JPH04353860A - Photosensitive material for electrophotography, electrophotographic device and facsimille equiped with this photosensitive material for electrophotography - Google Patents

Abstract

PURPOSE:To obtain an intermediate layer containing uniform dispersion of conductive powder which can enough cover defects on the supporting body by incorporating a specified resin and metal oxide superfine particles into the intermediate layer of an electrophotographic sensitive material. CONSTITUTION:The electrophotographic sensitive material consists of a conductive supporting body, intermediate layer and a photosensitive layer. The intermediate layer contains a resin obtd. by polymn. of phosphazene monomers expressed by formula I and metal oxide superfine particles. In formula I, R1 is a group having an ethylene type coupling. The metal oxide used is zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, and zirconium oxide, and primary particles of the metal oxide superfine particles have in average <=500Angstrom particle size. Thereby, stable potential characteristics and picture images can be obtd. in various environments from at low temp. and low humidity to at high temp. and high humidity. Moreover, dispersion of the metal oxide superfine particles is improved.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more particularly to an improvement in an intermediate layer provided between a conductive support and a photosensitive layer.

0002

[Prior Art] Generally, in a Carlson type electrophotographic photoreceptor, in order to form an image with a constant image density and no fog when charging and exposure are repeated, it is necessary to stabilize the dark area potential and bright area potential. Gender has become important.

[0003] For this reason, an intermediate having functions such as improving charge injection from the support to the photosensitive layer, improving adhesion between the support and the photosensitive layer, improving coatability of the photosensitive layer, and covering defects on the support has been developed. It has been proposed to provide a layer between the support and the photosensitive layer.

[0004]Also, a layered structure in which the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer has been proposed, but generally the charge generation layer is an extremely thin layer, for example, 0.5cm thick.
Since the thickness is on the order of μm, defects, dirt, deposits, scratches, etc. on the surface of the support cause the thickness of the charge generation layer to be non-uniform. If the thickness of the charge generation layer is non-uniform, uneven sensitivity will occur in the photoreceptor, so it is required that the charge generation layer be made as uniform as possible.

For these reasons, it has been proposed to provide an intermediate layer between the charge generation layer and the support, which functions as a barrier layer, an adhesive layer, and covers defects on the support. has been done. Until now, polyamide (Japanese Unexamined Patent Publication No. 46-4
7344, JP-A-52-25638), polyester (JP-A-52-20836, JP-A-Sho. 5)
4-26738), polyurethane (Japanese Unexamined Patent Publication No. 1983-
10044, Japanese Patent Application Laid-open No. 53-89435),
Casein (JP-A-55-103556), polypeptide (JP-A-53-48523), polyvinyl alcohol (JP-A-52-100240), polyvinylpyrrolidone (JP-A-48-30936) Public bulletin),
Vinyl acetate-ethylene copolymer (JP-A-40-261
41 Publication), maleic anhydride ester polymer (Japanese Unexamined Patent Publication No. 1982-10138), polyvinyl butyral (Unexamined Japanese Patent Publication No. 57-90639, Unexamined Japanese Patent Publication No. 56-60448)
Publication No.), Ethylcellulose (Japanese Unexamined Patent Publication No. 14356/1983)
It is known to use methods such as Publication No. 4).

