JPH09319129A - Electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase the mechanical strength of an electrophotographic photoreceptor while ensuring solvent cracking resistance and to improve the resistance to electricity by direct electrification, by incorporating fluororesin particles and a polymer having specified constituent units into the surface layer of the photoreceptor. SOLUTION: This electrophotographic photoreceptor has a surface layer contg. fluororesin particles an polymer having constituent units represented by the formula, wherein X is CR13 R14 (each of R13 and R14 it H, trifluoromethyl, a 1-6C alkyl or a 6-12C aryl), an optionally substd. 5-11C 1,1-cycloalkylene, a 2-10C α,ω-alkylene, a single bond, O, S, SO, or SO2 , each of R1 -R12 is H, a halogen, an optionally substd. alkyl, aryl or alkylene and (n) is an integer.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an electrophotographic photoreceptor,
More particularly, the present invention relates to an electrophotographic photosensitive member having a photosensitive layer containing a specific resin, a process cartridge, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art An electrophotographic photosensitive member is disclosed in US Pat.
As shown in Japanese Patent No. 91, a photoconductive material is used, which comprises a support coated with an insulating substance in the dark, the electric resistance of which changes depending on the amount of irradiation received during image exposure. The basic characteristics required for an electrophotographic photoreceptor using this photoconductive material are (1) being able to be charged to an appropriate potential in a dark place, (2) having little potential dissipation in a dark place, ( 3) It is possible to quickly dissipate the electric charge by light irradiation.

Conventionally, selenium has been used as an electrophotographic photoreceptor.
Inorganic photoreceptors having a photosensitive layer containing an inorganic photoconductive compound such as zinc oxide and cadmium sulfide as a main component have been widely used. However, these satisfies the conditions (1) to (3), but are not necessarily satisfactory in thermal stability, moisture resistance, durability and productivity.

In order to overcome the disadvantages of inorganic photoconductors, electrophotographic photoconductors containing various organic photoconductive compounds as main components have been actively developed in recent years. For example, US Pat.
No. 7851 discloses a photoreceptor having a charge transport layer containing triallylpyrazolin, and US Pat. No. 3,871,880 discloses a charge generating layer comprising a derivative of a perylene pigment and a charge comprising a condensation product of 3-propylene and formaldehyde. Photoconductors and the like comprising a transport layer are known.

Further, the organic photoconductive compound can freely select the photosensitive wavelength range of the electrophotographic photosensitive member depending on the compound.
JP-A-2754 and JP-A-56-167759 disclose substances exhibiting high sensitivity in the visible region, and JP-A-57-19576 and JP-A-61-228.
Japanese Patent No. 453 discloses a compound having sensitivity in the infrared region.

Of these materials, those exhibiting sensitivity in the infrared region are used in laser beam printers (hereinafter abbreviated as LBP) and LED printers, which have made remarkable progress in recent years, and their demand frequency is increasing.

Electrophotographic photoreceptors using these organic photoconductive compounds are used as function-separated type photoreceptors in which a charge transport layer and a charge generation layer are laminated in order to satisfy both electrical and mechanical properties. In many cases. On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, and further optical characteristics according to the electrophotographic process applied.

Particularly in an electrophotographic photosensitive member that is repeatedly used, an electric and mechanical external force such as corona or direct charging, image exposure, toner development, transfer process and surface cleaning is directly applied to the surface of the electrophotographic photosensitive member. Therefore, durability against them is also required.

Specifically, electrical deterioration due to ozone and nitrogen oxides during charging, mechanical deterioration such as abrasion and scratches on the surface due to discharge during charging, rubbing of a cleaning member, and electrical deterioration Durability against deterioration is required.

The electrical deterioration is particularly problematic in the development in which the carrier stays in the light-irradiated portion and a potential difference occurs between the light-irradiated portion and the non-light-irradiated portion. In addition, there is a phenomenon in which positive charges generated during transfer or rubbing are accumulated and a potential difference is generated between other portions, which appears as positive memory.

