JPH0683093A - Electrophotographic sensitive body and electrophotographic device and facsimile having the same - Google Patents

Abstract

PURPOSE:To obtain an image preserving material having good surface lubricity and excellent duarability by adding a copolymer having concurrently plural constitutional units in the surface layer of the electrophotographic sensitive body. CONSTITUTION:The surface layer of the electrophotographic sensitive body contains a compound having the constitutional unit represented by the formula I and the copolymer having concurrently the constitutional units represented by the formulas II and III. Also the charge generating layer of this electrophotographic sensitive body contains oxy-titanium-phthalocyanine having the Cu Kalpha characteristic X-ray diffraction pattern which shows strong peaks at the following 2theta+ or -0.2 deg. values of the diffraction angles: 9.0, 14.2, 23.9 and 27.1 deg.. In the formulas I-III, A is a cycloalkylidene group of 1 to 15 carbon atoms or -O-, etc.; each of R1-R16 is a hydrogen or a halogen atom, etc.; (x) and (y) are ratios of the comonomeric units to the compound (mol%); B is a cycloalkylidene group of 1 to 10 carbon atoms or -O-, etc.; each of R21-R28 is a hydrogen or a halogen atom, etc.; R31 is an alkylene or an alkylidene group of 2 to 6 carbon atoms; each of R32-R35 is an alkyl group of 1 to 3 carbon atoms, etc.; (n) is 1 to 200.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image holding member using a specific resin, and more particularly to an image holding member having good surface lubricity and excellent durability.

[0002]

2. Description of the Related Art In recent years, organic photoconductive materials have been widely used as materials used for electrophotographic photoreceptors because of their advantages in pollution-free property and high productivity. These electrophotographic photoreceptors are often used as function-separated photoreceptors in which a charge generation layer and a charge transport layer are laminated 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 in the case of photoreceptors that are repeatedly used, electrical and mechanical external forces such as corona charging, image exposure, toner development, transfer to paper, and cleaning are directly applied to the surface layer of the photoreceptor. , Durability against them is required.

Specifically, durability against deterioration of sensitivity, decrease of electric potential and increase of residual electric potential due to deterioration due to ozone generated at the time of corona charging, abrasion of the surface due to rubbing and scratches, etc. Are required.

The surface of the photoreceptor is generally a thin resin layer,
The properties of the resin are very important. Polycarbonate resins having bisphenol A as a skeleton have been attracting attention as resins satisfying the above conditions, but not all of the electrophotographic characteristics described above are satisfied by bisphenol A type polycarbonate resins. I have 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-dichloroethane. Since these halogenated aliphatic hydrocarbons have a low boiling point, the coated surface is likely to be whitened when a photoreceptor is manufactured using a coating solution prepared with these solvents.
Further, it takes a lot of time to manage the process such as the solid content of the coating liquid. (2) For solvents other than halogenated aliphatic hydrocarbons, it is partially soluble in tetrahydrofuran, dioxane, cyclohexanone, or a mixture thereof, but the solution gels within a few days. It has poor stability over time and is not suitable for the production of photoreceptors. (3) Further, even if the drawbacks mentioned in the above (1) and (2) are improved, solvent cracks are likely to occur in the polycarbonate resin having only bisphenol A or a bisphenol A derivative as a main chain skeleton. (4) In addition, in the conventional polycarbonate resin, the coating formed by the resin does not have much lubricity, so that the photoconductor is apt to be scratched, resulting in an image defect, or cleaning failure due to early deterioration of the cleaning blade. In some cases, defective cleaning may occur due to reversal of the cleaning blade.

Conventionally, the solution stability mentioned in (1) and (2) has been solved by using a polycarbonate Z resin having a bulky cyclohexylene group as a structural unit of a polymer. However, the polycarbonate Z resin has a relatively large volume shrinkage particularly when a coating film is formed from a solution by a casting method, and stress may remain inside the coating film. Therefore, it has a drawback that it is relatively weak against stress corrosion. 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.
Further, Japanese Patent Laid-Open No. 61-62039 discloses a method of reducing stress corrosion cracking by copolymerizing bisphenol A and bisphenol Z, but none of them is sufficient for solvent cracking.

