JPH0736199A - Electrophotographic receptor, electrophotographic device and device unit having this electrophotographic receptor - Google Patents

Abstract

PURPOSE:To provide the electrophotographic receptor which has excellent durability and with which excellent images are obtainable in spite of repetitive use by containing a polycarbonate resin having a chain alkyl fluoride group having specific pieces or above of carbon atoms in a surface layer. CONSTITUTION:The surface layer of the electrophotographic receptor having a photosensitive layer on a conductive base contains the polycarbonate resin having the chain alkyl fluoride group having >=4 pieces or above of the carbon atoms in the surface layer. This polycarbonate resin is preferably an arom. polycarbonate resin in terms of mechanical strength. While the carbon atoms that the chain alkyl fluoride possesses are 4 pieces, >=8 pieces are more preferable. The sufficient surface lubricity of the photoreceptor is not obtainable in some cases unless the carbon atoms are <4 pieces. The alkyl fluoride group may exists as a side chain in the monomer unit of the polycarbonate resin and may exist as a group at the terminal of the polymer or may exist at both of the side chain and the terminal.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
Specifically, it relates to an electrophotographic photoreceptor having a surface layer containing a resin having a specific structure. The present invention also relates to an electrophotographic apparatus and apparatus unit having the electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as selenium, cadmium sulfide and zinc oxide have been known as photoconductive materials used for electrophotographic photoreceptors. Organic materials such as polyvinylcarbazole, phthalocyanine, and azo pigments have attracted attention for their advantages such as high productivity and pollution-free property, and although they tend to be inferior to inorganic materials in terms of photoconductive characteristics and durability, they are widely used. It has come to be used. In recent years, new materials having improved drawbacks have been studied, and in particular, photoconductive properties are surpassing those of inorganic materials.

On the other hand, the electrophotographic photosensitive member is repeatedly subjected to actions such as charging, exposure, development, transfer, cleaning and charge removal in an electrophotographic process such as a copying machine and a laser beam printer. Durability against various external forces such as electrical is required. In particular, mechanical strength such as abrasion resistance and scratch resistance is one of the important factors that determine the durable life of the electrophotographic photoreceptor. Since the organic photoconductive material does not have a film-forming property by itself, it is generally formed together with a binder resin or the like when forming the photosensitive layer. The factor that gives the property includes the characteristics of the binder resin. Therefore,
Attempts have been made to increase the molecular weight of the binder resin, to use a curable resin, and to use a lubricant such as Teflon.

[0004]

However, the use of the high molecular weight binder resin has a problem that it causes an increase in the viscosity of the layer forming coating material. Further, use of a curable resin may lead to deterioration of the organic photoconductive material at the time of curing and deterioration of electrophotographic properties due to the presence of impurities such as unreacted functional groups and polymerization initiators. Furthermore, the use of lubricants is not fully satisfactory in terms of film forming properties and compatibility.

With the recent trend toward higher image quality and higher durability, electrophotographic photoreceptors capable of stably supplying superior images over a long period of time have been studied.

An object of the present invention is to provide an electrophotographic photosensitive member having excellent durability and capable of obtaining an excellent image even when repeatedly used.

Another object of the present invention is to provide an electrophotographic apparatus and an apparatus unit having the above electrophotographic photosensitive member.

[0008]

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 has a chain-like structure having 4 or more carbon atoms. An electrophotographic photoreceptor comprising a polycarbonate resin having a fluorinated alkyl group.

The present invention is also an electrophotographic apparatus and apparatus unit having the above electrophotographic photosensitive member.

The polycarbonate resin used in the present invention is preferably an aromatic polycarbonate resin from the viewpoint of mechanical strength.

The chain-like fluorinated alkyl group in the present invention has 4 carbon atoms, but more preferably 8 or more carbon atoms. If the number of carbon atoms is less than 4, the surface lubricity of the photoreceptor may not be sufficiently obtained. Such a fluorinated alkyl group may be present as a side chain in the monomer unit of the polycarbonate resin, may be present as a terminal group of the polymer, or may be present in both the side chain and the terminal. Good.

When the chain-like fluorinated alkyl group exists as a side chain in the monomer unit of the polycarbonate resin, the monomer unit is preferably represented by the following formula (1).

[0013]

[Outside 4] (In the formula, R ₁ and R ₂ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted chain fluorinated alkyl group, and The group formed is represented by R ₁ and R ₂
At least one of them contains a chain fluorinated alkyl group having 4 or more carbon atoms. )

Below, R containing a chain-like fluorinated alkyl group
Specific preferred examples of ₁ and R ₂ are shown below, but the present invention is not limited thereto. Further, p in the formula represents an integer of 1 or more,
q represents an integer of 3 or more.

[0015]

[Outside 5]

Next, preferred specific examples of R ₁ and R _{2 which} do not contain a chain-like fluorinated alkyl group are shown, but the present invention is not limited thereto. _{-H, -CH 3, -CH 2 -CH} 3, -CH 2 -CH 2 -C
_{H 3, -CH (CH 3)} -CH 3, -CH 2 -CH 2 -CH
_{2 -CH 3, -CH 2 -CH (} CH 3) -CH 3, -C (C
_{H 3) 3, -CH 2 -CH} 2 -CH 2 -CH 2 -CH 3, -C
_{H 2 -CH 2 -CH 2 -CH 2} -CH 3,

[0017]

[Outside 6] _{-CF 2 -CF 3, -CF 2 -CF} 2 -CF 3

[0018]

[Outside 7] Among the monomer units represented by the formula (1), particularly preferable are the monomer units represented by the following formula.