Mechanical deterioration is particularly poor in durability against mechanical deterioration in organic photoreceptors, which are different from inorganic photoreceptors and are often soft in terms of material.

Various attempts have been made to satisfy the durability characteristics required for the photoreceptor as described above.

Polycarbonate resin having bisphenol A as a skeleton has been attracting attention as a resin which is often used for the surface layer and has good wear properties and electric characteristics. However, it cannot solve all the problems mentioned above and It has such a problem.

(1) It has poor solubility and shows good solubility only in a part of halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-cycloloethane, and since these solvents have low boiling points, When a photoconductor is manufactured using a coating liquid prepared from any of these solvents, the coated surface is likely to whiten. It takes time to control the solid content of the coating liquid.

(2) Tetrahydrafuran, dioxane, cyclohexanone or a mixed solvent thereof is partially soluble in solvents other than halogenated aliphatic hydrocarbons, but the solution gels in a few days. It is not suitable for photoconductor production due to its poor aging property.

(3) Even if the above (1) and (2) are improved, solvent cracks are easily generated in the polycarbonate resin having bisphenol A as a skeleton.

(4) In addition, in the conventional polycarbonate resin, since the film formed of the resin has no lubricity, the photoconductor is easily scratched, and the cleaning setting is set to reduce the abrasion amount of the electrophotographic photoconductor. Image defects may occur, and cleaning defects and toner fusion may occur due to early deterioration of the cleaning blade.

Regarding the solution stability mentioned in the above (1) and (2), a polycarbonate Z resin having a bulky cyclohexylene group as a structural unit of the polymer is used or is copolymerized with bisphenol Z or bisphenol C. Has been solved by.

Solvent cracks can also be solved by using silicon-modified polycarbonate or ether-modified polycarbonate as disclosed in JP-A-6-51544 and JP-A-6-75415. . However, these modified polycarbonates have a structure that has flexibility against internal stress in the polymer in order to prevent solvent cracks as compared with conventional polycarbonate resins, and as a result, the mechanical strength of the polymer body is reduced. It had the drawback of falling.

Further, in recent years, there has been a direct charging system as disclosed in JP-A-57-17826 and JP-A-58-40566, in which a voltage is directly applied to a charging member to apply a charge to an electrophotographic photosensitive member. It is becoming mainstream.

This is a method in which a roller-shaped charging member made of conductive rubber or the like is directly brought into contact with the electrophotographic photosensitive member to apply an electric charge, and the amount of ozone generated is much smaller than that of a scorotron. About 80% of the current passed through the charger is wasted because it flows through the shield, whereas direct charging has the merit that it is extremely economical without this wasted amount.

However, direct charging has a disadvantage that charging stability is very poor because of charging by the discharge according to the Pashton's rule. As a countermeasure, a so-called AC / DC charging method in which an AC voltage is superimposed on a DC voltage has been devised (Japanese Patent Application Laid-Open No. 63-149668).

This charging method improves the stability at the time of charging, but the amount of discharge on the surface of the electrophotographic photosensitive member is greatly increased due to the superposition of AC, so that the scraped amount of the electrophotographic photosensitive member is increased. A new problem has arisen, and not only mechanical strength but also electrical strength has come to be required.

[0024]

DISCLOSURE OF THE INVENTION The object of the present invention is to have cleaning property and scratch resistance, solvent crack resistance, strong mechanical strength, and good electrical resistance due to direct charging. Also, a highly durable and high-quality electrophotographic photoreceptor, which has an excellent memory characteristic of positive charge that affects the photoreceptor during transfer or rubbing, and can always obtain a high-quality image in repeated electrophotographic processes, A process cartridge having a photographic photosensitive member and an electrophotographic apparatus.