In addition to this, as shown in (4), the ordinary polycarbonate resin has relatively low lubricity with respect to the cleaning blade used in the electrophotographic process, and the cleaning blade is reversed due to the progress of durability. It has been pointed out that this causes a cleaning failure or a scratch due to a strong force applied to the photosensitive drum. To improve this, silicone oil is added, or JP-A-61-1329
As disclosed in Japanese Patent Laid-Open No. 54-54, a method of copolymerizing a polydimethylsiloxane block with a polycarbonate resin is known. However, in the method of adding silicone oil, electrical characteristics in electrophotography, specifically sensitivity and residual potential characteristics are deteriorated,
In addition, there is a drawback in that the silicone oil in the surface layer is lost due to the progress of durability and permanent lubricity cannot be obtained.

Further, if a product obtained by copolymerizing the above-mentioned polydimethylsiloxane block is used, the lubricity becomes good, but the conventional polydimethylsiloxane copolymer becomes cloudy or gels when made into a solution. However, even if it is used as a surface layer of an electrophotographic photoreceptor, it is not satisfactory in terms of durability.

Further, in recent years, a relatively large amount of a low molecular weight compound such as a charge-transporting substance is added due to the demand for higher sensitivity of the organic electrophotographic photosensitive member, and when the electrophotographic photosensitive member is stored for a long period of time. There is a problem that the above-mentioned low molecular weight component is deposited and the layers are separated.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems of the electrophotographic photosensitive member using the conventional polycarbonate resin as the surface layer, and to improve the lubricity and abrasion resistance. An object of the present invention is to provide an electrophotographic photoreceptor having excellent mechanical properties and durability, good storage stability, and easy to manufacture.

[0010]

That is, the present invention provides an electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photoreceptor is represented by the following formula (1):

[0011]

[Chemical 4] (In the formula, A is a linear, branched or cyclic alkylidene group having 1 to 15 carbon atoms, an aryl-substituted alkylidene group, an arylenedialkylidene group, or -O-, -S-, -C.
O -, - SO- or -SO ₂ - indicates, R ₁ through R
₁₆ represents a hydrogen atom, a halogen atom, or an alkyl group, an alkenyl group, or an aryl group having 1 to 4 carbon atoms, and x and y represent a copolymerization ratio (mol%)), and a compound having a structural unit Formula (2) below

[0012]

[Chemical 5] (In the formula, B is a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylidene group, an arylenedialkylidene group, or -O-, -S-, -C.
O -, - SO- or -SO ₂ - indicates, R ₂₁ through R
₂₈ represents a hydrogen atom, a halogen atom, or an alkyl group or an alkenyl group having 1 to 4 carbon atoms) and the following formula (3)

[0013]

[Chemical 6] (In the formula, R ₃₁ is an alkylene group having 2 to 6 carbon atoms or an alkylidene group, R _{32 to} R ₃₅ are alkyl groups having 1 to 3 carbon atoms,
A phenyl group or a substituted phenyl group, n is an integer of 1 to 200), and the charge generation layer has a diffraction angle 2θ ± 0.2 in CuKα characteristic X-ray diffraction. ° is 9.0 °, 14.2 °, 2
An electrophotographic photoreceptor, which contains oxytitanium phthalocyanine having strong peaks at 3.9 ° and 27.1 °, an electrophotographic apparatus having the same, and a facsimile.

Specific examples of the structural unit represented by the formula (1) used in the present invention are shown below, but the present invention is not limited thereto.

Exemplified Compound No.

[0016]

[Chemical 7]

[0017]

[Chemical 8]

Specific examples of the structural unit represented by the formula (2) used in the present invention include the same as the specific examples of the structural unit represented by the above formula (1) and represented by the formula (7). The thing is a typical example.

[0019]

[Chemical 9]

Specific examples of the structural unit represented by the formula (3) used in the present invention are shown below, but the invention is not limited thereto.

Exemplified Compound No.

[0022]

[Chemical 10]

[0023]

[Chemical 11] Among these, especially No. The structural unit represented by 11 is preferable.

The copolymer having the constitutional units represented by the formulas (2) and (3) used in the present invention has the following formula (4).

[0025]

[Chemical 12] (In the formulae, B and R _{21 to} R ₂₈ are the same as described above.)
Bisphenol and the following formula (5)

[0026]

[Chemical 13] (In the formula, R _{31 to} R ₃₅ are the same as those mentioned above.) The bisphenol can be obtained by interfacial polymerization in the presence of phosgene, a carbonic acid ester, a chloroformate or the like.

