JP3273717B2 - Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art In recent years, organic photoconductive materials have been widely used as materials used for electrophotographic photosensitive members because of their advantages in terms of their non-polluting properties and high productivity. These electrophotographic photoconductors are often used as function-separated photoconductors in which a charge generation layer and a charge transport layer are stacked in order to satisfy both electrical and mechanical properties. On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, and optical characteristics according to the electrophotographic process applied. Particularly for photoreceptors that are used repeatedly, the surface layer of the photoreceptor is charged with corona,
Since electrical and mechanical external forces such as image exposure, toner development, transfer to paper, and cleaning are directly applied,
Durability against them is required.

[0003] Specifically, durability such as a decrease in sensitivity, a decrease in potential and an increase in residual potential due to deterioration due to ozone generated during corona charging, abrasion of the surface due to rubbing and the like, and the like. Is required.

[0004] The surface of the photoreceptor is generally a thin resin layer,
The properties of the resin are very important. As a resin that satisfies the above conditions, a polycarbonate resin having bisphenol A as a skeleton has attracted attention. However, not all of the above-mentioned electrical characteristics are satisfied by the bisphenol A-type polycarbonate resin. Has problems.

(1) Poor solubility, showing good solubility only in a part of halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane. Since these halogenated aliphatic hydrocarbons have a low boiling point, when a photoreceptor is manufactured using a coating solution prepared with these solvents, the coated surface tends to be whitened. It also takes time to control the process such as the solid content of the coating liquid.

(2) Solvents other than halogenated aliphatic hydrocarbons are partially soluble in tetrahydrofuran, dioxane, cyclohexanone or a mixed solvent thereof, but the solution gels within a few days. It is not suitable for the production of a photoreceptor because of poor aging properties.

(3) Even if the disadvantages mentioned in the above (1) and (2) are improved, solvent cracks are liable to occur in a polycarbonate resin having only a bisphenol A derivative as a main chain skeleton.

(4) In addition, in the case of the conventional polycarbonate resin, the coating formed of the resin does not have much lubricity, so that the photosensitive member is liable to be scratched, resulting in image defects,
In some cases, poor cleaning due to early deterioration of the cleaning blade and insufficient cleaning due to reversal of the cleaning blade may occur.

(5) In addition, in recent years, as a charging method for copying machines and laser beam printers, a direct charging method in which a conductive member such as conductive rubber is brought into contact with the electrophotographic photosensitive member to charge the electrophotographic photosensitive member has become mainstream. In general, an alternating current (hereinafter abbreviated as AC) is applied to a conductive member in order to stabilize the current (refer to JP-A-63-149668).

As a result, the amount of electric charge discharged onto the drum is greatly increased unlike the past corona charging, and the surface of the electrophotographic photosensitive member is directly deteriorated, and the durability is remarkably reduced. .

Conventionally, the solution stability mentioned in the above (1) and (2) has been solved by using a polycarbonate Z resin having a bulky cyclohexylene group as a structural unit of the polymer. However, the polycarbonate Z resin has a relatively large volume shrinkage particularly when a film is formed by a casting method from a solution, and may leave stress inside the film. For this reason, it had a disadvantage that it was relatively weak against stress corrosion. In order to solve this, for example, JP-A-61-62040 discloses a method of reducing stress corrosion cracking by mixing a polycarbonate A resin and a polycarbonate Z resin. Japanese Patent Application Laid-Open No. 61-62039 discloses a method of reducing stress corrosion cracking by copolymerizing bisphenol A and bisphenol Z. However, any of these methods is insufficient for solvent cracking. Absent.