[0019]

[Outside 8] When the chain-like fluorinated alkyl group is present as the terminal group of the polymer of the polycarbonate resin, the monomer unit is preferably represented by the following formula (2).

[0020]

[Outside 9] (In the formula, R ₃ and R ₄ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted chain fluorinated alkyl group, and R ₃ and R ₄ are bonded to each other. A cycloalkylidene group formed by the above is shown.) Specific preferred examples of the monomer unit represented by the formula (2) include the following monomer units in addition to the ones represented by the above formula (1).

[0021]

[Outside 10] The terminal group of the polymer in the invention is preferably represented by the following formula (3).

[0022]

[Outside 11] In the formula, Ar represents a substituted or unsubstituted arylene group, R is a substituted or unsubstituted alkylene group, oxygen atom, sulfur atom,

[0023]

[Outside 12] And Rf represents a group formed by combining these groups, Rf represents a chain fluorinated alkyl group having 4 or more carbon atoms, and m represents 0 or 1.

The preferred specific examples of Ar are shown below.
It is not limited to these.

[0025]

[Outside 13] (Wherein, Y is _{-CH 3, -C1, -Br, -F} , -I,
-CN, -CF _3, indicating, for example, -N _2, and -H. )

Next, preferred specific examples of R will be shown, but the present invention is not limited thereto. _{-CH 2 -, - CH 2 CH} 2 -, - OCH 2 -, OCH 2 C
_{H 2 -, - COCH 2 -} , - COCH 2 CH 2 -, - COO
_{CH 2 -, - COOCH 2 CH} 2 -, - OCOCH 2 -, -
_{OCOCH 2 CH 2 -, - CONHCH} 2 -, - CONH
_{CH 2 CH 2 -, - NHCOCH} 2 -, - NHCOCH 2 C
_{H 2 -, - O -,} - CO -, - COO -, - OCO-,
-NHCO -, - S -, - SO 2 - Next, while indicating preferred embodiments of Rf, not limited thereto.

[0027]

[Outside 14] Further, preferred specific examples of the terminal group represented by the formula (3) are shown, but the terminal group is not limited to these.

[0028]

[Outside 15] Among the polycarbonate resins of the present invention having a chain-like fluorinated alkyl group as the terminal group of the polymer, the resins represented by the following formulas are particularly preferable.

[0029]

[Outside 16] (Where X is

[0030]

[Outside 17] And r represents the degree of polymerization. The polycarbonate resin used in the present invention may be a homopolymer or a copolymer, and has a weight average molecular weight of 1,000 to 100,000.
It is preferably 0, particularly 10,000 to 80,
It is preferably 000.

The polycarbonate resin of the present invention having a chain fluorinated alkyl group in the side chain of the monomer unit is, for example, a ketone having R ₁ and R ₂ , R ₁ COR ₂ and an excess amount of phenol, hydrochloric acid or sulfuric acid. A strong acid condensing agent such as and a ferric chloride, calcium chloride, boric acid, and hydrogen sulfide are added and condensed to obtain a bisphenol having a fluorinated alkyl side chain, and the bisphenol is then added to sodium hydroxide and ammonium hydroxide. It can be synthesized by mixing the compound in methylene chloride and passing phosgene.

The polycarbonate resin of the present invention having a chain fluorinated alkyl group at the end of the polymer can be synthesized, for example, as follows.

Compound C, which is the polycarbonate resin of the present invention, is obtained by mixing bisphenol Z and the following compound A with an aqueous sodium hydroxide solution in which dichloromethane and the following compound B are mixed and then passing phosgene.

[0034]

[Outside 18]

The photosensitive layer of the electrophotographic photosensitive member of the present invention may have either a single layer structure or a laminated structure. The single-layer type photosensitive layer contains a charge generating material and a charge transporting material, and carriers are generated and transported in the same layer. The laminated photosensitive layer has a charge generating layer containing a charge generating material and generating carriers, and a charge transporting layer containing a charge transporting material and transporting carriers, and these layers are the upper layers. However, the charge transport layer is preferably an upper layer. Regardless of the layer structure, the polycarbonate resin of the present invention is contained in at least the surface layer of the electrophotographic photosensitive member.

The thickness of the single-layer type photosensitive layer is preferably 5 to 100 μm, and particularly preferably 10 to 60 μm. The content of the charge generating material and the charge transporting material is preferably 20 to 80% by weight, and particularly preferably 30 to 70% by weight based on the total weight of the photosensitive layer.

The film thickness of the charge generation layer of the laminated type photoreceptor is 0.0
It is preferably from 0 to 6 μm, and particularly preferably from 0.01 to
It is preferably 2 μm. The content of the charge generation material is preferably 10 to 100% by weight, and particularly preferably 40 to 100% by weight, based on the total weight of the charge generation layer. The thickness of the charge transport layer is preferably 5 to 100 μm, and particularly preferably 10 to 60 μm. The content of the charge transport material is preferably 20 to 80% by weight, and particularly 30 to 70% by weight.

The charge generating material used in the present invention includes phthalocyanine pigments, polycyclic quinone pigments, azo pigments,
Perylene pigments, indigo pigments, thioindigo pigments, quinacridone pigments, azulenium salt dyes, squarylium dyes, cyanine dyes, pyrylium dyes, thiapyrylium dyes, xanthene dyes, quinoneimine dyes, triphenylmethane dyes, styryl dyes, selenium, selenium-tellurium,
Examples include amorphous silicon and cadmium sulfide. The charge transport material used in the present invention includes pyrene compounds, carbazole compounds, hydrazone compounds, N, N-dialkylaniline compounds, diphenylamine compounds, triphenylamine compounds, triphenylmethane compounds, pyrazoline compounds, styryl compounds and stilbene compounds. A compound etc. are mentioned.