[0025]

That is, the present invention provides an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photosensitive member is a fluorine-based resin particle and the following formula (1) )

[0026]

[Outside 4] (In the formula, X is —CR ₁₃ R ₁₄ — (R ₁₃ and R ₁₄ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms). ,
An optionally substituted 1,1-cycloalkylene group having 5 to 11 carbon atoms, an α, ω-alkylene group having 2 to 10 carbon atoms, a single bond, —O—, —S—, —SO— or —SO ₂ -. R _{1 to} R ₁₂ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group or an alkylene group, and n is an integer. And an electrophotographic photosensitive member containing a polymer having a structural unit represented by the formula (1).

The present invention also provides a process cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The halogen atom in the present invention includes a fluorine atom, a chlorine atom and a bromine atom, the alkyl group includes a methyl group, an ethyl group and a propyl group, and the aryl group includes a phenyl group. Groups and naphthyl groups, and the alkylene groups include methylene group, dimethylene group, trimethylene group and the like. Further, as the substituent which these may have,
The halogen atom, the alkyl group and the aryl group as described above can be mentioned.

In the present invention, the wear resistance of the surface layer is improved by appropriately selecting the binder for forming the photosensitive layer of the electrophotographic photosensitive member, particularly the surface layer, and incorporating the fluorine-based resin particles in the surface layer. Thus, it is possible to provide a highly durable and high-quality electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus that solve the above-mentioned problems.

Examples of the fluorine resin particles include tetrafluoroethylene resin, trifluoroethylene chloride resin, hexafluoroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin and difluorodichloroethylene resin. To be You may mix these 1 type individually or 2 or more types. Moreover, you may mix with antiwear agents and lubricants other than the above.

The particle size and molecular weight of the fluororesin particles can be appropriately selected and are not particularly limited.

Specific examples of the constitutional unit represented by the formula (1) are shown in Table 1, but the constitutional unit is not limited to these.

[0033]

[Outside 5]

[0034]

[Outside 6]

Preferred examples include the structural unit examples 1, 2 and 7, and the structural unit 1 is particularly preferred. Further, the copolymers of Structural Unit Examples 1 and 2 are preferable.

The polymer having a constitutional unit represented by the formula (1) used in the present invention is a terephthalic acid chloride and an isophthalic acid chloride for increasing the solubility of the bisphenol represented by the following formula (2). Interfacial polymerization can be carried out by stirring the mixture in a solvent / water system under alkali.

The ratio of terephthalic acid chloride and isophthalic acid chloride is determined in consideration of the solubility of the polymer, and there is no established theory. However, any chloride is 30 mol
It should be noted that the solubility of the synthesized polymer is extremely lowered when the content is less than 100%. Usually, it is preferable to synthesize at a ratio of 1/1.

[0038]

[Outside 7] (In the formula, X is —CR ₁₃ R ₁₄ — (R ₁₃ and R ₁₄ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms). ,
An optionally substituted 1,1-cycloalkylene group having 5 to 11 carbon atoms, an α, ω-alkylene group having 2 to 10 carbon atoms, a single bond, —O—, —S—, —SO— or —SO ₂ -. R _{1 to} R ₈ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group or an alkylene group. In the electrophotographic photoreceptor of the present invention, even if the polymer is composed of the same structural unit represented by the formula (1), the polymer may be composed of two or more different types of structural units represented by the formula (1). It may be a polymer.

Further, a copolymer may be prepared with other general bisphenols such as bisphenol Z, bisphenol A, bisphenol C and bisphenol AF in consideration of solubility at the time of polymerization. However, in this case, the constitutional unit represented by the formula (1) is 20 to 90 mol% of the total polymer.
It is preferably present, more preferably 50-99 mo
1%.

Further, other binder resin may be added if necessary. Examples of other binder resins include thermoplastic resins such as polycarbonate resin, acrylic resin, polyester resin, polyamide resin, polyvinyl acetate resin and polyvinyl butyral resin; thermosetting resins such as polyurethane resin, phenol resin and epoxy resin; Curing resin etc. are mentioned.