In addition, as shown in the above (4) and (5), ordinary polycarbonate resins have relatively low lubricity and durability against a cleaning blade used in an electrophotographic process, and thus have poor cleaning performance. It has been pointed out that the blade is inverted due to the progress of the durability, which causes a cleaning failure, and that a strong discharge or a strong force is applied to the photosensitive drum, thereby causing damage or scraping. In order to improve this, a method of adding silicone oil or copolymerizing a polydimethylsiloxane block with a polycarbonate resin as disclosed in JP-A-61-132954 or disclosed in JP-A-63-65444. As described above, there is known a method of using bisphenol A obtained by changing the (CH ₃ ) ₂ -C = moiety at the center of the bisphenol A to (CF ₃ ) ₂ -C =. However, the method of adding silicone oil deteriorates the electrical properties in electrophotography, specifically, the sensitivity and residual potential properties, and loses the silicone oil in the surface layer due to the progress of durability, resulting in permanent lubrication. There is a drawback that the property cannot be obtained. Also, the use of a copolymer of the above-mentioned methylsiloxane block provides good lubricity, but conventional polydimethylsiloxane copolymers become cloudy or gel when used as a solution. There is a difficulty, and even when used as a surface layer of an electrophotographic photoreceptor, it is not satisfactory in durability, especially in mechanical strength. Similarly, the solubility of fluorine-based polycarbonate in monomers is extremely poor, cloudiness,
In addition to the drawbacks such as gelation, the well-known copolymerized with bisphenol A is insufficient for gelation, and there is a drawback that increasing the fluorine content decreases the mechanical strength. Was.

To solve these problems, Japanese Patent Laid-Open No. 6-295075 discloses a method of increasing mechanical strength while increasing lubricity by using a copolymer of a fluorine-based monomer, a silicon-based monomer and bisphenol Z. This is a system using very direct charging, especially AC
There is a drawback that the durability is low with respect to the charging method to which is applied.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the conventional electrophotographic photoreceptor using a polycarbonate resin as a surface layer, and to improve the lubricity and abrasion resistance, especially the direct charging. The present invention provides an electrophotographic photosensitive member which maintains film strength while improving abrasion resistance, has good solvent cracking properties, and is easy to manufacture, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus. is there.

[0015]

SUMMARY OF THE INVENTION The present invention relates to an electrophotographic photosensitive member having a photosensitive layer on a conductive support , comprising:
And the electrophotographic photosensitive member by a conductive member to which an alternating current is applied.
An electrophotographic photoreceptor for an electrophotographic apparatus for directly charging a body, wherein a surface layer of the electrophotographic photoreceptor has a structural unit represented by the following general formula (1):

[0016]

Embedded image (Wherein, R _{1 to} R ₈ are the same or different and each represent a hydrogen atom,
And at least one group selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and a substituted or unsubstituted aryl group. A structural unit represented by the following general formula (2):

[0017]

Embedded image(Where R₉ Are the same or different and are substituted or absent
A substituted or unsubstituted alkylene group having 1 to 6 carbon atoms
A substituted alkylidene group having 1 to 6 carbon atoms; _Ten~ R
_FifteenIs the same or different and is substituted or unsubstituted carbon number
1 to 12 alkyl groups or substituted or unsubstituted carbon
R 1 represents an aryl group represented by Formulas 1 to 12,₁₆And R₁₇Is the same
Or differently, a halogen atom, a substituted or unsubstituted
Consists of an alkyl group and a substituted or unsubstituted aryl group
At least one group selected from the group;
Are each independently an integer from 0 to 4, and n is an integer from 1 to 200.
The number and m are integers of 0 to 200. ) And the following general formula
Structural unit shown in (3)

[0018]

Embedded image (Wherein, R _{18 to} R ₂₅ are the same or different and each represents a hydrogen atom,
A halogen atom, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group, each of which represents at least one group selected from the group consisting of X and -S- or -O-
Show. An electrophotographic photoreceptor comprising a copolymer having the following formula:

Further, the present invention is a process cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member.

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. Examples of the alkylidene group include a cyclohexylidene group. Examples of the substituent which these may have include a halogen atom, an alkyl group and an aryl group as described above.

Table 1 shows specific examples of the structural unit represented by the general formula (1). Preferred examples include Structural Units 1, 2, and 5, and Structural Unit Example 1 is particularly preferred.

[0022]

[Table 1] Tables 2 and 3 show specific examples of the structural unit represented by the general formula (2). Preferred examples include Structural Unit Example 8.

[0023]

[Table 2]

[0024]

[Table 3] Next, specific examples of the structural unit represented by the general formula (3) are shown in Table 4.
Shown in Preferred examples include Structural Unit Examples 15 and 16, and Structural Unit Example 15 is particularly preferred.