These materials are used by dispersing or dissolving them in the polycarbonate resin of the present invention or other resin. Examples of such other resin include polyester, polyurethane, polyarylate, polyethylene, polystyrene, polybutadiene, polycarbonate. , Polyamide, polypropylene, polyimide, polyamide imide, polysulfone, polyallyl ether, polyacetal, nylon, phenol resin, acrylic resin, silicone resin, epoxy resin, urea resin, allyl resin, alkyd resin and butyral resin. Among these, polycarbonate, polyarylate, polyallyl ether and polystyrene are particularly preferable. Further, it is also preferable to mix reactive epoxy or (meth) acrylic monomers or oligomers with these resins and then cure them.

In the present invention, the surface layer of the electrophotographic photoreceptor contains the polycarbonate resin of the present invention, but other resins may be mixed and used for the purpose of controlling mechanical strength and the like. In that case, the content of the polycarbonate of the present invention is preferably 0.1% by weight or more, and particularly preferably 10% by weight or more, based on the total weight of the resin. Further, the layers other than the surface layer may contain the polycarbonate resin of the present invention, but the other resins may be used alone or in combination.

Further, in the present invention, the electrophotographic photosensitive member may have a protective layer on the photosensitive layer. In this case, since the surface layer is the protective layer, the protective layer contains at least the polycarbonate resin of the present invention. Other resins are the same as the photosensitive layer. The thickness of the protective layer is 0.01 to 20.
The thickness is preferably μm, and particularly preferably 0.1 to 10 μm.

In the present invention, the surface layer preferably further contains a fluorine atom-containing compound in order to further improve the abrasion resistance. Examples of the fluorine atom-containing compound include polymers such as tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, and perfluoroalkyl vinyl ethers and copolymers thereof, and further , Fluorine-carbon-substituted fluorocarbons having a graphite structure, and fluorine-atom-substituted oils and other inorganic fluorides.

Of these, tetrafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether and fluorocarbon are particularly preferable. The particle diameter of the fluorine atom-containing compound is 0.00 in terms of weight average particle diameter.
It is preferably 5 to 2.5 μm, and particularly 0.01
To 0.7 μm is preferable, and further 0.01 to
It is preferably 0.35 μm. The molecular weight of the fluorine atom-containing compound is 3,000 in terms of weight average molecular weight.
It is preferably from 0 to 10,000,000.

The content of the fluorine atom-containing compound is
5 to 75% by weight of the total weight of the layer containing the fluorine atom-containing compound is preferable.

Since the polycarbonate resin of the present invention has a fluorinated alkyl group, it has an excellent affinity with a fluorine atom-containing compound, and the fluorine atom compound can be dispersed as fine particles very uniformly and stably. Examples of the dispersing means include a sand mill, a ball mill, a roll mill, a homogenizer, a nanomizer, a paint shaker, and an ultrasonic wave. At the time of dispersing, a fluorinated surfactant, a graft polymer, a coupling agent, etc. may be supplementarily used. .

In the present invention, an undercoat layer may be provided between the conductive support and the photosensitive layer. The undercoat layer is mainly made of resin, but may contain a conductive material or an acceptor used in a conductive support described later. Resins that can be used include polyester, polyurethane,
Polyarylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamideimide, polysulfone,
Examples thereof include polyallyl ether, polyacetal, nylon, phenol resin, acrylic resin, silicone resin, epoxy resin, urea resin, allyl resin, alkyd resin and butyral resin.

These various layers are formed on the conductive support by a method such as vapor deposition or coating. As a coating method,
Examples thereof include bar coating method, knife coating method, roll coating method, spray coating method, dip coating method, electrostatic coating method and powder coating method.

The conductive support used in the present invention includes iron, copper, nickel, aluminum, titanium, tin,
Examples thereof include metals and alloys such as antimony, indium, lead, zinc, gold and silver, oxides or carbons thereof, conductive resins, and resins in which these conductive materials are dispersed. The shape may be a cylindrical shape, a sheet shape, or a belt shape, but is the most suitable shape for the electrophotographic apparatus to which it is applied. The conductive material may be molded and processed, but may be applied as a paint or vapor-deposited.

The electrophotographic photoreceptor of the present invention can be used not only in electrophotographic copying machines but also in electrophotographic applications such as facsimiles, laser beam printers, CRT printers, LED printers, liquid crystal printers and laser plate making. You can

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

In the figure, reference numeral 1 is an electrophotographic photosensitive member of the present invention as an image bearing member, which is rotationally driven around an axis 1a in a direction of an arrow at a predetermined peripheral speed. The photosensitive member 1 receives uniform charging of a positive or negative predetermined potential on the peripheral surface of the photosensitive member 1 by the charging unit 2 during its rotation process, and then an optical image exposure L (slit exposure) by an image exposing unit (not shown) in the exposure unit 3.・ Receive 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 synchronized with the rotation of the photoconductor 1 between the photoconductor 1 and the transfer means 5 from a paper feeding portion (not shown). The transfer material P is sequentially transferred to the transferred and fed transfer material P.