However, in an electrophotographic photoreceptor using the above-mentioned material as an intermediate layer, the resistance of the intermediate layer changes with changes in temperature and humidity, so it is always stable in all environments from low temperature and low humidity to high temperature and high humidity. It was difficult to obtain the desired potential characteristics and image quality. For example, if a photoconductor is used repeatedly under low temperature and low humidity conditions where the resistance of the intermediate layer increases, charges remain in the intermediate layer, resulting in an increase in bright area potential and residual potential, which may cause fogging or inversion of copied images. When such a photoreceptor is used in an electrophotographic printer that performs development, there are problems in that the image density becomes low and copies with a certain image quality cannot be obtained. In addition, under high temperature and high humidity conditions, the barrier function decreases due to the lower resistance of the intermediate layer, and carrier injection from the support side increases, resulting in a decrease in dark area potential. Therefore, under high temperature and high humidity conditions, the density of copied images may be reduced, and when such photoreceptors are used in electrophotographic printers that perform reversal development, black dot-like defects (black spots) may appear on images. There was a problem in that it was more likely to cause scratches and fog.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor that can provide stable potential characteristics and images in all environments from low temperature and low humidity to high temperature and high humidity. The conductive powder, especially the metal oxide ultrafine particle powder, has good dispersibility in the resin of the coating solution, forming an intermediate layer in which the conductive powder is uniformly dispersed and can sufficiently cover defects on the support. Therefore, it is an object of the present invention to provide an electrophotographic photoreceptor from which good images without defects can be obtained.

[0008]

[Means for Solving the Problems] The present invention provides an electrophotographic photoreceptor in which a photosensitive layer is provided on a conductive support via an intermediate layer.
The electrophotographic photoreceptor is characterized in that the intermediate layer contains a resin obtained by polymerizing a phosphazene monomer represented by the following general formula (1) and ultrafine metal oxide particles. General formula (1)

[C4] In the formula, R1 represents a group having an ethylenically unsaturated bond.

The present invention also comprises an electrophotographic photoreceptor according to claim 1, wherein the phosphazene monomer is a monomer represented by the following general formula (2). General formula (2)

[C5] In the formula, R1 is

In the above formula, R2 represents an alkyl group, an aryl group, an alkyl-substituted aryl group, an alkylamido group, an arylamide group, a polyoxylene group, and R3 represents a hydrogen atom or a methyl group. .

The present invention also provides an electrophotographic photoreceptor according to claim 1, wherein the primary particle diameter of the ultrafine metal oxide particles is 500 angstroms or less.

The present invention also comprises an electrophotographic apparatus equipped with the electrophotographic photoreceptor according to claim 1.

The present invention also comprises an electrophotographic apparatus equipped with the electrophotographic photoreceptor according to claim 1, and a facsimile machine having means for receiving image information from a remote terminal.

In the intermediate layer of an electrophotographic photoreceptor, it is essential to control the resistance in view of chargeability, residual potential, sensitivity, etc. For this reason, attempts have been made to control resistance by dispersing metal oxide particles in the binder resin of the intermediate layer, but in conventional photoreceptors, the dispersibility of metal oxide particles is poor, and coating Since the metal oxide particles are unevenly distributed on the surface of the subsequent intermediate layer coating film, there is a problem that black dot-like defects (black spots) and fog tend to occur in images produced by the reversal development method. Furthermore, in order to obtain a uniformly dispersed coating film as an intermediate layer, it is necessary that the average particle diameter of the primary particles of metal oxide particles be as small as 1000 angstroms or less, preferably 500 angstroms or less. The dispersibility of conventional binder resins has been difficult.

The present inventors have discovered that ultrafine metal oxide particles with a small average primary particle diameter have good dispersibility and prevent the formation of secondary particles due to aggregation of ultrafine metal oxide particles in the resin over time after dispersion. We discovered phosphazene resin as a binder resin.

The resin used in the present invention may be a polymer of one type of phosphazene monomer or a copolymer of two or more types of monomers.

Next, taking tin oxide particles as an example, we will discuss (1) the average particle size of the primary particles before dispersion, (2) the average particle size when dispersed in a resin and made into a coating film, and (3) the dispersion time of 1 month. The average particle size in the subsequent dispersion is shown. The average particle size of tin oxide particles is
It is the same in the dispersion and in the film formed from the dispersion.

Average particle size of tin oxide (angstrom)
Measured object Phosphazene monomer 60 shown by the following structural formula
Department,

[Chemical formula 7] 0.06 parts of isopropyl triisostearoyl titanate (coupling agent), 30 parts of tin oxide, 30 parts of toluene
After mixing 0 parts and dispersing in a sand mill for 48 hours, Meyer
A coating film was obtained on an aluminum plate using a bar.