[0025]

[Table 4] Tables 1 to 4 are given as examples and are not limited to these structures.

The general formula (1) used in the present invention,
The copolymers having the structural units represented by (2) and (3) can be obtained by combining bisphenols represented by the following general formula (5) and bisphenols represented by the following general formula (6) with phosgene, carbonate, or chloroform. It can be obtained by interfacial polymerization in the presence of a mate or the like.

[0027]

Embedded image B is -O-, -S- or

[0028]

Embedded image R ₃₆ ~R ₄₃ R ₁₈ is when B is -O- or -S- to R ₂₅
Same as B

[0029]

Embedded image Is the same as R _{1 to} R ₈ .

[0030]

Embedded image (In the formula, R ₉ is the same or different and represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, and R _{10 to} R ₁₅ are the same or different and have a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms.
12 alkyl groups or substituted or unsubstituted carbon atoms of 1
And R ₁₆ and R ₁₇ are the same or different and represent at least one group selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group, a and b are each independently an integer of 0 to 4, n is an integer of 1 to 200,
m is an integer of 0 to 200. In the electrophotographic photoreceptor of the present invention, when the weight of a structural unit represented by other than the general formula (2) is α and the structural unit represented by the general formula (2) is β, β / (α + β) The value is preferably in the range of 0.01 to 0.9, and particularly preferably in the range of 0.01 to 0.1.

In the general formula (2), n is 1 to 20.
It represents an integer of 0, and particularly preferably 5 to 100. R
Examples of ₉ include ethylene, propylene, isopropylene, butylene and pentylene, and particularly preferred are ethylene, propylene and isopropylene.

(Synthesis Example) While introducing dry nitrogen gas into a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube, and a condenser, 500 parts (parts by weight, hereinafter the same) of a 10% aqueous sodium hydroxide solution was added to the following structural formula. Of bisphenol was charged and dissolved.

[0033]

Embedded image Next, 250 parts of methylene chloride and a 10% aqueous solution of triethylamine were added, and the mixture was heated to 100 ° C. and blown with phosgene gas at a flow rate of 1 liter / min for 15 minutes while stirring.

Thereafter, a methylene chloride layer of the reaction solution was separated, and p-tertbutylphenol 0.1 was added to the solution.
g, 5 parts of a hydroxyaryl compound having the following structure and methylene chloride were added to make the total amount 700 parts, and then mixed with 250 parts of an aqueous sodium hydroxide solution to obtain an aqueous solution of triethylamine 5 parts.
And stirred at room temperature for 2 hours.

[0035]

Embedded image After completion of the reaction, the methylene chloride layer was separated, 1,000 parts of methylene chloride was newly added, washed with water, diluted hydrochloric acid and water in that order, and then poured into methanol to obtain a polymer. The polymer was dried, dissolved in methylene chloride, and purified by reprecipitation from methanol. The yield is 97%. The weight average molecular weight by gel permeation chromatography was 120,000.

The above copolymer may be further made into a quaternary copolymer by further adding a structural unit represented by the general formula (4), depending on the use condition of the electrophotographic photosensitive member using the same.

The copolymer to which the structural unit represented by the general formula (4) is added can be easily obtained by using bisphenol A, bisphenol C, bisphenol Z or the like as a monomer.

By adding these, parameters such as solubility can be freely controlled.

The electrophotographic photoreceptor of the present invention has particularly excellent solvent crack resistance, surface lubricity, and storage stability. This is because the surface layers have the chemical resistance of formulas (1) and (2). It is considered that the introduction of the copolymer having the structural unit represented by the formula (1) reduces the rate at which the chemical causing the solvent crack enters the photosensitive layer, thereby lowering the rate at which an abnormality occurs in the coating. . This is because the copolymer itself used in the present invention has an effect of relaxing internal stress to some extent, and does not cause solvent cracks even if a certain amount of chemicals enters. This effect can be further improved by blending the copolymer with polycarbonate Z resin. Furthermore, the addition of such a polymer prevents layer separation due to precipitation of low molecular weight components added to the photosensitive layer. This is considered to be because the polydimethylsiloxane skeleton of the structural unit represented by the formula (2) also functions as a compatibilizer particularly for the charge transporting substance, and furthermore, a fluorine atom having a large electronegativity in the main chain. To function as a compatibilizer with respect to the charge transporting substance,
It is considered that since the structural units represented by (3) and (3) are copolymerized to a certain degree or more, the inside of the polymer becomes random, and the porosity inside the polymer decreases, so that the charge transport material becomes difficult to move.