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 photoconductor 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. It

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. In the present invention, among the above-described components such as the photoconductor, the developing unit, and the cleaning unit, a plurality of components are integrally combined and configured as an apparatus unit, and this unit is configured to be detachable from the apparatus main body. May be. For example, at least one of a charging unit, a developing unit, and a cleaning unit is integrally supported together with a photoconductor to form a unit, which is a detachable single unit in the main body of the apparatus and a guide unit such as a rail of the main body It may be detachable.

When the electrophotographic apparatus is used as a copying machine or a printer, the optical image exposure L irradiates the photoconductor with the reflected light or the transmitted light from the original, or the original is read by a sensor and converted into a signal. According to this signal, the laser beam is scanned, the LED array is driven, or the liquid crystal shutter array is driven to irradiate the photoconductor with light.

When used as a printer for a facsimile, the light image exposure L becomes an exposure for printing 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 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. Predetermined image data is stored in the image memory. The printer controller 18 is the printer 1
9 is controlled. 14 is a telephone.

The image received from the line 15 (image information from the remote terminal connected via the line) is demodulated by the receiving circuit 12, and then the CPU 17 decodes the image information to sequentially decode the image memory 16. Stored in. And
When the image of at least one page is stored in the memory 16, the image of that page is recorded. The CPU 17 reads the image information of one page from the memory 16 and sends the decoded image information of one page to the printer controller 18. When the printer controller 18 receives 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.

As described above, the image is received and recorded.

[0062]

【Example】

(Example 1) 5 parts by weight of conductive titanium oxide (weight average particle size 0.4 μm) coated with tin oxide and antimony oxide (weight part, hereinafter the same), high resistance titanium oxide coated with alumina (weight average particle size) 0.4 μm), 10 parts of phenol resin precursor (resole type), 10 parts of methanol and 10 parts of butanol are dispersed in a sand mill to obtain an outer diameter of 80.
A conductive layer having a volume resistance of 5 × 10 ⁹ Ωcm and a thickness of 20 μm was formed by coating the aluminum cylinder having a length of 360 mm and a length of 360 mm by a dip coating method and curing by heating.

Next, 3 parts of methoxymethylated nylon (weight average molecular weight of 30,000, degree of methoxymethylation of about 30%) represented by the following formula:

[0064]

[Outside 19] (B and c indicate copolymerization ratio.) 6/66/610/1
2 quaternary copolymer nylon 9 parts and isopropanol 150
A solution obtained by mixing and dissolving parts was applied onto the conductive layer by a dip coating method and dried to form an undercoat layer having a thickness of 1 μm.

Next, the disazo pigment 10 represented by the following formula
Department,

[0066]

[Outside 20] Vinyl acetate-vinyl alcohol-vinyl benzal copolymer represented by the following formula (weight average molecular weight 80,0
00) 5 copies,

[0067]

[Outside 21] And a dispersion liquid in which 700 parts of cyclohexanone are dispersed by a sand mill is applied on the undercoat layer by a dip coating method,
By drying, a charge generation layer having a thickness of 0.05 μm was formed.

Next, 10 parts of a triphenylamine compound represented by the following formula:

[0069]

[Outside 22] 5 parts of a polycarbonate resin (bisphenol Z type, weight average molecular weight 25,000) represented by the following formula,

[0070]

[23 outside] 5 parts of a polycarbonate resin represented by the following formula (weight average molecular weight of 30,000):

[0071]

[Outside 24] Polytetrafluoroethylene fine powder (emulsion polymer, weight average molecular weight 35,000, weight average particle size 0.23 μm) 3
Part, monochlorobenzene 50 parts and dichloromethane 25
A solution in which the parts were dispersed and dissolved by a sand mill was applied on the charge generation layer by a dip coating method, and dried by hot air to form a charge transport layer having a thickness of 20 μm. Thus, an electrophotographic photosensitive member was prepared.

(Comparative Example 1) In the preparation of the coating material for the charge transport layer in Example 1, 1 part of the triphenylamine compound was used.
0 parts, bisphenol Z type polycarbonate resin 10
Part, monochlorobenzene 50 parts and dichloromethane 25
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that a part was dissolved in a sand mill to form a charge transport layer solution.

The electrophotographic photosensitive member of Example 1 and the electrophotographic photosensitive member of Comparative Example 1 were evaluated by the following methods. The results are shown in Table 1.

Contact Angle The contact angles of the photoconductors of Example 1 and the photoconductor of Comparative Example 1 with respect to pure water were compared by a drop type contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). . As a result, the contact angle of the photoconductor of Example 1 was as large as 109 ° and low surface energy was obtained, whereas the contact angle of the photoconductor of Comparative Example 1 was as small as 80 ° and low surface energy was obtained. There wasn't.

Evaluation of Actual Machine The photoconductor of Example 1 and the photoconductor of Comparative Example 1 were mounted on a copying machine (CLC-500, manufactured by Canon Inc.), respectively, and 2
An image output durability test was performed on 10,000 sheets. In the case of the photoconductor of Comparative Example 1, the image fog on the white background became remarkable after 13,000 sheets and the image was unusable, but in the case of the photoconductor of Example 1, the image was good even after 20,000 sheets. . Further, the abrasion loss of the photoreceptor after endurance was significantly smaller in the photoreceptor of Example 1 than in the photoreceptor of Comparative Example 1.

Further, transfer efficiency and transfer failure after 1,000 sheets were examined under the same conditions. The transfer efficiency was calculated from the ratio of the reflection density of the developer transferred to the transfer material and the reflection density of the developer remaining on the photoconductor when a halftone image of magenta monochromatic color having a reflection density of 0.8 was output. The photoconductor of Comparative Example 1 had a transfer efficiency of 75%, while the photoconductor of Example 1 maintained a high transfer efficiency of 91%.