Regarding (1) above, the particle size of 100 tin oxide particles was measured using an electron microscope and the average was taken as the particle size, and regarding (2) and (3), a particle size distribution analyzer (Horiba CAPA-700) was used. ). The results are shown in Table 1.

[Table 1] As can be seen from this result, in the present invention, the particle size after dispersion is very close to the particle size of the primary particles, the particles are very well dispersed, and the particle size increases even with time. No change was observed, indicating good dispersibility.

In the present invention, metal oxides include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony-doped tin oxide, and zirconium oxide. Ultrafine particles such as can be used. The above-mentioned metal oxides may be used singly or in a mixture of two or more types, and when two or more types are mixed, they may be in the form of a solid solution or fused.

[0020] The content of metal oxide is 5 to 90% in the intermediate layer.
% by weight, preferably 10-80% by weight. When the content is less than 5% by weight, the resistance value as an intermediate layer is too high, and when it is more than 90% by weight, the intermediate layer functions as a barrier layer and has a low resistance, resulting in a decrease in charging ability and pinhole resistance. -Causes problems.

Additives such as a coupling agent and an antioxidant can be added to the intermediate layer to improve dispersibility, adhesion, and weather resistance. Examples of additives include titanium oxide,
Examples include powders such as alumina and resin, surfactants, silicone leveling agents, silane coupling agents, and titanate coupling agents.

The phosphazene resin represented by the general formula (1) can be obtained by curing and polymerizing a phosphazene curable monomer using ultraviolet rays, electron beams, or heat. Phosphazene curable monomer
(Structural formula A) is phosphazene (
It is obtained by a condensation reaction between structural formula B) and a compound represented by structural formula C.

[Chemical formula 8] In the above reaction formula, the phosphazene monomer (structural formula A)
The substitution rate of the substituents in is suitably 80% or more, and optimally 90% or more. The substitution rate of the substituents is suitably 80% or more, and optimally 90% or more.

Specific examples of compounds of structural formula C include 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate
2-hydroxypropyl methacrylate, 1,3
-Butanediol monoacrylate, 1,3-butanediol monomethacrylate, 1,4-butanediol monoacrylate, 1,4-butanediol monomethacrylate, 1,6-hexanediol monoacrylate −
2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, pentaerythritol monoacrylate,
Pentaerythritol monomethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, 1
, 3-bis(3″-acryloxyethoxy-2′-hydroxypropyl)-5,5-dimethylhydantoin,
1,3-bis(3”-methacryloxyethoxy-2
'-hydroxypropyl)-5,5-dimethylhydantoin, bisphenol A-diglycidyl ether diacrylate, bisphenol A-diglycidyl ether methacrylate, N-methylol-acrylamide, N-methylol-methacrylamide, etc. Can be mentioned.

When this curable monomer is polymerized by ultraviolet rays, a photoinitiator can be used, and compounds generally known as photoinitiators as shown in Tables 2 and 3 can be used.

[0025]

[Table 2]

[Table 3]

In the present invention, since a phosphazene resin, which is a photocurable resin, is used for the intermediate layer, a photoinitiator is added to the intermediate layer preparation when forming the intermediate layer. The amount added is 0.1 to 50% by weight, preferably 0.5 to 30% by weight based on the phosphazene resin. Photoinitiators include the compounds of Tables 2 and 3.

[0027] The thickness of the intermediate layer is 0.1 to 50 μm;
Preferably 1 to 30 μm is suitable. The intermediate layer can be applied by dip coating, spray coating, or roll coating.
This can be done by methods such as tinging.

Further, in the present invention, a second intermediate layer containing resin as a main component can be provided on the intermediate layer as necessary for controlling barrier properties. Examples of the resin include polyamide, polyester, polyurethane, polyurea, and phenol resin. The thickness of the second intermediate layer is preferably 0.1 to 5 μm, and is coated by the same method as the above-mentioned intermediate layer.