The ratio of the fluororesin particles in the surface layer is appropriately selected depending on the type of the fluororesin particles and the constitution of the photosensitive layer. When the addition amount is large, there are problems such as a decrease in light transmittance, a decrease in sensitivity, and scattering of image exposure light to cause image bleeding. On the other hand, if the addition amount is too small, it is easily worn and the effect of the present invention cannot be sufficiently obtained. It is generally 0.1 to 50% by weight, particularly preferably 0.5 to 40% by weight, based on the total solids of the surface layer. Further, it is possible to add additives such as a dispersion aid, if necessary.

Among the dispersing aids for the fluorine-based resin particles, particularly preferable ones are fluorine-based comb-type graft polymers. The fluorine-based comb-type graft polymer has a molecular weight of 100 having a polymerizable functional group at one end of each molecular chain.
It is obtained by copolymerizing a macromonomer composed of an oligomer having a relatively low molecular weight of about 0 to 10000 and a fluoropolymerizable monomer, and the fluoropolymer has a backbone and the macromonomer polymer hangs in a branch shape. It has a structure.

The macromonomer is selected such that the resin to which the graft polymer is added has an affinity, and for example, a polymer or copolymer of acrylic acid ester, methacrylic acid ester, styrene compound or the like is used.

On the other hand, as the fluorine-based polymerizable monomer,
Hereinafter, one or more polymerizable monomers having a fluorine atom in the side chain as in (3) to (7) are used, but the invention is not limited thereto.

[0045]

[Outside 8] (In the formula, R ₁ ′ represents a hydrogen atom or a methyl group.
R ₂ 'represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a nitrile group, and may be a combination of several kinds thereof. n is an integer of 1 or more, m is an integer of 1 to 5, k
Represents an integer of 1 to 4, and m + k = 5. ) The content of the fluorinated comb-type graft polymer is suitably 0.01 to 10% by weight based on the solid content measurement, particularly preferably 0.02 to 2% by weight, and the dispersibility is less than 0.01% by weight. The improvement effect is not sufficient. On the other hand, if it exceeds 10% by weight, the graft polymer will be present not only on the surface of the coating film but also in the bulk. Accumulation of residual charges will occur when the operation is performed.

In forming the surface layer of the present invention, generally, the above-mentioned fluororesin particles are dispersed in the above-mentioned binder resin, the charge-transporting material and the solvent are added thereto to prepare a coating solution, which is prepared by a coating means. A photoconductor is prepared by coating. As the solvent used at this time, a solvent having good solubility in the binder resin and the charge transport material and good dispersibility of the fluorine-based resin particles is selected. Particularly good examples are ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; ethers such as diethyl ether and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; hydrocarbons such as toluene and benzene; chlorobenzene. And halogenated hydrocarbons such as dichloromethane.

As a method for preparing a coating liquid for forming the surface layer of the electrophotographic photosensitive member of the present invention, fluorine resin particles,
The charge transport material and the binder resin may be simultaneously dispersed with the solvent. Alternatively, a coating liquid may be prepared by preparing a dispersion liquid in which the fluorine-based resin particles and the binder resin are previously dispersed, and mixing the dispersion liquid with the binder resin and the charge transport material dissolved in advance. In the preparation of the coating liquid for the electrophotographic photosensitive member used in the present invention, or the fluorinated resin particle dispersion liquid, simple stirring and mixing may be used, but if necessary, a dispersing means such as a ball mill, a roll mill, a sand mill and a high pressure homogenizer may be used. Good. Ideally, the dispersed particle size is close to the intrinsic primary particle size of the fluororesin particles used and has a uniform distribution.

The electrophotographic photoreceptor according to the present invention has particularly excellent solvent crack resistance, positive charge memory characteristics,
It also has good electrophotographic characteristics, as well as mechanical strength and electrical resistance characteristics against AC charging.