Furthermore, the polymer according to the present invention has improved durability especially against direct charging, which is presumed to be due to the following reasons. Structural units represented by (1) and (2) with respect to the discharge energy of charging hardly form radicals and thus are not easily degraded, but have low mechanical strength. Therefore, by providing a rigid skeleton as shown in (3), a fibril having a partially high glass transition point is formed inside, and not only the mechanical strength is increased, but also the structural unit of (3) is stacked inside the molecule. By doing so, it is considered that the constitutional units (1) and (2) are more likely to appear on the surface layer, and the durability against discharge is further increased. In particular, the structure (3) is effective because there is no proton bonded to its central atom.

The copolymer contained in the surface layer of the electrophotographic photoreceptor of the present invention must be determined in consideration of the scratch resistance and hardness, production stability, storage stability and the like required according to the electrophotographic process. No. At this time, the proportion of the polymer to be blended and the copolymer having the structural units represented by the formulas (1), (2) and (3) is as follows.
It is necessary to control in consideration of environmental stability with respect to durability and electrical characteristics, and manufacturing stability depending on solution stability, but it is necessary to control the structural units having the structural units represented by the formulas (1), (2) and (3). Preferably, the polymerization ratio is in the range of 0.1 to 95% by weight with respect to the polymer to be blended with the polymer,
A range of 0.5 to 80% by weight is particularly preferred.

The polymer to be blended with the copolymer is preferably one which is compatible with the copolymer to some extent, and particularly preferably polycarbonate, polyarylate and the like. It is preferable to use a polymer such as bisphenol A, bisphenol C, or bisphenol Z as the structure, and polycarbonate C is particularly effective.

When the weight of the structural unit represented by other than the formula (2) is represented by α and the structural unit represented by the formula (2) is represented by β, the value of β / (α + β) is 0.01 to 0.3. When it is in the range of 1, the proportion of the copolymer is preferably in the range of 10 to 60% by weight, particularly preferably in the range of 30 to 60% by weight.

When the weight of the structural unit represented by other than the formula (1) is represented by α and the structural unit represented by the formula (1) is represented by β, the value of β / (α + β) is 0.1 to 0.1. 6, preferably 0.15 to 0.45.

When the weight of the structural unit other than the formula (3) is α and the structural unit of the formula (3) is β, the value of β / (α + β) is 0.2 to 0.3. 8 is preferable, and the range of 0.4 to 0.8 is particularly preferable.

In the electrophotographic photoreceptor of the present invention, even if the photosensitive layer is of a single-layer type in which the charge generating substance and the charge transporting substance are contained in the same layer, the charge generating layer containing the charge generating substance and the charge transporting substance May be laminated, but in order to satisfy various characteristics required of the electrophotographic photosensitive member, a laminated (separated function) electrophotographic photosensitive member is preferable.

Further, if necessary, a binder composition can be used as a surface protective layer. When the binder composition is used as a surface protective layer, a conductive powder such as tin oxide, indium oxide, ITO, titanium oxide or the like is used to impart electric characteristics according to the applied electrophotographic process. Mixtures or charge transport materials can also be added. The addition amount is 1 to 50% by weight based on the binder composition, and a lubricant such as tetrafluoroethylene particles may be further added to the surface protective layer.

When producing the electrophotographic photosensitive member of the present invention,
As the conductive support, a metal or alloy such as aluminum or stainless steel, paper, plastic, or the like is used, and the shape thereof can be arbitrary depending on the electrophotographic apparatus to be applied, such as a cylindrical cylinder or a film. .

In the present invention, on the conductive support,
An undercoat layer having a barrier function and an adhesive function can be provided.