The transfer failure was evaluated by a halftone image with a reflection density of 0.6 of four full colors after 1,000 sheets were printed. The photoconductor of Comparative Example 1 had a messy non-uniform image due to poor transfer, but the photoconductor of Example 1 had a uniform high-quality halftone image.

Example 2 30 parts of the triphenylamine compound used in Example 1 and 50 parts of a polycarbonate resin (weight average molecular weight 20,000) represented by the following formula:

[0079]

[Outside 25] 20 parts of the bisphenol Z type polycarbonate resin (weight average molecular weight 90,000) used in Example 1, 30 parts of polytetrafluoroethylene fine powder (emulsion polymerized product, weight average molecular weight 35,000, weight average particle size 0.23 μm), Monochlorobenzene 1050 parts and dichloromethane 425
A solution of which part was dispersed and dissolved with a sand mill was applied onto the photoreceptor of Comparative Example 1 by a spray coating method, and dried with hot air to form a protective layer having a thickness of 6 μm. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1. The surface of this photoreceptor showed a high contact angle of 110 °. In the durability evaluation with an actual machine, abrasion of the photosensitive member after 20,000 sheets was remarkably small, and white background fog and black streaks did not occur. The transfer efficiency after 1,000 sheets is 9
It was as high as 3%, and no transfer failure occurred.

Example 3 30 parts of the triphenylamine compound used in Example 1 and 30 parts of a polycarbonate resin (weight average molecular weight 25,000) represented by the following formula:

[0081]

[Outside 26] 20 parts of bisphenol Z-type polycarbonate resin (weight average molecular weight 90,000) used in Example 1, 35 parts of polytetrafluoroethylene fine powder (emulsion polymerized product, weight average molecular weight 35,000, weight average particle size 0.23 μm), Monochlorobenzene 1,050 parts and dichloromethane 42
A solution obtained by dispersing and dissolving 5 parts by a sand mill was applied onto the photoreceptor of Comparative Example 1 by a spray coating method and dried with hot air to form a protective layer having a thickness of 6 μm. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1. The surface of this photoreceptor showed a high contact angle of 110 °. Endurance evaluation in actual machine is 20,000
After the sheet, the photoconductor was not significantly scraped, and white background fog and black streaks did not occur. The transfer efficiency after 1,000 sheets was as high as 94%, and no transfer failure occurred.

Example 4 30 parts of the triphenylamine compound used in Example 1 and 30 parts of a polycarbonate resin (weight average molecular weight 15,000) represented by the following formula:

[0083]

[Outside 27] 20 parts of bisphenol Z type polycarbonate resin (weight average molecular weight 90,000) used in Example 1, 40 parts of polytetrafluoroethylene fine powder (emulsion polymer, weight average molecular weight 35,000, weight average particle size 0.23 μm), Monochlorobenzene 1,050 parts and dichloromethane 42
A solution obtained by dispersing and dissolving 5 parts by a sand mill was applied onto the photoreceptor of Comparative Example 1 by a spray coating method and dried with hot air to form a protective layer having a thickness of 6 μm. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1. The surface of this photoreceptor showed a high contact angle of 113 °. Endurance evaluation in actual machine is 20,000
After the sheet, the photoconductor was not significantly scraped, and white background fog and black streaks did not occur. The transfer efficiency after 1,000 sheets was as high as 92%, and no transfer failure occurred.

(Example 5) 30 parts of the triphenylamine compound used in Example 1 and 30 parts of a polycarbonate resin represented by the following formula (weight average molecular weight 20,000):

[0085]

[Outside 28] 20 parts of bisphenol Z type polycarbonate resin (weight average molecular weight 90,000) used in Example 1, tetrafluoroethylene-hexafluoropropylene copolymer fine powder (emulsion polymerized product, weight average molecular weight 35,000, weight average particle size 0) .23 μm) 40 parts, monochlorobenzene 1,
A solution in which 050 parts and 425 parts of dichloromethane were dispersed and dissolved by a sand mill was applied onto the photoreceptor of Comparative Example 1 by a spray coating method, and dried with hot air to form a protective layer having a thickness of 6 μm. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1. The surface of this photoreceptor showed a high contact angle of 112 °.
In the durability evaluation with an actual machine, abrasion of the photosensitive member after 20,000 sheets was remarkably small, and white background fog and black streaks did not occur. The transfer efficiency after 1,000 sheets was as high as 93%, and no transfer failure occurred.

[0086]

[Table 1] (Example 6) A liquid obtained by mixing and dissolving 10 parts by weight of methoxymethylated nylon used in Example 1 and 150 parts by weight of isopropanol was applied onto an aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm by a dip coating method, An undercoat layer having a thickness of 1 μm was formed by drying.

Next, the disazo pigment 10 used in Example 1 was used.
Part, polycarbonate resin (bisphenol A type, weight average molecular weight 30,000) 5 parts and cyclohexanone 7
A dispersion liquid prepared by dispersing 00 parts by a sand mill was applied on the undercoat layer by a dip coating method, and dried to form a charge generation layer having a thickness of 0.05 μm.

Next, 10 parts of a triphenylamine compound represented by the following formula:

[0089]

[Outside 29] 7 parts of a polycarbonate resin (weight average molecular weight 20,000) represented by the following formula,

[0090]

[Outside 30] 3 parts of a polycarbonate resin (bisphenol Z type, weight average molecular weight 25,000) represented by the following formula,

[0091]

[Outside 31] Monochlorobenzene 150 parts and dichloromethane 100
A solution obtained by mixing and dissolving parts was applied onto the charge generating layer by a dip coating method and dried to form a charge transporting layer having a thickness of 20 μm, thereby preparing an electrophotographic photoreceptor.