The arylate structure of the polymer of the present invention is A
It is resistant to electrical deterioration due to C-charging, and has higher electrical resistance than conventional carbonate bonds. Although the reason for this has not been confirmed, it is assumed that the carbonate bond has a large dipole moment due to oxygen atoms on both sides of the carboxy group and is weak against electric energy.

By having this arylate structure, the rigidity is improved and the mechanical strength is also improved. By adding fluorine resin particles thereto, further durability can be provided, and by having fluorine resin particles in the film, internal stress can be relieved considerably. Therefore, it is presumed that the surface is also protected by the fluorine-based resin particles to prevent the invasion of the chemical agent that causes the solvent crack, and even if it invades inside, the stress is relaxed and the crack is not generated.

It was also found that the presence of the arylate structure improves the matching with the charge transport material and improves the memory characteristics, and that the addition of the fluorine-based resin particles further improves the positive memory characteristics. This is because the stacking property inside the film is changed by including the fluorine-based resin particles in the resin having the arylate structure with increased rigidity, and the effect of improving the charge transfer rate in addition to the matching property of the charge transport material is also exhibited. Presumed to be present.

The constitution of the electrophotographic photosensitive member used in the present invention will be described below.

The electrophotographic photosensitive member according to the present invention may be a single layer type in which the photosensitive layer contains the charge transport material and the charge generating material in the same layer, or a laminated type in which the charge transport layer and the charge generating layer are separated. Although it is good, the laminated type is preferable in terms of electrophotographic characteristics.

The conductive support to be used may be any one having conductivity, and examples thereof include metals such as aluminum and stainless steel, metals provided with a conductive layer, paper and plastic, and the shape is a sheet or a cylinder. And so on.

When the image input such as LBP is laser light, a conductive layer may be provided for the purpose of preventing interference fringes due to scattering or covering scratches on the support. This can be formed by dispersing conductive powder such as carbon black and metal particles in a binder resin. The thickness of the conductive layer is suitably 5 to 40 μm, preferably 10 to 30 μm.

An intermediate layer having an adhesive function is provided thereon. Examples of the material for the intermediate layer include polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, casein, polyurethane, and polyether urethane. These are applied by dissolving in an appropriate solvent. The thickness of the intermediate layer is 0.05 to 5 μm, preferably 0.1 to 5 μm.
3 to 1 μm is appropriate.

A charge generation layer is formed on the intermediate layer.
Examples of the charge generation material used in the present invention include selenium-tellurium, pyrylium, thiapyrylium dyes, phthalocyanine, anthantrone, dibenzapyrene quinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone, and asymmetric quinocyanine pigments. Can be In the case of the function-separated type, the charge generation layer includes a homogenizer, ultrasonic dispersion, ball mill, vibrating ball mill, sand mill, attritor, roll mill and liquid collision type high speed with 0.3 to 4 times the amount of the charge generation material as the binder resin and solvent. Disperse well with a method such as a disperser, apply the dispersion,
It is formed by drying. The thickness of the charge generation layer is 5 μm or less, preferably 0.1 to 2 μm.

The charge transport layer is mainly formed by coating and drying a paint in which a charge transport material and the binder resin of the present invention are dissolved in a solvent. Examples of charge transport materials used include triarylamine compounds, hydrazone compounds,
Examples thereof include stilbene compounds, pyrazoline compounds, oxazole compounds, triallylmethane compounds and thiazole compounds.

These are combined with 0.5 to 2 times the amount of binder resin and coated and dried to form a charge transport layer. The thickness of the charge transport layer is 5 to 40 μm, preferably 15 to 30
μm is suitable.

FIG. 1 shows a schematic structure of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

In the figure, reference numeral 1 is a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in the direction of an arrow at a predetermined peripheral speed. The photoreceptor 1 rotates during the rotation process.
The peripheral surface of the primary charging means 3 is uniformly charged with a positive or negative predetermined potential, and then image exposure light 4 from an image exposure means (not shown) such as slit exposure or laser beam scanning exposure is received. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then developed by the developing means 5.
The toner-developed image developed by the toner image is transferred from a paper supply unit (not shown) between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1 and fed to a transfer material 7 fed therefrom. The image is sequentially transferred by the transfer unit 6.