The undercoat layer is used for improving the adhesiveness of the photosensitive layer, improving the coating property, protecting the support, covering defects on the support, improving the charge injection property from the support, protecting the photosensitive layer against electrical breakdown, etc. Formed for Examples of the material for the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, copolymer nylon, glue, gelatin and the like. It has been known. These are dissolved in a suitable solvent and applied on a support. The thickness at this time is preferably about 0.1 to 2 μm.

As the charge generating substance in the electrophotographic photoreceptor of the present invention, selenium-tellurium, pyrylium, thiapyrylium dyes, various kinds of central metals and crystals, specifically, for example, α, β, γ, ε, X type Phthalocyanine compound having a crystal form such as, anthantrone pigment, dibenzpyrene quinone pigment, pyranthrone pigment, trisazo pigment,
Examples thereof include disazo pigments, monoazo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments, quinocyanines, and amorphous silicon described in JP-A-54-143645.

In the case of a function-separated type photoreceptor, the charge generation layer is formed by adding the above-mentioned charge generation substance to a homogenizer, an ultrasonic dispersion, a ball mill, a vibrating ball mill, a sand mill, an atomizer together with 0.3 to 4 times the amount of a binder resin and a solvent. It is well dispersed by a method such as a lighter and a roll mill, and a dispersion is applied and dried to form a dispersion. The film thickness is 5 μm or less, especially 0.1 to 2 μm.
It is preferably in the range of m.

As the charge transporting substance, pyrene, N
Carbazole compounds such as -ethylcarbazole, N-isopropylcarbazole, N-methyl-N-phenylhydrazino-3-methylidene-9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-10-ethylphenothiazine,
N, N-diphenylhydrazino-3-methylidene-10
-Ethylphenoxazine, p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, p-diethylaminobenzaldehyde-N-α-naphthyl-N-phenylhydrazone, p-pyrrolidinobenzaldehyde-
Hydrazone-based compounds such as N, N-diphenylhydrazone, 1,3,3-trimethylindolenine-ω-aldehyde-N, N-diphenylhydrazone, p-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone; 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1-phenyl-
3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [quinolyl (2)]-3- (p-diethylaminostyryl) -5-
(P-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (p-diethylaminostyryl)
-5- (p-diethylaminophenyl) pyrazoline, 1
-[6-Methoxy-pyridyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1- [pyridyl (3)]-3- (p
-Diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1- "pyridyl (2)]-3
-(P-diethylaminostyryl) -4-methyl-5-
(P-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (α-methyl-p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1-phenyl-3- (p-diethylamino Pyrazoline compounds such as styryl) -4-methyl-5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (α-benzyl-p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline and spiropyrazoline , 2- (p-diethylaminostyryl) -6-diethylaminobenzoxazole, 2-
Oxazole compounds such as (p-diethylaminophenyl) -4- (p-dimethylaminophenyl) -5- (2-chlorophenyl) oxazole and thiazole compounds such as 2- (p-diethylaminostyryl) -6-diethylaminobenzthiazole And triarylmethane compounds such as bis (4-diethylamino-2-methylphenyl) phenylmethane and 1,1-bis (4-N, N-
Diethylamino-2-methylphenyl) heptane, 1,
And polyarylalkanes such as 1,2,2-tetrakis-4-N, N-dimethylamino-2-methylphenyl) ethane.

The charge transport layer is formed by applying and drying a solution obtained by dissolving the charge transport material and the binder resin in a solvent. The mixing ratio of the charge transport material and the binder resin is preferably about 2: 1 to 1: 2. Examples of the solvent include aromatic solvents such as toluene, xylene and monochlorobenzene, as well as dioxane, tetrahydrofuran and tetrahydropyran. And the like can be used. As a method of applying the solution, for example, a dip coating method, a spray coating method, a curtain coating method, a spin coating method, and the like are known. For efficient mass production of electrophotographic photosensitive members, the dip coating method is the best, and dip coating using the copolymer used in the present invention is possible. 10 to 200 ° C, preferably 20 to 150 ° C for 5 minutes to 5 after coating
Ventilation drying or still drying is performed for a period of time, preferably 10 minutes to 2 hours, to form a charge transport layer having a thickness of 5 to 30 μm.