In the present invention, when the weight of the structural unit represented by the formula (2) is α and the weight of the structural unit represented by the formula (3) is β, the value of β / (α + β) is 0. .01
The range is preferably from 0.9 to 0.9, particularly 0.01.
It is preferably in the range of 0.1.

Further, n in the formula (3) represents an integer of 1 to 200, and particularly preferably 5 to 100. Examples of R ₃₁ include ethylene, propylene, isopropylene, butylene, pentylene and the like, with ethylene, propylene and isopropylene being particularly preferred.

The electrophotographic photosensitive member of the present invention has particularly excellent solvent crack resistance, surface lubricity, and storage stability. The reason for this is that the surface layer has chemical resistance (2) and (). It is considered that by introducing the copolymer having the constitutional unit shown in 3), the rate at which the chemical agent that causes solvent cracks penetrates into the photosensitive layer is reduced, and the rate at which abnormality occurs in the coating is reduced. To be Furthermore, the addition of such a polymer prevents layer separation due to precipitation of low molecular weight components added to the photosensitive layer. It is considered that this is because the polydimethylsiloxane skeleton of the structural unit represented by the formula (3) particularly functions as a compatibilizing agent for the charge transport substance.

The polymer contained in the surface layer of the electrophotographic photosensitive member of the present invention is determined in consideration of scratch resistance required according to the electrophotographic process, hardness, production, stability, storage stability and the like. There must be. Equation (1) used at this time
The ratio of the polymer having the constitutional unit represented by the formula (1) to the polymer having the constitutional units represented by the formulas (2) and (3) depends on solvent crack resistance, durability, and environmental stability and solution stability with respect to electrical characteristics. The polymer having the constitutional units represented by the formulas (2) and (3) should be controlled with respect to the polymer having the constitutional units represented by the formula (1). Polymerization rate from 0.1 to 9
It is preferably in the range of 5% by weight, particularly preferably in the range of 0.5 to 80% by weight.

Particularly, when the weight of the constitutional unit represented by the formula (2) is α and the weight of the constitutional unit represented by the formula (3) is β, the value of β / (α + β) is 0.01 to. When it is in the range of 0.1, the proportion of the polymer is preferably in the range of 1 to 15% by weight, particularly preferably in the range of 3 to 10% by weight.

The electrophotographic photoreceptor of the present invention has a charge generating layer containing a charge generating substance even if the photosensitive layer is a so-called single layer type in which the charge generating substance and the charge transporting substance are contained in the same layer. It may be a laminated type in which charge transport layers containing a charge transport substance are laminated, but the latter laminated electrophotographic photoreceptor is preferable in order to satisfy various characteristics required for the electrophotographic photoreceptor.

If desired, the binder composition of the present invention can be used as a surface protective layer in contact with the charge transport layer. When the binder composition of the present invention is used as a surface protective layer, tin oxide, indium oxide, IT may be added in order to impart electric characteristics depending on the electrophotographic process to be applied.
It is also possible to add a conductive powder such as O or titanium oxide, a mixture thereof, or a charge transport material. The addition amount is preferably 1% by weight to 50% by weight with respect to the binder composition of the present invention. A lubricant such as Teflon particles may be 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 may be arbitrary according to the applied electrophotographic apparatus such as a cylindrical cylinder or a film. it can.

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

The subbing layer improves the adhesion of the photosensitive layer, the coating property, the protection of the support, the coating of defects on the support, the improvement of the charge injection property from the support, the protection of the photosensitive layer against electrical breakdown, etc. Formed for. Known materials for the undercoat layer include polyvinyl alcohol, pol-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, copolymerized nylon, glue and gelatin. These are dissolved in a suitable solvent and coated on a support.
The film thickness at that time is preferably about 0.1 to 2 μm.

Examples of the charge generating substance in the electrophotographic photosensitive member of the present invention include selenium-tellurium, pyrylium, thiopyrylium dyes, various central metals and crystal systems, specifically, α, β, γ, ε, X. Phthalocyanine compound having a crystal type such as a type, anthanthrone pigment, dibenzpyrenequinone pigment, pyranthrone pigment, trisazo pigment,
Examples thereof include disazo pigments, azo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments, quinocyanines, and amorphous silicon described in JP-A-54-143645. 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, and roll mill together with the binder resin and solvent in an amount of 0.3 to 4 times the amount of the charge generation material. It is formed by being well dispersed by the above method, applied and dried. The film thickness is 5 μm or less, and particularly 0.
It is preferably in the range of 1 to 2 μm.