The transfer material 7 which has received the image transfer is separated from the surface of the photoconductor and introduced into the image fixing means 8 to undergo image fixing, and is printed out to the outside of the apparatus as a copy.

The surface of the photoconductor 1 after the image transfer is cleaned by the cleaning means 9 after removal of the transfer residual toner, and the pre-exposure light 10 from the pre-exposure means (not shown).
Is used for image formation repeatedly after the charge removal processing. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure is not necessarily required.

In the present invention, among the constituent elements such as the electrophotographic photosensitive member 1, the primary charging means 3, the developing means 5 and the cleaning means 9 described above, a plurality of components are integrally combined to form a process cartridge, The process cartridge may be detachably attached to the main body of the electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photoconductor 1 to form a cartridge, and the cartridge can be attached to and detached from the apparatus body by using a guide unit such as a rail 12 of the apparatus body. It can be the process cartridge 11.

When the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 is reflected and transmitted from the original, or the original is read by a sensor and converted into a signal. Laser beam scanning,
Light emitted by driving the LED array, driving the liquid crystal shutter array, and the like.

On the other hand, when used as a printer for a facsimile, the image exposure light 4 becomes exposure light for printing received data. FIG. 2 is a block diagram showing an example of this case.

The controller 14 controls the image reading section 13 and the printer 22. The entire controller 14 is controlled by the CPU 20. The read data from the image reading unit 13 is transmitted to the partner station through the transmission circuit 16. The data received from the partner station is sent to the printer 22 through the receiving circuit 15. Predetermined image data is stored in the image memory. The printer controller 21 controls the printer 22. 17 is a telephone.

The image received from the line 18 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 15, and then the image information is decoded by the CPU 20 and sequentially stored in the image memory 19. To be done. When the image of at least one page is stored in the memory 19, the CPU 20 performs image recording of the page. The CPU 20 reads out the image information of one page from the image memory 19, and Sends out image information. The printer controller 21
When receiving one page of image information from the CPU 20, the printer 22 is controlled to record image information of the page. The CPU 20 is receiving the next page during recording by the printer 22.

In this way, the image is received and recorded.

The electrophotographic photosensitive member of the present invention can be used not only for an electrophotographic copying machine but also for a laser beam printer,
RT printer, LED printer, LCD printer,
It can be widely used in electrophotographic applications such as laser plate making.

The following is a description of the embodiment. In the examples
Parts are parts by weight. [Example 1] An aluminum cylinder having a diameter of 30 mm 254 mm was used as a support, and a coating material composed of the following materials was applied to the support by a dipping method and heat-cured at 140 ° C for 30 minutes to form a conductive layer of 15 µm. .

Conductive pigment: S _n O ₂ coated barium sulfate 10 parts Resistance adjusting pigment: titanium oxide 2 parts Binder resin: phenol resin 6 parts Leveling material: silicone oil 0.001 part Solvent: methanol, methoxypropanol 0. 2 / 0.8 20 copies

Next, a solution prepared by dissolving 3 parts of N-methoxymethylated nylon and 3 parts of copolymerized nylon in a mixed solvent of 65 parts of methanol and 30 parts of n-butanol was applied by a dipping method to 0.5 μm. Was formed.

Next, the Bragg angle 2 of X-ray diffraction of CuKα
4 parts of oxytitanium phthalocyanine (TiOPc) having a strong peak at θ ± 0.2 ° of 9.0 °, 14.2 °, 23.9 ° and 27.1 ° and polyvinyl butyral (trade name: S-REC BM2, Sekisui 2 parts by mass and 60 parts by mass of cyclohexanone were dispersed in a sand mill using φ1 mm glass beads for 4 hours, and then 100 parts of ethyl acetate was added to prepare a dispersion liquid for a charge generation layer. This was applied by a dipping method to form a 0.3 μm charge generation layer.