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

In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around a shaft 2 at a predetermined peripheral speed in a direction indicated by an arrow. The photoreceptor 1 rotates during the rotation process.
The peripheral surface thereof is uniformly charged with a predetermined positive or negative potential by the primary charging unit 3 and then receives image exposure light 4 from an image exposure unit (not shown) such as slit exposure or laser beam scanning exposure. 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 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 having undergone the image transfer is separated from the surface of the photoreceptor, introduced into the image fixing means 8 and subjected to image fixing to be printed out as a copy out of the apparatus.

The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by removing the untransferred toner by the cleaning means 9, and furthermore, a pre-exposure light 10 from a 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, a plurality of components such as the above-described electrophotographic photosensitive member 1, primary charging means 3, developing means 5, and cleaning means 9 are integrally connected as a process cartridge. The process cartridge may be configured to be detachable from a main body of an 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 photoreceptor 1 to form a cartridge, which can be attached to and detached from the apparatus main body using a guide unit such as a rail 12 of the apparatus main body. The process cartridge 11 can be used.

When the electrophotographic apparatus is a copier or a printer, the image exposure light 4 is read and transmitted from the original, or the original is read by a sensor and converted into a signal, and the exposure is performed according to the 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 facsimile printer, 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. 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.

An 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 decoded by the CPU 20 to be sequentially stored in the image memory 19. Is 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.

Thus, the reception and recording of the image are performed.

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.

[0067]

Next, the present invention will be described with reference to examples. In the examples, “parts” indicates “parts by weight”.

Example 1 Conductive titanium oxide powder 50 coated with tin oxide containing 10% antimony oxide
Parts, phenolic resin 25 parts, methyl cellosolve 20 parts,
Five parts of methanol and 0.002 part of silicone oil (polydimerylsiloxane polyoxyalkylene copolymer, average molecular weight 3,000) were dispersed in a sand mill using φ1 mm glass beads for 2 hours to prepare a coating for the conductive layer. This paint was applied onto a 30φ aluminum cylinder by a dip coating method, and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

Next, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare an intermediate layer paint. This paint was applied onto the conductive layer by a dip coating method, and dried at 100 ° C. for 20 minutes to form a 0.6 μm intermediate layer.

Next, the black angle 2θ ± 0.2 degrees in the X-ray diffraction of CuKα was 9.0 degrees, 14.2 degrees, and 23.9 degrees.
Of oxytitanium phthalocyanine having a strong peak at 27.1 degrees and 27.1 degrees, 2 parts of polyvinyl butyral (trade name: SLECK BM2, manufactured by Sekisui Chemical Co., Ltd.) and 35 parts of cyclohexanone were mixed with a sand mill using φ1 mm glass beads. Disperse over time, then add ethyl acetate 6
0 parts were added to prepare a charge generation layer coating. This paint is applied on the intermediate layer by a dip coating method,
For 15 minutes to form a charge generation layer having a thickness of 0.2 μm.

Next, 8 parts of a compound having the following structural formula:

[0072]

Embedded image 2 parts of a compound of the following structural formula,

[0073]

Embedded image 3 parts of a polymer (weight average molecular weight 17 × 10 ⁴ ) composed of a structural unit represented by the following formula

[0074]

Embedded image And 7 parts of the polymer synthesized in Synthesis Example
0 parts and 30 parts of monochlorobenzene were dissolved in a mixed solvent to prepare a charge transport layer coating. This paint was applied on the charge generation layer by a dip coating method, and dried at 120 ° C. for 60 minutes to form a charge transport layer having a thickness of 23 μm, thereby producing an electrophotographic photosensitive member.

Using the prepared electrophotographic photosensitive member, surface lubricity and solvent crack resistance were measured. Regarding the surface lubricity, a cleaning blade made of urethane rubber for a copying machine was used, which was brought into contact with the surface of the photoreceptor at a contact angle of 30 degrees, and the sliding resistance was measured using a HEIDON-14 type surface tester (Shinto Chemical Co., Ltd.) )).