The photosensitive layer of the electrophotographic photoreceptor of the present invention may be of a single layer type or a laminated type with functionally separated charge generation layer and charge transport layer.

The charge generation layer of the laminated photoreceptor is made of azo pigments such as Sudan Red and Diamble, quinone pigments such as pyrenequinone and anthrone, quinocyanine pigments,
Charge-generating substances such as indigo pigments such as perylene pigments, indigo, and thioindigo, azulenium salt pigments, phthalocyanine pigments such as copper phthalocyanine, and titanyl oxophthalocyanine can be used with polyvinyl butyral, polystyrene, polyvinyl acetate, acrylic resin, polyvinylpyrrolidone, and ethyl cellulose. The intermediate layer can be formed by dispersing it in a binder resin such as cellulose acetate or cellulose acetate, and coating this dispersion on the intermediate layer. The thickness of the charge generation layer is 5 μm or less,
Preferably it is 0.05 to 2 μm.

The charge transport layer is made of a polycyclic aromatic compound having a structure such as biphenylene, anthracene, pyrene, or phenanthrene in the main chain or side chain, indole, or carbazole.
It is formed using a coating liquid in which a charge transporting substance such as a nitrogen-containing cyclic compound such as silica, oxadiazole, or pyrazoline, a hydrazone compound, or a styryl compound is dissolved in a resin having film-forming properties. Examples of resins having such film-forming properties include polyester, polycarbonate, polymethacrylate, and polystyrene. The thickness of the charge transport layer is 5 to 40 μm, preferably 10 to 30 μm.

The electrophotographic photoreceptor of the present invention also includes a layer of an organic photoconductive polymer such as polyvinyl carbazole or polyvinylanthracene, a selenium vapor deposition layer, a selenium-tellurium vapor deposition layer, an amorphous silicon layer, etc. as a photosensitive layer. Can be used.

[0033] The conductive support may be any material as long as it has conductivity; for example, metals or alloys such as aluminum, copper, chromium, nickel, zinc, or stainless steel molded into a drum or sheet shape, aluminum or A conductive layer is provided by laminating a metal foil such as copper onto a plastic film, by vapor-depositing aluminum, indium oxide, tin oxide, etc. onto a plastic film, or by applying a conductive substance alone or together with an appropriate binder resin. Examples include metal, plastic film, and paper. Conductive substances include metal powders such as aluminum, copper, nickel, and silver, metal foils and short metal fibers, conductive metal oxides such as antimony oxide, indium oxide, and tin oxide, polypyrrole, polyaniline, and polymer electrolytes. polymeric conductive materials such as carbon fiber, carbon black,
Examples include graphite powder, organic and inorganic electrolytes, or conductive powders whose surfaces are coated with these conductive substances. Binder resins used for the conductive layer include polyamide, polyester, acrylic resin, polyamino acid ester, polyvinyl acetate, polycarbonate, polyvinyl formal, polyvinyl butyral, polyvinyl alkyl ether, and polyvinyl acetate. Alkylene ether, thermoplastic resin such as polyurethane elastomer, thermosetting polyurethane,
Examples include thermosetting resins such as phenol resin and epoxy resin. The mixing ratio of conductive substance and binder resin is 5:1 to 1
: About 5. This mixing ratio is determined in consideration of the resistance value, surface properties, coating suitability, etc. of the conductive layer. When the conductive substance is a powder, a mixture is prepared by a conventional method using a ball mill, roll mill, sand mill, or the like. Further, as other additives, surfactants, silane coupling agents, titanate coupling agents, silicone oil, silicone leveling agents, etc. may be added.

The electrophotographic photoreceptor of the present invention can be applied to general electrophotographic devices such as copying machines, laser printers, LED printers, and liquid crystal shutter type printers, but it can also be applied to display devices to which electrophotographic technology is applied. - It can be widely applied to devices such as recording, light printing, plate making, and facsimile.