Further, as the charge transport material, pyrene and N
-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-pyrrolinodibenzaldehyde N, N-diphenylhydrazone, 1,3,3-trimethylindolenine-ω-aldehyde-N, N-diphenylhydrazone, p-diethylbenzaldehyde-3 -Methylbenzthiazolinone-2-
Hydrazones such as 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) pyrazoline, 1- [pyridyl (2)]-3-) p-diethylaminostyryl) -5- ( p-diethylaminophenyl) pyrazoline, 1- [6-methoxy-pyridyl (2)]-3- (p-diethylaminostyryl) -5-
(P-Diethylaminophenyl) pyrazoline, 1- [pyridyl (3)]-3- (p-diethylaminostyryl)
-5- (p-diethylaminophenyl) pyrazoline, 1
-[Pyridyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -4-methyl-5 -(P-diethylaminophenyl) pyrazoline, 1- [pyridyl (2)]-3-
(Α-Methyl-p-diethylaminostyryl) -5-
(P-diethylaminophenyl) pyrazoline, 1-phenyl-3- (p-diethylaminostyryl) -4-methyl-5- (p-diethylaminophenyl) pyrazoline,
Pyrazolines such as 1-phenyl-3- (α-benzyl-p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline and spiropyrazoline, 2-
(P-Diethylaminostyryl) -6-diethylaminobenzoxazole, 2- (p-diethylaminophenyl) -4- (p-dimethylaminophenyl) -5- (2
-Chlorophenyl) oxazole and other oxazole compounds, 2- (p-diethylaminostyryl) -6-diethylaminobenzothiazole and other thiazole compounds,
Triarylmethane compounds such as bis (4-diethylamino-2-methylphenyl) phenylmethane, 1,1-
Bis (4-N, N-diethylamino-2-methylphenyl) heptane, 1,1,2,2-tetrakis-4-N,
Examples thereof include polyarylalkanes such as N-dimethylamino-2-methylphenyl) ethane.

The charge transport layer is applied and formed by dissolving the above charge transport material and the binder resin in a solvent.
The mixing ratio of the charge transport material and the binder resin is 2: 1 to 1: 2.
It is preferable that the amount of the solvent is toluene, xylene, or an aromatic solvent such as monochlorobenzene, dioxane, tetrahydrofuran, or the like.
Cyclic ethers such as tetrahydropyran can also be used. As a method of applying this solution, for example, a dip coating method, a spray coating method, a curtain coating method, a spin coating method and the like are known. The dip coating method is the best for efficient mass production of electrophotographic photoreceptors, and it is possible by using the polycarbonate resin of the present invention. After application 10 ℃ -200 ℃
At 5 ° C. to 150 ° C. for 5 minutes to 5 hours, preferably 10 minutes to 2 hours, ventilation drying or static drying is performed to obtain a charge transport layer having a thickness of 5 to 30 μm.

FIG. 1 shows a schematic structural example of a general transfer type electrophotographic apparatus using the electrophotographic photosensitive member of the present invention.

In the figure, reference numeral 1 denotes a drum type photosensitive member of the present invention as an image bearing member, which is rotationally driven around a shaft 1a in a direction of an arrow at a predetermined peripheral speed. The photosensitive member 1 is uniformly charged at its peripheral surface by a charging unit 2 at a predetermined positive or negative potential in the course of its rotation, and then at an exposure unit 3 an optical image exposure L (slit exposure Laser beam scanning exposure). As a result, electrostatic latent images corresponding to the exposed image are sequentially formed on the peripheral surface of the photoconductor.

The electrostatic latent image is then toner-developed by the developing means 4, and the toner-developed image is rotated by the transfer means 5 between the photoconductor 1 and the transfer means 5 from a paper feeding portion (not shown). The images are sequentially transferred onto the surface of the transfer material P that is synchronously taken out and fed.

The transfer material P which has received the image transfer is separated from the surface of the photoconductor and is introduced into the image fixing means 8 where it is subjected to the image fixing and printed out as a copy.

After the image transfer, the surface of the photosensitive member 1 is cleaned by the cleaning means 6 to remove the residual toner after transfer, and is further discharged by the pre-exposure means 7 to be repeatedly used for image formation.