Thickness 5 instead of aluminum cylinder
An electrophotographic photosensitive member was prepared in the same manner as above using a 0 μm aluminum sheet.

Comparative Example 2 An electrophotographic photosensitive member for comparison was prepared in the same manner as in Example 6 except that only the bisphenol Z type polycarbonate resin was used as the binder resin for the charge transport layer.

The electrophotographic photosensitive members of Example 6 and Comparative Example 2 were evaluated by the following methods.

Abrasion resistance test Using a Taber abrasion tester, a weight of 500 g (two), 5,0 was applied to the photoreceptor using the aluminum sheet.
An abrasion test of 00 cycles was performed. The reduction in weight due to abrasion was about 25% less in the photoconductor of Example 6 than in the photoconductor of Comparative Example 2, and the effect of the specific polycarbonate resin used in the present invention was confirmed.

Contact Angle The contact angles of water with respect to the photoconductors using the aluminum sheet were compared by a dropping type contact angle meter. As a result, the contact angle of the photoconductor of Example 6 was as large as 109 °, while that of the photoconductor of Comparative Example 2 was as small as 81 °.

Evaluation of Actual Machine Each of the photoconductors of Example 1 and Comparative Example 2 was mounted on a copying machine (CLC-500, manufactured by Canon Inc.), and a durability test of 20,000 images was carried out. The photoreceptor of Comparative Example 2 has 13,
Fogging on a white background became remarkable after 000 sheets and the image was unusable, but the image bearing member of Example 6 was a good image even after 20,000 sheets. Further, the abrasion loss of the photoconductor after endurance was 25% less in the photoconductor of Example 6 than in the photoconductor of Comparative Example 2.
The results are shown in Table 2.

Example 7 30 parts of the triphenylamine compound used in Example 6, 50 parts of a polycarbonate resin represented by the following formula (weight average molecular weight 15,000),

[0099]

[Outside 32] 20 parts of a polycarbonate resin represented by the following formula (bisphenol Z type, weight average molecular weight 70,000),

[0100]

[Outside 33] Monochlorobenzene 1,000 parts and dichloromethane 5
A liquid prepared by mixing and dissolving 00 parts was applied onto the photoreceptor of Comparative Example 2 by a spray coating method, and dried with hot air to form a protective layer having a thickness of 6 μm. The obtained electrophotographic photosensitive member was evaluated (as in Example 6). The results are shown in Table 2, which has excellent wear resistance and releasability.

(Example 8) 30 parts of the triphenylamine compound used in Example 6, 30 parts of a polycarbonate resin represented by the following formula (weight average molecular weight 10,000),

[0102]

[Outside 34] 30 parts of a polycarbonate resin (bisphenol Z type, weight average molecular weight 70,000) represented by the following formula,

[0103]

[Outside 35] Monochlorobenzene 1,000 parts and dichloromethane 5
A liquid prepared by mixing and dissolving 00 parts was applied onto the photoreceptor of Comparative Example 2 by a spray coating method, and dried with hot air to form a protective layer having a thickness of 6 μm. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 6. The results are shown in Table 2, which has excellent wear resistance and releasability.

Example 9 30 parts of the triphenylamine compound used in Example 6, 30 parts of a polycarbonate resin represented by the following formula (weight average molecular weight 25,000),

[0105]

[Outside 36] 20 parts of a polycarbonate resin represented by the following formula (bisphenol Z type, weight average molecular weight 70,000),

[0106]

[Outside 37] Monochlorobenzene 1,000 parts and dichloromethane 5
A liquid prepared by mixing and dissolving 00 parts was applied onto the photoreceptor of Comparative Example 2 by a spray coating method, and dried with hot air to form a protective layer having a thickness of 6 μm. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 6. The results are shown in Table 2, which has excellent wear resistance and releasability.

Example 10 30 parts of the triphenylamine compound used in Example 6, 30 parts of a polycarbonate resin represented by the following formula (weight average molecular weight 20,000),

[0108]

[Outside 38] 20 parts of a polycarbonate resin represented by the following formula (bisphenol Z type, weight average molecular weight 70,000),

[0109]

[Outside 39] Monochlorobenzene 1,000 parts and dichloromethane 5
A liquid prepared by mixing and dissolving 00 parts was applied onto the photoreceptor of Comparative Example 2 by a spray coating method, and dried with hot air to form a protective layer having a thickness of 6 μm. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 6. The results are shown in Table 2, which has excellent wear resistance and releasability.

[0110]

[Table 2] (Example 11) In the same manner as in Example 6, an undercoat layer and a charge generation layer were formed on an aluminum cylinder.

Next, 10 parts of triphenylamine represented by the following formula:

[0112]

[Outside 40] Polytetrafluoroethylene resin fine powder (weight average particle diameter 0.33 μm, weight average molecular weight 300,000) 3 parts,
7 parts of a polycarbonate resin (weight average molecular weight 20,000) represented by the following formula,

[0113]

[Outside 41] (G indicates the degree of polymerization.) A polycarbonate resin represented by the following formula (bisphenol Z type, polymerization average molecular weight 25,
000) 3 copies,

[0114]

[Outside 42] Monochlorobenzene 150 parts and dichloromethane 100
A solution in which a part of the charge-generating layer was dispersed and dissolved was applied onto the charge-generating layer by a dip coating method, and dried by hot air to form a charge-transporting layer having a thickness of 20 μm, thereby preparing an electrophotographic photoreceptor. .