Next, an electrophotographic apparatus and a facsimile equipped with the electrophotographic photoreceptor of the present invention will be explained.

FIG. 1 shows a schematic configuration of a general transfer type electrophotographic apparatus using the drum type photoreceptor of the present invention. In the figure, 1 is a drum-type photoreceptor as an image carrier, and a shaft 1
It is rotated at a predetermined circumferential speed in the direction of the arrow around point a. During the rotation process, the photoreceptor 1 is uniformly charged to a predetermined positive or negative potential on its circumferential surface by the charging means 2, and then subjected to light image exposure L (slit exposure/ (laser beam scanning exposure, etc.). As a result, electrostatic latent images corresponding to the exposed images are sequentially formed on the circumferential surface of the photoreceptor. The electrostatic latent image is then developed with toner by a developing means 4, and the toner-developed image is transferred by a transfer means 5 from a paper feed section (not shown) between the photoreceptor 1 and the transfer means 5, when the photoreceptor 1 is rotated. The images are sequentially transferred onto the surface of the transfer material P that is fed in synchronization with the image data. The transfer material P that has undergone the image transfer is separated from the photoreceptor surface and introduced into the image fixing means 8, where the image is fixed and printed out outside the machine as a copy. After the image has been transferred, the surface of the photoreceptor 1 is cleaned by a cleaning means 6 to remove residual toner after transfer, and is subjected to a charge removal process by a pre-exposure means 7 and used repeatedly for image formation. As the uniform charging means 2 for the photoreceptor 1, a corona charging device is generally widely used. Further, as for the transfer device 5, a corona transfer means is generally widely used. An electrophotographic apparatus is constructed by combining a plurality of components such as the above-mentioned photoreceptor, developing means, and cleaning means into an apparatus unit, and this unit is detachably attached to the main body of the apparatus. It may be configured. For example, the photoreceptor 1 and the cleaning means 6 may be integrated into one apparatus unit, and may be configured to be detachable using a guide means such as a rail on the main body of the apparatus. At this time, the above-mentioned device unit may include a charging means and/or a developing means. When the electrophotographic apparatus is used as a copying machine or a printer, the light image exposure L can be carried out by using reflected light or transmitted light from the original, or by reading the original and converting it into a signal, and then using a laser according to this signal. This is performed by scanning a beam, driving a light emitting diode array, or driving a liquid crystal shutter array.

Furthermore, when used as a facsimile printer, the optical image exposure L is exposure for printing received data.

FIG. 2 is a block diagram showing an example of this case. A controller 11 controls an image reading section 10 and a printer 19. The entire controller 11 is controlled by a CPU 17. The read data from the image reading section is transmitted to the other party's station through the transmitting circuit 13. 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. A printer controller 18 controls a printer 19. 14 is a telephone. line 15
After the image received from the remote terminal (image information from a remote terminal connected via a line) is demodulated by the receiving circuit 12, the CPU 17 performs signal processing on the image information and sequentially stores it in the image memory 16. . When at least one page of images is stored in the memory 16, the image of that page is stored. The CPU 17 reads one page of image information from the memory 16 and sends the signaled one page of image information to the printer controller 18. printer control
When the printer 18 receives one page of image information from the CPU 17, it controls the printer 19 to record the image information of that page. Note that the CPU 17 receives the next page while the printer 19 is recording. As described above, images are received and recorded.

[0039]

[Example] The average particle diameter of the tin oxide particles dispersed in the intermediate layer in the example was determined by forming a film in which tin oxide particles were dispersed in a binder resin on an aluminum substrate, and oxidizing it using an electron microscope. The particle size of the tin particles is measured and the average of 100 tin oxide particles is determined as the average particle size of the film.