As the uniform charging means 2 for the photosensitive member 1, a corona charging device is generally widely used. In addition, the transfer device 5
Corona transfer means are also widely used. The electrophotographic apparatus is configured by integrally combining a plurality of constituent elements such as the photoconductor, the developing unit, and the cleaning unit described above as an apparatus unit, and the unit is configured to be detachable from the apparatus body. May be. For example, the photoconductor 1
Alternatively, the cleaning unit 6 and the cleaning unit 6 may be integrated into one unit, and may be detachably configured by using a guide unit such as a rail of the apparatus main body. At this time, the above device unit may be provided with a charging unit and / or a developing unit.

When the electrophotographic apparatus is used as a copying machine or a printer, the optical image exposure L is reflected light or transmitted light from a document or a document is read and converted into a signal, and scanning of a laser beam or an LED array is performed by this signal. Drive or liquid crystal shutter array drive.

When used as a facsimile printer, the optical image exposure L becomes an exposure for printing the received data. FIG. 2 is a block diagram showing an example of this case.

The controller 11 controls the image reading section 10 and the printer 19. The entire controller 11 is CP
It is controlled by U17. The read data from the image reading unit 10 is transmitted to the partner station through the transmission circuit 13. The data received from the partner station is sent to the printer 19 through the receiving circuit 12. The image memory 16 stores predetermined image data. The printer controller 18 controls the printer 19. 14 is a telephone.

The image information received from the line 15 (image information from the remote terminal connected via the line) is demodulated by the receiving circuit 12, then decoded by the CPU 17, and sequentially stored in the image memory 16. Is stored. When the image information of at least one page is stored in the memory 16, the image recording of that page is performed. The CPU 17 reads out one page of image information from the memory 16 and sends the decoded one page of image information to the printer controller 18. Upon receiving the image information of one page from the CPU 17, the printer controller 18 controls the printer 19 to record the image information of the page.

The CPU 17 is receiving the next page while the printer 19 is recording.

Images are received and recorded as described above.

The electrophotographic photoreceptor of the present invention can be used not only in electrophotographic copying machines, but also in laser beam printers and C
RT printer, LED printer, liquid crystal printer,
It can be widely used in electrophotographic application fields such as laser plate making.

Next, the present invention will be described in more detail with reference to examples.

[0054]

【Example】

Example 1 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide (parts by weight, the same applies hereinafter), 25 parts of phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol, and silicone oil ( Polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 300
0) 0.002 part was dispersed for 2 hours in a sand mill using φ1 mm glass beads to obtain a conductive layer coating material. This paint is applied onto a 30φ aluminum cylinder by a dip coating method and dried at 140 ° C. for 30 minutes to give a film thickness of 20 μm.
m conductive layer was formed.

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

Next, the black angle 2θ ± 0.2 ° in the X-ray diffraction of CuKα is 9.0 °, 14.2 °, 23.9.
3 parts of oxytitanium phthalocyanine having a strong peak at 2 ° and 27.1 °, 2 parts of polyvinyl bitillal resin (Sekisui Chemical Co., Ltd., S-REC BM2) and 35 parts of cyclohexanone were dispersed for 2 hours in a sand mill using φ1 mm glass beads. After that, 60 parts of ethyl acetate was added thereto to obtain a charge generation layer dispersion liquid. This dispersion was applied onto the above intermediate layer by a dip coating method and dried at 100 ° C. for 15 minutes to obtain a charge generation layer having a film thickness of 0.2 μm.

Then, the following formula

[0058]

[Chemical 14] 8 parts of 4 compounds shown by

[0059]

[Chemical 15] 2 parts of the compound represented by

[0060]

[Chemical 16] 9 parts of a polymer (viscosity average molecular weight 2.05 × 10 ⁴ ) consisting of the structural unit represented by

[0061]

[Chemical 17] 1 part of a copolymer (viscosity average molecular weight 2.21 × 10 ⁴ ) in which the component (a) is 95% by weight of the total amount of the copolymer, and 20 parts of dichloromethane and 40 parts of monochlorobenzene. 120% by dissolving in a mixed solvent of 1. and applying this solution on the above-mentioned charge generation layer by a dip coating method.
After drying at 60 ° C. for 60 minutes, a charge transport layer having a film thickness of 23 μm was formed.