Next, as a step of preparing a dispersion of a fluorine resin particle, tetrafluoroethylene resin powder (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) 25 parts Polymer of condition No. 1 in Table 2 25 parts Fluorine comb Type graft polymer (trade name: GF-300, manufactured by Toagosei) 1 part After thoroughly mixing 75 parts of monochlorobenzene, dispersed for 4 hours with a sand mill using φ1 mm glass beads to prepare a fluororesin particle dispersion. did.

This polymer had a predetermined biphenol (0.01
mol), sodium hydroxide (0.8 g) and tetramethylammonium chloride (1 g) were dissolved in 100 ml of water, and the mixture was put into a 1 liter mixer, and 1,2-
Dichloroethane (30 ml) and terephthalic acid chloride (0.005 mol) and isophthalic acid chloride (0.05 mol)
(05 mol) was added with stirring and 1
After high-speed stirring for 0 minutes and standing for 2 hours, a 1,2-dichloroethane solution was recovered, and a large amount of hexane was added thereto to recover it as a polymer. It should be noted that the product used was one that had been purified with water after recovery, dissolved in chloroform and purified by dropping methanol.

Next, 9 parts of an amine compound having the following structural formula,

[0079]

[Outside 9] 1 part of amine compound of the following structural formula

[0080]

[Outside 10] Further, 10 parts of the polymer of Condition No. 1 in Table 2 and 12.5 parts of the fluororesin particle dispersion liquid were dissolved in a mixed solvent of 30 parts of monochlorobenzene and 70 parts of dichloromethane. The content of the fluororesin particles with respect to the solid content is 10% by weight.

This coating composition was applied by the dipping method, and the coating was applied at 120 ° C. for 2 hours.
It was dried for an hour to form a 25 μm charge transport layer.

Next, the evaluation will be described.

The device is a Hewlett-Packard LBP
"Laser jet 4plus" (process speed 7
1 mm / sec). In the remodeling, primary charging was controlled by constant current control and constant voltage control. The produced electrophotographic photosensitive member was subjected to paper passing durability (HH durability) at 28 ° C. and 90% RH using this apparatus. The sequence was an intermittent mode in which the print was stopped once for each print.

When the toner is used up, the toner is replenished and the image is durable until problems occur. In addition, a part of the electrophotographic photosensitive member was charged to +500 V, and after standing for 24 hours, the light potential was measured, and the value of how much the potential decreased before being positively charged was defined as the plus memory value.

Furthermore, 3000 L is used as a part of the electrophotographic photosensitive member.
The light potential was measured after illuminating the light of a white fluorescent lamp for 10 minutes with ux and left for 10 minutes, and how much the light potential decreased from before the light was applied was taken as a photomemory value.

Further, regarding the solvent cracking property, resin was adhered to the surface and left for 48 hours, and the presence or absence of solvent cracking was observed by microscopic observation.ク indicates that no crack was observed, and x indicates that it was observed.

The results are shown in Table 3.

[Examples 2 to 12] Electrophotographic photoreceptors were prepared and evaluated in the same manner as in Example 1 except that the binder resins used in the charge transport layer were those of conditions No. 2 to 12 in Table 2. Table 3 shows the results.

[0089] The mixing ratio between terephthalic acid chloride and isophthalic acid chloride was 1: 1 in molar ratio.

Example 13 An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the content of the fluororesin particles in the surface layer was changed to 30% by weight. Furthermore, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3.

Example 14 An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that polytrifluorochloroethylene resin (trade name: Daiflon, manufactured by Daikin Industries, Ltd.) was used as the fluorine-based resin particles in the surface layer. Was produced. Furthermore, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3.