Example 1 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of phenolic resin,
20 parts of methyl cellosolve, 5 parts of methanol, and 0.002 parts of silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 3,000) were added to a diameter of 1 m.
The paint for the conductive layer was prepared by dispersing for 2 hours in a sand mill device using glass beads, and
30mm x 260mm), apply the above paint by dip coating,
It was dried at 140° C. for 30 minutes to form a conductive layer with a thickness of 20 μm.

Next, 60 parts of a phosphazene monomer of the following structural formula (a),

[Chemical Formula 9] 30 parts of ultrafine tin oxide particles with an average particle size of 400 angstroms before dispersion, 0.1 part of 1-hydroxycyclohexylphenyl ketone as a photoinitiator, and 3 parts of methyl ethyl ketone.
00 parts were mixed and dispersed in a sand mill for 48 hours to prepare an intermediate layer paint. This paint was dip-coated onto the conductive layer, dried at 120°C for 20 minutes, and then applied at a voltage of 1.5 kV while rotating the cylinder at a speed of 20 rpm.
UV rays were irradiated for 30 seconds at a distance of 25 cm under a high-pressure mercury lamp to perform photocuring and form an intermediate layer with a thickness of 0.6 μm.

The dispersibility of the paint for the intermediate layer was good, and the surface of the intermediate layer was even and uniform. Furthermore, the average particle diameter of the primary particles of the ultrafine tin oxide particles dispersed in the intermediate layer was 400 angstroms as determined by the above-mentioned measuring method.

Next, the structural formula

3 parts of disazo pigment of formula 10, polyvinylbenzal (benza-
After dispersing 2 parts (with a weight average molecular weight of 80% and a weight average molecular weight of 11,000) and 35 parts of cyclohexanone for 12 hours in a sand mill using φ1 mm glass beads, 60 parts of methyl ethyl ketone was added to prepare a charge generation layer dispersion. Prepared. This dispersion was applied onto the intermediate layer by dip coating and dried at 80° C. for 20 minutes to form a charge generation layer with a thickness of 0.22 μm.

Next, the structural formula

10 parts of the styryl compound of formula 11 and 10 parts of polycarbonate (weight average molecular weight 46,000) were mixed with 20 parts of dichloromethane,
This solution was dissolved in a mixed solvent of 40 parts of chlorobenzene, and this solution was dip-coated onto the above charge generation layer and dried at 120° C. for 60 minutes to form a charge transport layer with a thickness of 19 μm.

The electrophotographic photoreceptor thus produced was charged.
A reversal development type laser printer that repeats the exposure-development-transfer-cleaning process in a 1.5 second cycle.
The electrophotographic properties were evaluated under normal temperature and humidity (23° C., 50% RH) and high temperature and high humidity (30° C., 85% RH) environments. The results are shown below. Environment: 23℃, 50%RH VD: -720V VL: -145V Environment: 30℃, 85%RH VD: -715V Image: Good The difference between the dark area potential (VD) and the light area potential (VL) is large, and the Contrast was obtained, the dark area potential was stable even under high temperature and high humidity conditions, and a good image was obtained without black dot-like defects (black spots) or fog.

Example 2 A phosphazene monomer of the following structural formula (b) was added to the paint for the intermediate layer.

Electrophotographic photoreceptors were manufactured in the same manner as in Example 1 except that [Chemical 12] was used, and evaluated in the same manner as in Example 1. In both cases, the dark area potential was stable even under high temperature and high humidity, and there were no black spots. A good image was obtained with no visible defects or fog. Environment: 23℃, 50%RH VD: -705V VL: -135V Environment: 30℃, 85%RH VD: -700V Image: Good

004
3] Example 3 An electrophotographic photoreceptor was produced in the same manner as in Example 1, except that a phosphazene monomer of the following structural formula (c) was used for the intermediate layer coating, and evaluated in the same manner as in Example 1. As a result, the dark area potential was stable in all cases even under high temperature and high humidity conditions, and good images without black spot defects or fogging were obtained. Environment: 23℃, 50%RH VD: -730V VL: -150V Environment: 30℃, 85%RH VD: -720V Image: Good