Thickness 5 instead of aluminum cylinder
An electrophotographic photosensitive member was prepared in the same manner as above using a 0 μm aluminum sheet.

(Comparative Example 3) 10 parts of triphenylamine used in Example 11 and a polycarbonate resin represented by the following formula (bisphenol Z type, weight average molecular weight 25,000)
0) 10 copies

[0117]

[Outside 43] Monochlorobenzene 150 parts and dichloromethane 100
A solution obtained by mixing and dissolving parts is applied onto the charge generation layer by a dip coating method and dried with hot air to give a thickness of 20 μm.
A charge transport layer of m was formed to prepare an electrophotographic photoreceptor.
Similarly, an electrophotographic photoreceptor was prepared using an aluminum sheet having a thickness of 50 μm.

The electrophotographic photosensitive members of Example 11 and Comparative Example 3 were evaluated by the following methods.

Abrasion resistance test A taper type abrasion tester was used to apply a weight of 500 g (2) to the electrophotographic photoreceptor using the aluminum sheet.
Abrasion test for 5,000 cycles. The weight loss due to abrasion was about 30% less in the photoconductor of Example 11 than in the photoconductor of Comparative Example 3, and the effect of using the polycarbonate resin of the present invention was observed.

Contact Angle The contact angles of water with respect to the photoconductors using the above aluminum sheets were compared by a dropping type contact angle meter. As a result, the contact angle of the photoconductor of Example 11 was as large as 109 °, while that of the photoconductor of Comparative Example 3 was as small as 80 °.

Transfer Efficiency Each photoconductor was attached to a copying machine (NP-4835, manufactured by Canon Inc.) and the initial transfer efficiency was measured. The transfer efficiency of the photoconductor of Example 11 was 93%, whereas the transfer efficiency of the photoconductor of Comparative Example 3 was 86%, which was low.

Evaluation of Actual Machine An electrophotographic photosensitive member was mounted on a copying machine (NP-4835, manufactured by Canon Inc.), and a durability test of 20,000 images was carried out. The photoconductor of Comparative Example 3 became unusable because the image density became extremely low at 12,000 sheets, but the photoconductor of Example 11 was a good image even after 20,000 sheets. Further, the abrasion loss of the photoconductor after endurance was smaller in the photoconductor of Example 11 by about 35% than that of the photoconductor of Comparative Example 3, and the durability was improved.

(Example 12) 30 parts of the triphenylamine compound used in Example 11, 20 parts of the polycarbonate resin of the present invention used in Example 11, polycarbonate resin (bisphenol Z type, weight average molecular weight 70,000)
A solution prepared by dispersing and dissolving 20 parts, 30 parts of the polytetrafluoroethylene fine powder used in Example 11, 1,000 parts of monochlorobenzene and 500 parts of dichloromethane in the same manner as in Example 11 was placed on the photoreceptor of Comparative Example 3. The thickness is 6μ by applying by spray coating method and drying with hot air.
m protective layer was formed. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 11. As a result, the abrasion amounts in the Taber abrasion test and the durability test by the actual machine of the copying machine were reduced by 70% and 75%, respectively, as compared with the comparative example, showing excellent abrasion resistance. Further, the contact angle was as large as 113 °, which showed excellent releasability.

Example 13 20 parts of the triphenylamine compound used in Example 11, 20 parts of a polycarbonate resin represented by the following formula (weight average molecular weight 15,000),

[0125]

[Outside 44] 20 parts of a polycarbonate resin represented by the following formula (bisphenol Z type, weight average molecular weight 80,000),

[0126]

[Outside 45] A solution prepared by dispersing and dissolving 40 parts of the polytetrafluoroethylene fine powder used in Example 11, 1,000 parts of monochlorobenzene and 500 parts of dichloromethane was applied onto the photoreceptor of Comparative Example 3 by a spray coating method, and dried with hot air. By doing so, a protective layer having a thickness of 6 μm was formed. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 11. As a result, the abrasion amounts of the Taber abrasion test and the durability test by the actual machine of the copying machine were 80% and 80%, respectively, as compared with the comparative example.
%, Indicating excellent wear resistance. Further, the contact angle was as large as 115 °, and excellent releasability was exhibited.

Example 14 20 parts of the triphenylamine compound used in Example 11, 20 parts of a polycarbonate resin represented by the following formula (weight average molecular weight 25,000),

[0128]

[Outside 46] 25 parts of a polycarbonate resin represented by the following formula (bisphenol Z type, weight average molecular weight 80,000),

[0129]

[Outside 47] A solution prepared by dispersing and dissolving 40 parts of the polytetrafluoroethylene bifine powder used in Example 11, 1,000 parts of monochlorobenzene and 500 parts of dichloromethane was applied onto the photoreceptor of Comparative Example 3 by a spray coating method, and hot air was applied. By drying, a protective layer having a thickness of 6 μm was formed. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 11. As a result, the abrasion amounts of the Taber abrasion test and the durability test by the actual machine of the copying machine were 75% and 80%, respectively, as compared with the comparative example.
%, Indicating excellent wear resistance. Further, the contact angle was as large as 114 °, and excellent releasability was exhibited.