Using the thus obtained photoreceptor, surface lubricity, precipitation with time and solvent crack resistance were measured. Regarding the surface lubricity, a urethane rubber cleaning blade for a copying machine was used, and this was brought into contact with the surface of the photoconductor at a contact angle of 30 °, and the sliding resistance was measured by HEIDON-14 type surface tester (Shinto Kagaku Co., Ltd. )). further,
Urethane cleaning blade is pressed against this surface layer,
It was stored at 75 ° C. and an accelerated test for precipitation was performed. Regarding the evaluation, after 2 weeks, the photoreceptor was observed with a microscope,
The presence or absence of precipitation was evaluated. Regarding the solvent cracking property, finger grease was adhered to this surface layer and left for 24 hours and 2 days at room temperature and normal humidity, and then the presence or absence of solvent cracking was observed by a microscope. Furthermore, this photosensitive member is kept at 40 ° C. for 9
After leaving under 3% RH for 24 hours, Canon LBP-
The sheets were placed in an LX and continuously passed 5000 sheets, and black spots caused by the toner adhering to the surface of the photoconductor were observed.

The results are shown in Table 2.

Examples 2 to 20 during copolymerization

[0065]

[Chemical 18] An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the polymerization ratio and the weight part of the copolymer were changed as shown in Table 1.

The results are shown in Table 2.

[0067]

[Table 1]

[0068]

[Table 2]

Example 21 In the same manner as in Example 1, a conductive layer and an intermediate layer were formed on an aluminum cylinder.

Then, the following structural formula

[0071]

[Chemical 19] 3 parts of disazo pigment represented by polyvinyl benzal (80% benzalization rate, 11,000 weight average molecular weight)
2 parts and 35 parts of cyclohexanone were dispersed for 12 hours with a sand mill using φ1 mm glass beads, and then 60 parts of methyl ethyl ketone was added to obtain a dispersion liquid for the charge generation layer. This dispersion was applied onto the above-mentioned intermediate layer by a dip coating method and dried at 80 ° C. for 20 minutes to give a film thickness of 0.
A 2 μm charge generation layer was obtained.

Then, the following equation

[0073]

[Chemical 20] 10 parts of the compound represented by

[0074]

[Chemical 21] 5 parts of a polymer (viscosity average molecular weight 2.05 × 10 ⁴ ) consisting of the structural unit represented by

[0075]

[Chemical formula 22] 5 parts of a copolymer (viscosity average molecular weight of 2.21 × 10 ⁴ ) consisting of the structural unit represented by the formula (C), which is 95% by weight of the total weight of the copolymer, 20 parts of dichloromethane and 40 parts of monochlorobenzene. Dissolved in the mixed solvent of No. 1, and this solution was coated on the above-mentioned charge generation layer in the same manner as in Example 1.
It was dried at 0 ° C. for 60 minutes to form a charge transport layer having a film thickness of 23 μm.

The photoreceptor thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 3.

Example 22 In the same manner as in Example 1, a conductive layer, an intermediate layer and a charge generation layer were formed on an aluminum cylinder.

Next, as a resin, the following formula

[0079]

[Chemical formula 23] 8 parts of a polymer (viscosity average molecular weight 8.56 × 10 ⁴ ) consisting of the structural unit represented by

[0080]

[Chemical formula 24] Example 1 except that 2 parts of a copolymer (viscosity-average molecular weight 2.25 × 10 ⁴ ) in which the component (e) is 99% by weight of the total weight of the copolymer, which is composed of the structural unit represented by A charge transport layer was formed in the same manner.

The photoreceptor thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 3.

Example 23 A conductive layer, an intermediate layer and a charge generation layer were formed on an aluminum cylinder in the same manner as in Example 1.

Next, as a resin, the following formula

[0084]

[Chemical 25] 2 parts of a polymer (viscosity average molecular weight 3.31 × 10 ⁴ ) consisting of the structural unit represented by

[0085]

[Chemical formula 26] Example 1 except that 8 parts of a copolymer (viscosity average molecular weight 2.25 × 10 ⁴ ) in which the component (g) is 90% by weight based on the total weight of the copolymer, which is composed of the structural unit represented by A charge transport layer was formed in the same manner.

The photoreceptor thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 3.

Example 24 In the same manner as in Example 1, a conductive layer, an intermediate layer and a charge generation layer were formed on an aluminum cylinder.