The solvent cracking resistance is measured after a resin is adhered to the surface of the photoreceptor and after 24 hours and 2 days.
The presence or absence of cracks in the photoreceptor was observed under a microscope at a magnification of ×, and an image obtained when the photoreceptor was used was visually observed. The evaluation was performed in the following five stages.

A: No cracks were found on the photoreceptor, and no image defects were found in the image due to cracks.

：: Cracks are observed on the photoreceptor,
No image defect confirmed.

Δ: Cracks are confirmed on the photoreceptor, and one image defect is confirmed.

X: Cracks were observed on the photoreceptor, and 2 to 10 image defects were observed.

XX: Cracks are observed on the photoreceptor, and 11 or more image defects are observed.

Further, the photoreceptor was allowed to stand at 30 ° C. and 93% RH for 24 hours, and then was directly charged by Apple Inc.
Into a laser writer 16 / 600PS
Paper passing durability was performed continuously for 00 sheets, and black spots caused by toner adhering to the surface of the photoreceptor were observed.

Further, paper passing durability was performed in an intermittent mode in which the printing was stopped once for each print using another photosensitive member, and the number of sheets on which charge failure occurred due to scraping of the charge transport layer was examined.

Further, the measuring instrument was modified so that the AC peak-to-peak voltage could be output 1.8 times the normal value, and the same intermittent mode durability was performed to examine the durability against charging. Table 6 shows the results.

(Examples 2 to 20) Example 2 was repeated in the same manner as in Example 1 except that the component ratio at the time of copolymerization, the parts by weight of the copolymer and the polymer to be blended were changed as shown in Table 5. ~ 20
An electrophotographic photosensitive member corresponding to was prepared and evaluated. Table 6 shows the results.

[0086]

[Table 5]

[0087]

[Table 6]

Comparative Examples 1 to 4 Comparative Examples 1 to 4 were conducted in the same manner as in Example 1 except that the binder resin was changed to those shown in Table 7.
An electrophotographic photosensitive member corresponding to was prepared and evaluated. Table 9 shows the results.

[0089]

[Table 7]

Comparative Example 5 9 parts of a polymer (weight average molecular weight: 16 × 10 ⁴ ) composed of structural units represented by the following formula:

[0091]

Embedded image And a structural unit represented by the following formulas (a) and (c)

[0092]

Embedded image One part of a copolymer (weight average molecular weight 6.2 × 10 ⁴ ) in which the component (a) is 96% by weight of the total weight of the copolymer is dissolved in a mixed solvent of 20 parts of dichloromethane and 40 parts of monochlorobenzene. This solution was applied onto the charge generating layer in Example 1 by dip coating, and dried at 120 ° C. for 60 minutes to form a charge transporting layer having a thickness of 23 μm. Table 9 shows the results.

(Comparative Examples 6 to 9) An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the weight ratio of the formula (a) and the parts by weight of the copolymer during copolymerization were changed as shown in Table 8. Was created and evaluated. Table 9 shows the results.

[0094]

(Comparative Example 10) 5 parts of a polymer (weight average molecular weight: 18 × 10 ⁴ ) composed of a structural unit represented by the following formula:

[0096]

Embedded image And a structural unit represented by the following formulas (a), (b) and (c)

[0097]

Embedded image 5 parts of a copolymer (weight average molecular weight 6.0 × 10 ⁴ ) in which the component (a) is 45% by weight of the total weight of the copolymer and the component (b) is 45% by weight are used as the binder resin. Other than the above, an electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1. Table 9 shows the results.

[0098]

[Table 8]

[0099]

According to the present invention, it has excellent solvent crack resistance without impairing mechanical strength, good surface lubricity and cleaning properties, and is excellent in discharge by a direct charging method. Electrophotographic photoreceptor which exhibits low durability and has a reduced durability life even under severe discharge conditions, and which can withstand use even under high-pressure discharge such as high-speed models, a process cartridge having the electrophotographic photoreceptor, and an electrophotographic process The device became possible.