[Example 15] The same as Example 1 except that polytetrafluoroethylene-6-fluoropropylene resin (trade name: NEOFLON, manufactured by Daikin Industries, Ltd.) was used as the fluorine-based resin particles in the surface layer. An electrophotographic photoreceptor was produced. Furthermore, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3.

[0093]

Comparative Example 1 Amine compound 9 having the following structural formula
Department,

[0095]

[Outside 11] 1 part of amine compound of the following structural formula

[0096]

[Outside 12] And 10 parts of the binder resin under the condition No. 1 in Table 2 was dissolved in a mixed solvent of 30 parts of monochlorobenzene and 70 parts of dichloromethane. This coating material was applied onto an aluminum cylinder on which a charge generation layer had been applied in the same manner as in Example 1 by a dipping method and dried at 120 ° C. for 2 hours to form a 25 μm charge transport layer.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The results are shown in Table 5.

[Comparative Examples 2 and 3] Electrophotographic photoreceptors were prepared in the same manner as in Comparative Example 1 except that the binder resins for the charge transport layer were those of conditions No. 1 and 2 in Table 4. This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The results are shown in Table 5.

[Comparative Examples 4 and 5] An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the binder resins of the charge transport layer were those of conditions No. 1 and 2 shown in Table 4. This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The results are shown in Table 5.

[0100]

[Outside 13]

[0101]

[0102]

EFFECTS OF THE INVENTION According to the present invention, it has excellent solvent crack resistance and positive memory characteristics, has high mechanical strength, and has good electric resistance characteristics against discharge due to direct charging, and is easy to manufacture. It has become possible to provide an electrophotographic photosensitive member suitable for charging, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

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[Procedure amendment]

[Submission date] August 30, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Added

[Correction contents]

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.

FIG. 2 is a diagram illustrating an example of a block diagram of a facsimile having the electrophotographic photosensitive member of the present invention.

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor of the present invention 2 axis 3 primary charging means 4 image exposure light 5 developing means 6 transfer means 7 transfer material 8 image fixing means 9 cleaning means 10 pre-exposure light 11 process cartridge 12 rail 13 image Reading unit 14 Controller 15 Reception circuit 16 Transmission circuit 17 Telephone 18 Line 19 Image memory 20 CPU 21 Printer controller 22 Printer

Claims (7)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photosensitive member comprises fluorine resin particles and the following formula (1): (In the formula, X is —CR ₁₃ R ₁₄ — (R ₁₃ and R ₁₄ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms). ,
An optionally substituted 1,1-cycloalkylene group having 5 to 11 carbon atoms, an α, ω-alkylene group having 2 to 10 carbon atoms, a single bond, —O—, —S—, —SO— or —SO ₂ -. R _{1 to} R ₁₂ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group or an alkylene group, and n is an integer. ) An electrophotographic photoreceptor comprising a polymer having a structural unit represented by 2. The polymer according to claim 2, And [Outside 3] The electrophotographic photosensitive member according to claim 1, which has a structural unit represented by: 3. The fluororesin particles are tetrafluoroethylene resin, trifluoroethylene chloride resin, hexafluoroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluorodichloroethylene resin, and The electrophotographic photosensitive member according to claim 1, which is at least one resin selected from these copolymers. 4. The electrophotographic photosensitive member according to claim 1, wherein the content of the fluorine-based resin particles is 0.1 to 50% by weight based on the total solid content of the surface layer. 5. The electrophotographic photosensitive member according to claim 1, wherein the surface layer contains a fluorine-based comb-type graft polymer. 6. An electrophotographic apparatus main body integrally supporting at least one unit selected from the group consisting of an electrophotographic photosensitive member according to claim 1 and a charging unit, a developing unit and a cleaning unit. Process cartridge characterized by being removable. 7. An electrophotographic apparatus comprising: the electrophotographic photosensitive member according to claim 1; a charging unit; an image exposing unit; a developing unit; and a transfer unit.