Next, as a resin, the following formula

[0089]

[Chemical 27] 5 parts of a polymer (viscosity average molecular weight 3.01 × 10 ⁴ ) consisting of the structural unit represented by

[0090]

[Chemical 28] Example 1 except that 5 parts of a copolymer (viscosity average molecular weight 3.13 × 10 ⁴ ) in which the component (i) is 95% by weight of the total weight of the copolymer, which is composed of the structural unit represented by A charge transport layer was formed in the same manner.

The photoreceptor thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 3.

Example 25 In the same manner as in Example 1, a conductive layer, an intermediate layer and a charge generation layer were formed on an aluminum cylinder.

Next, as a charge transport material, the following formula

[0094]

[Chemical 29] And 10 parts of the compound represented by

[0095]

[Chemical 30] 5 parts of a polymer (viscosity average molecular weight 2.53 × 10 ⁴ ) consisting of the structural unit represented by

[0096]

[Chemical 31] Example 1 except that 5 parts of a copolymer (viscosity average molecular weight 3.25 × 10 ⁴ ) consisting of the structural unit represented by the formula (k) in which the component (k) is 95% by weight of the total weight of the copolymer is used. A charge transport layer was formed in the same manner.

The obtained photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0098]

[Table 3]

Comparative Example 1 Polycarbonate Z as a resin (viscosity average molecular weight 1.9
A photoreceptor was prepared and evaluated in exactly the same manner as in Example 1 except that the charge transport layer was formed by using 10 parts of 2 × 10 ⁴ ).

The results obtained are shown in Table 4.

[0101]

[Table 4]

[0102]

As described above, according to the present invention, it is possible to provide an electrophotographic photoreceptor having excellent lubricity, storage stability, cleaning characteristics, and solvent crack resistance.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a general transfer type electrophotographic apparatus.

FIG. 2 is a block diagram of a facsimile using the electrophotographic apparatus as a printer.

[Explanation of symbols]

 1 Photoreceptor 2 Charging Means 3 Exposure Part 4 Developing Means 5 Transfer Means 6 Cleaning Means 7 Pre-Exposure Means 8 Image Fixing Means

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Hiroshi Aoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Hidetoshi Hirano 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Incorporated (72) Inventor Nobuyuki Hanami 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Junichi Kishi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Shinya Mayama 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (5)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photoreceptor is represented by the following formula (1): (In the formula, A is a linear, branched or cyclic alkylidene group having 1 to 15 carbon atoms, an aryl-substituted alkylidene group, an arylenedialkylidene group, or -O-, -S-, -C.
O -, - SO- or -SO ₂ - indicates, R ₁ through R
₁₆ represents a hydrogen atom, a halogen atom, or an alkyl group, an alkenyl group, or an aryl group having 1 to 4 carbon atoms, and x and y represent a copolymerization ratio (mol%)), and a compound having a constitutional unit, Formula (2) below (In the formula, B is a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylidene group, an arylenedialkylidene group, or -O-, -S-, -C.
O -, - SO- or -SO ₂ - indicates, R ₂₁ through R
₂₈ represents a hydrogen atom, a halogen atom, or an alkyl group or an alkenyl group having 1 to 4 carbon atoms) and a unit represented by the following formula (3): (In the formula, R ₃₁ is an alkylene group having 2 to 6 carbon atoms or an alkylidene group, R _{32 to} R ₃₅ are alkyl groups having 1 to 3 carbon atoms,
A phenyl group or a substituted phenyl group, n represents an integer of 1 to 200), and the charge generation layer has a diffraction angle 2θ ± 0.2 in CuKα characteristic X-ray diffraction. ° is 9.0 °, 14.2 °, 2
An electrophotographic photoreceptor containing oxytitanium phthalocyanine having strong peaks at 3.9 ° and 27.1 °. 2. The weight α of the constitutional unit represented by the formula (2) and the weight β of the constitutional unit represented by the formula (3) are 0.01 ≦ β / (α + β) ≦ 0.1. The electrophotographic photosensitive member according to claim 1. 3. The content of the copolymer having the constitutional unit represented by the formula (2) and the constitutional unit represented by the formula (3) at the same time is 15 with respect to all the resin components contained in the surface layer.
The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is less than or equal to wt%. 4. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1. 5. A facsimile comprising the electrophotographic photosensitive member according to claim 1 and a receiving unit for receiving image information from a remote terminal.