Example 15 20 parts of the triphenylamine compound used in Example 11, 10 parts of a polycarbonate resin represented by the following formula (weight average molecular weight 10,000),

[0131]

[Outside 48] 30 parts of a polycarbonate resin (bisphenol Z type, weight average molecular weight 80,000) represented by the following formula,

[0132]

[Outside 49] A solution prepared by dispersing and dissolving 40 parts of the polytetrafluoroethylene fine powder used in Example 11, 1,000 parts of monochlorobenzene and 500 parts of dichloromethane was applied onto the photoreceptor of Comparative Example 3 by a spray coating method, and dried with hot air. By doing so, a protective layer having a thickness of 6 μm was formed. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 11. As a result, the abrasion amounts of the Taber abrasion test and the durability test by the actual machine of the copying machine were 80% and 80%, respectively, as compared with the comparative example.
%, Showing excellent wear resistance. Further, the contact angle was as large as 116 °, and excellent releasability was exhibited.

Example 16 20 parts of the triphenylamine compound used in Example 11, 10 parts of a polycarbonate resin represented by the following formula (weight average molecular weight 15,000),

[0134]

[Outside 50] 30 parts of a polycarbonate resin (bisphenol Z type, weight average molecular weight 80,000) represented by the following formula,

[0135]

[Outside 51] A solution prepared by dispersing and dissolving 40 parts of the polytetrafluoroethylene fine powder used in Example 11, 1,000 parts of monochlorobenzene and 500 parts of dichloromethane was applied onto the photoreceptor of Comparative Example 3 by a spray coating method, and dried with hot air. By doing so, a protective layer having a thickness of 6 μm was formed. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 11. As a result, the wear amounts in the taper wear test and the durability test by the actual machine of the copying machine were 80% and 80%, respectively, as compared with the comparative example.
%, Indicating excellent wear resistance. Further, the contact angle was as large as 116 °, and excellent releasability was exhibited.

Comparative Example 4 40 parts of the triphenylamine compound used in Example 1, a polycarbonate resin represented by the following formula (bisphenol Z type, weight average molecular weight 80,
000) 30 copies,

[0137]

[Outside 52] 80 parts of the polytetrafluoroethylene fine powder used in Example 11, 1,000 parts of monochlorobenzene and 500 parts of dichloromethane were dispersed and dissolved, but tetrafluoroethylene was not dispersed up to the primary particle size, I couldn't get it.

Table 3 shows the evaluation results of the electrophotographic photosensitive members of Examples 11 to 16 and Comparative Examples 2 and 3.

[0139]

[Table 3] (Comparative Examples 5 to 8) An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the polycarbonate resin represented by the following formula was used in place of the polycarbonate resin of the present invention.

[0140]

[Outside 53] The results are shown in Table 4.

[0141]

[Table 4]

[0142]

As described above, according to the present invention, an electrophotographic photosensitive member having excellent durability and capable of obtaining an excellent image even when repeatedly used, an electrophotographic apparatus having the electrophotographic photosensitive member, and A device unit can be provided.

[Brief description of drawings]

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

FIG. 2 is a diagram showing 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 the present invention 2 Charging means 3 Exposure section 4 Developing means 5 Transfer means 6 Cleaning means 7 Pre-exposure means 8 Image fixing means L Optical image exposure P Transfer material 10 Image reading section 11 Controller 12 Reception circuit 13 Transmission circuit 14 telephone 15 line 16 image memory 17 CPU 18 printer controller 19 printer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location G03G 5/147 502 7621-2H H04N 1/29 D 9186-5C (72) Inventor Shoji Amemiya Tokyo 3-30-2 Shimomaruko, Ota-ku Canon Inc.

Claims (11)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photoreceptor comprises a polycarbonate resin having a chain fluorinated alkyl group having 4 or more carbon atoms. An electrophotographic photoreceptor containing the same. 2. The electrophotographic photosensitive member according to claim 1, wherein the polycarbonate resin is an aromatic polycarbonate resin. 3. The electrophotographic photosensitive member according to claim 1, wherein the chain-like fluorinated alkyl group has 8 or more carbon atoms. 4. The electrophotographic photosensitive member according to claim 1, wherein the chain-like fluorinated alkyl group is a side chain in the monomer unit of the polycarbonate resin or a terminal group of the polymer. 5. A monomer unit of a polycarbonate resin having a chain fluorinated alkyl group as a side chain of the monomer unit has the following formula (1): (In the formula, R ₁ and R ₂ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted chain fluorinated alkyl group, and The group formed is represented by R ₁ and R ₂
At least one of them contains a chain fluorinated alkyl group having 4 or more carbon atoms. 5. The electrophotographic photosensitive member according to claim 4, wherein 6. A chain alkyl fluoride group is a terminal group of a polymer of a polycarbonate resin, and has the following formula (3): (In the formula, Ar represents a substituted or unsubstituted arylene group, R represents a substituted or unsubstituted alkylene group, an oxygen atom, a sulfur atom, or And Rf represents a group formed by combining these groups, Rf represents a chain fluorinated alkyl group having 4 or more carbon atoms, and m represents 0 or 1. 5. The electrophotographic photosensitive member according to claim 4, wherein 7. The electrophotographic photosensitive member according to claim 1, wherein the surface layer further contains a compound containing a fluorine atom. 8. The electrophotographic photosensitive member according to claim 1, wherein the surface layer is a photosensitive layer. 9. The electrophotographic photosensitive member according to claim 1, wherein the surface layer is a protective layer. 10. An electrophotographic photosensitive member according to claim 1, comprising means for forming an electrostatic latent image, means for developing the formed electrostatic latent image, and means for transferring the developed image to a transfer material. Characteristic electrophotographic device. 11. An electrophotographic photosensitive member according to claim 1, at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported, and detachable from the apparatus main body. Characterized device unit.