[Brief description of the 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.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor of this 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 Receiving circuit 16 transmitting circuit 17 telephone 18 line 19 image memory 20 CPU 21 printer controller 22 printer

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-295075 (JP, A) JP-A-6-19160 (JP, A) JP-A-6-19161 (JP, A) JP-A-7- 70423 (JP, A) JP-A-6-19162 (JP, A) JP-A-2-189551 (JP, A) JP-A-7-128874 (JP, A) JP-A-7-225486 (JP, A) JP-A-6-19150 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 5/00 CA (STN)

Claims (4)

(57) [Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, comprising: a conductive material to which a direct current and an alternating current are applied.
Electrophotography in which the electrophotographic photosensitive member is directly charged by a member
In an electrophotographic photoreceptor for an apparatus, a surface layer of the electrophotographic photoreceptor is a structural unit represented by the following general formula (1): (Wherein, R _{1 to} R ₈ are the same or different and are at least one selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and a substituted or unsubstituted aryl group) A structural unit represented by the following general formula (2): (Wherein, R ₉ are the same or different, represent a substituted or unsubstituted alkylene group or a substituted or unsubstituted alkylidene group having 1 to 6 carbon atoms having 1 to 6 carbon atoms, R ₁₀ to R
₁₅ is the same or different and represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or an substituted or unsubstituted aryl group having 1 to 12 carbon atoms, and R ₁₆ and R ₁₇ are the same or different and are each a halogen atom Represents at least one group selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group, a and b
Are each independently an integer from 0 to 4, n is an integer from 1 to 200, and m is an integer from 0 to 200. ) And a structural unit represented by the following general formula (3): (Wherein, R _{18 to} R ₂₅ are the same or different and each represents a hydrogen atom,
A halogen atom, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group, each of which represents at least one group selected from the group consisting of X and -S- or -O-
Show. An electrophotographic photosensitive member comprising a copolymer having the following formula: 2. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the electroconductive photoreceptor has a direct current and an alternating current applied thereto.
Electrophotography in which the electrophotographic photosensitive member is directly charged by a member
In an electrophotographic photoreceptor for an apparatus, a surface layer of the electrophotographic photoreceptor is a structural unit represented by the following general formula (1): (Wherein, R _{1 to} R ₈ are the same or different and are at least one selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and a substituted or unsubstituted aryl group) A structural unit represented by the following general formula (2): (Wherein, R ₉ are the same or different, represent a substituted or unsubstituted alkylene group or a substituted or unsubstituted alkylidene group having 1 to 6 carbon atoms having 1 to 6 carbon atoms, R ₁₀ to R
₁₅ is the same or different and represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 1 to 12 carbon atoms, and R ₁₆ and R ₁₇ are the same or different and are each a halogen atom Represents at least one group selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group, a and b
Are each independently an integer from 0 to 4, n is an integer from 1 to 200, and m is an integer from 0 to 200. ) A structural unit represented by the following general formula (3) (Wherein, R _{18 to} R ₂₅ are the same or different and each represents a hydrogen atom,
X represents at least one group selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group, and X represents -S- or -O-
Show. An electrophotographic photosensitive member comprising a copolymer having the following formula: And a structural unit represented by the following general formula (4): (Wherein, R _{26 to} R ₃₃ are the same or different and each represents a hydrogen atom,
Represents at least one group selected from the group consisting of a halogen atom and a substituted or unsubstituted alkyl group, R ₃₄
And R ₃₅ are the same or different and each represents a substituted or unsubstituted alkyl group or the residue necessary for R ₃₄ and R ₃₅ to combine with each other to form a substituted or unsubstituted divalent alkylidene group together with a carbon atom in the formula. Represents a group. An electrophotographic photosensitive member comprising a copolymer having the following formula: 3. The electrophotographic photosensitive member according to claim 1 or 2, and a conductive member to which a direct current and an alternating current are applied.
A process unit which integrally supports at least one unit selected from the group consisting of a charging unit, a developing unit, and a cleaning unit for directly charging the electrophotographic photosensitive member, and is detachably mountable to an electrophotographic apparatus main body. . 4. The electrophotographic photoreceptor according to claim 1 , wherein the electroconductive member to which a direct current and an alternating current are applied is provided.
Charging means for directly charging the electrophotographic photosensitive member , image exposure means,
An electrophotographic apparatus comprising a developing unit and a transfer unit.