[Chem.13
]

Example 4 An electrophotographic photoreceptor was produced in the same manner as in Example 1, except that a phosphazene monomer of the following structural formula (d) was used for the intermediate layer coating. As a result of evaluation, the dark area potential was stable even under high temperature and high humidity conditions, and good images with no black spot defects or fogging were obtained. Environment: 23℃, 50%RH VD: -690V VL: -130V Environment: 30℃, 85%RH VD: -680V Image: Good

[Chem.14
]

Example 5 A phosphazene monomer of the following structural formula (e) was added to the paint for the intermediate layer.

Electrophotographic photoreceptors were produced in the same manner as in Example 1 except that [Chemical 15] was used, and evaluated in the same manner as in Example 1. In both cases, the dark area potential was stable even under high temperature and high humidity, and there were no black spots. A good image was obtained with no visible defects or fog. Environment: 23℃, 50%RH VD: -740V VL: -160V Environment: 30℃, 85%RH VD: -730V Image: Good

004
6] Comparative Example 1 N-methoxymethylated 6-nylon (weight average molecular weight 15
A coating material for the intermediate layer was prepared by dissolving 4 parts of methoxymethyl group (methoxymethyl group substitution rate: 28%) in 95 parts of methanol. This paint was dip coated onto the conductive layer in the same manner as in Example 1, and
It was dried at ℃ for 20 minutes to form an intermediate layer having a thickness of 0.6 μm. Furthermore, a charge generation layer and a charge transport layer were sequentially laminated on this intermediate layer in the same manner as in Example 1 to produce an electrophotographic photoreceptor, and evaluated in the same manner as in Example 1. The charging ability deteriorated, the dark area potential decreased, and black dot-like defects began to appear on the image. Environment: 23℃, 50%RH VD: -700V VL: -1
75V environment: 30℃, 85%RH VD: -645V Image: Black spots occur

Example 6 50 parts of a phosphazene monomer of the following structural formula (f),

[Chemical Formula 16] 30 parts of ultrafine tin oxide particles having an average particle size of 500 angstroms before dispersion, 0.06 parts of 1-hydroxycyclohexyl phenyl ketone as a photoinitiator, and 300 parts of methyl ethyl ketone were mixed and dispersed to prepare a paint for the intermediate layer. Prepared. Apply this paint to an aluminum cylinder (φ30mm x 360m)
m) After dipping and drying at 120°C for 30 minutes, apply 1 coat while rotating the cylinder at a speed of 20 rpm.
．． Ultraviolet rays were irradiated for 30 seconds at a distance of 20 cm under a 5KV high-pressure mercury lamp to form an intermediate layer with a thickness of 1.2 μm.

The dispersibility of the paint for the intermediate layer was good, and the surface of the intermediate layer was even and uniform. Furthermore, the average particle diameter of the primary particles of the ultrafine tin oxide particles dispersed in the intermediate layer was 500 angstroms as determined by the above-mentioned measuring method.

Next, the structural formula

4 parts of disazo pigment of [Chemical formula 17], polyvinyl butyral (butyral)
After dispersing 2 parts (68% weight average molecular weight, 24,000 weight average molecular weight) and 34 parts of cyclohexanone for 12 hours in a sand mill using φ1 mm glass beads, 60 parts of tetrahydrofuran was added to prepare a charge generation layer dispersion. Prepared. This dispersion was applied onto the intermediate layer by dip coating and dried at 80° C. for 15 minutes to form a charge generation layer with a thickness of 0.17 μm.

Next, styryl compound 1 used in Example 1
0 parts and 10 parts of polycarbonate (weight average molecular weight 63,000) were mixed with 15 parts of dichloromethane and 45 parts of chlorobenzene.
This solution was applied onto the above charge generation layer by dip coating, and dried at 120°C for 60 minutes to give a film thickness of 25%.
A charge transport layer of .mu.m was formed.

