1 to 14 of the present invention and the photoreceptors 15 to 23 for comparison were sequentially mounted on the above-mentioned electronic copying machine, and an actual photographing test was performed. The occurrence of image defects such as white stripes due to filming of a hygroscopic substance such as ground fog, toner and paper dust was observed. The results are shown in Table 2.

<Abrasion resistance> The above-mentioned photoreceptors 1 to 1 for the present invention.
4 and the photoconductors 15 to 23 for comparison, the film thickness of each photoconductor at the initial stage and after 50,000 copies were measured, and from the difference in film thickness between the initial stage and after 50,000 copies, The thickness loss (μm) of the photoreceptor was determined, and the results are shown in Table 2.

[0119]

[Table 2]

From Table 2, it can be seen that the photoreceptor for the present invention has a repetitive potential deterioration due to filming of a hygroscopic substance such as toner and paper dust, abrasion damage, and the like, or white in the course of repeated image formation. The electrophotographic performance is excellent with few image defects such as streaks, reduced image density, and background fogging, but the photoreceptor for comparison has filming of a hygroscopic substance such as toner and paper powder on the photoreceptor surface, and wear damage. It can be understood that any of the deterioration of the repetitive potential characteristics due to the above-mentioned factors, or image defects such as white streaks, a decrease in image density, and fog on the ground is poor, and the practicability is poor. Further, in the photoreceptor of the present invention, the use of a binder resin having silicon atoms in the surface layer and the addition of organic fine particles further improve the cleaning property, make filming less likely to occur, and use both organic fine particles and inorganic fine particles. This indicates that the thickness loss is synergistically reduced, and that the stability of the blank paper potential is particularly improved.

[0121]

According to the present invention, a specific amount of dioxolane or a derivative thereof is allowed to remain in a photoreceptor surface layer obtained by coating and processing a photoreceptor solution on a conductive support, so that a silicon atom or a fluorine atom is added to the photoreceptor surface layer. To further improve the effect of improving the abrasion resistance and cleaning properties of the photoreceptor surface by incorporating a binder resin containing, or organic fine particles, or inorganic fine particles, etc., and fatigue deterioration in the process of repeated image formation of the photoreceptor It has excellent effects such as no fog, no fog over a long period of time, and a high-density clear image can be stably obtained.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G03G 5/05 103 G03G 5/05 103B

Claims (11)

[Claims] 1. A dioxane or dioxolane derivative containing 0.001 to 10% by weight of a binder resin having a silicon atom or a fluorine atom in a surface layer of a photoreceptor obtained by applying and processing a photosensitive liquid on a conductive support. An electrophotographic photoreceptor comprising: 2. The electrophotographic photosensitive member according to claim 1, wherein the binder resin having a silicon atom or a fluorine atom is polycarbonate or a copolymer thereof. 3. A photoconductor surface layer obtained by coating a photoconductive solution on a conductive support and containing organic fine particles, and
An electrophotographic photoreceptor comprising 1 to 10% by weight of dioxolane or a dioxolane derivative. 4. The electrophotographic photosensitive member according to claim 3, wherein said organic fine particles have a fluorine atom. 5. The electrophotographic photoconductor according to claim 3, wherein the photoconductor surface layer contains a binder resin having a silicon atom or a fluorine atom. 6. A photoreceptor surface layer obtained by applying and processing a photosensitive solution on a conductive support, containing inorganic fine particles, and
An electrophotographic photoreceptor comprising 1 to 10% by weight of dioxolane or a dioxolane derivative. 7. The electrophotographic photosensitive member according to claim 6, wherein the inorganic fine particles are oxides of silicon atoms or tin atoms. 8. The electrophotographic photoconductor according to claim 6, wherein the photoconductor surface layer contains a binder resin having a silicon atom or a fluorine atom. 9. A photoreceptor surface layer obtained by applying a photoreceptor solution on a conductive support and containing inorganic fine particles and organic fine particles and 0.001 to 10% by weight of dioxolane or a dioxolane derivative. An electrophotographic photosensitive member characterized by the following. 10. The organic fine particles have a fluorine atom,
The electrophotographic photosensitive member according to claim 9, wherein the inorganic fine particles are oxides of silicon atoms or tin atoms. 11. The electrophotographic photoconductor according to claim 9, wherein the photoconductor surface layer contains a binder resin having a silicon atom or a fluorine atom.