The electrophotographic photoreceptor thus produced was charged.
It is installed in a copying machine that repeats the process of exposure, development, transfer, and cleaning in a 0.6 second cycle, and is operated at low temperature and low humidity (1
The electrophotographic properties were evaluated in an environment of 5° C. and 15% RH). As a result, the difference between the dark area potential and the bright area potential was large, and sufficient contrast was obtained. Furthermore, when 1,000 images were continuously produced, very stable images were obtained without any rise in bright area potential. Initial VD: -680V VL: -190V After 1,000 continuous prints VL: -200V Image: Good

Example 7 An electrophotographic photoreceptor was produced in the same manner as in Example 6, except that a phosphazene monomer having the following structural formula (g) was used for the intermediate layer coating, and evaluated in the same manner as in Example 6. As a result, the difference between the dark area potential and the bright area potential was large, and sufficient contrast was obtained. Furthermore, even when 1,000 images were continuously produced, there was almost no increase in bright area potential, and very stable images were obtained. Initial VD: -700V VL: -195V After 1,000 continuous prints VL: -205V Image: Good

[Chemical formula 18]

Example 8 An electrophotographic photoreceptor was produced in the same manner as in Example 6, except that a phosphazene monomer having the following structural formula (h) was used for the intermediate layer coating, and evaluated in the same manner as in Example 6. As a result, the difference between the dark area potential and the bright area potential was large, and sufficient contrast was obtained. Furthermore, even when 1,000 images were continuously produced, there was almost no increase in bright area potential, and very stable images were obtained.

An electrophotographic photoreceptor was produced in the same manner as in Example 6 except that [Chemical formula 19] was used, and it was evaluated in the same manner as in Example 6. As a result, the difference between the dark area potential and the bright area potential was large, and the contrast was sufficient. was gotten. Furthermore, even when 1,000 images were continuously produced, there was almost no increase in bright area potential, and very stable images were obtained. Initial VD: -690V VL: -205V After 1,000 continuous prints VL: -220V Image: Good

Example 9 An electrophotographic photoreceptor was produced in the same manner as in Example 6, except that a phosphazene monomer of the following structural formula (i) was used for the intermediate layer coating, and evaluated in the same manner as in Example 6. As a result, the difference between the dark area potential and the bright area potential was large, and sufficient contrast was obtained. Furthermore, even when 1,000 images were continuously produced, there was almost no increase in bright area potential, and very stable images were obtained. Initial Vd: -695V Vl: -200V After 1,000 continuous sheets Vl: -220V Image: Good

[C20]

Example 10 An electrophotographic photoreceptor was produced in the same manner as in Example 6, except that a phosphazene monomer of the following structural formula (j) was used for the intermediate layer coating, and evaluated in the same manner as in Example 6. As a result, the difference between the dark area potential and the bright area potential was large, and sufficient contrast was obtained. Furthermore, even when 1,000 images were continuously produced, there was almost no increase in bright area potential, and very stable images were obtained. Initial VD: -690V VL: -195V After 1,000 continuous sheets VL: -215V Image: Good

[C21]

Comparative Example 2 Alcohol-soluble copolymerized nylon (
After dissolving 5 parts (weight average molecular weight: 78,000) in 95 parts of methanol, it was applied by dip coating onto the same aluminum cylinder as in Example 6, and dried at 100°C for 15 minutes to give a film thickness of 1.
A 2 μm intermediate layer was formed. A charge generation layer and a charge transport layer were sequentially formed on this intermediate layer in the same manner as in Example 6 to produce an electrophotographic photoreceptor, and evaluated in the same manner as in Example 6. The partial potential increased and fog appeared on the image. Initial VD: -685V VL: -200V After 1,000 continuous prints VL: -490V Image: Fogging occurs

Example 11 30 parts of ultrafine tin oxide particles with an average particle diameter of 400 angstroms before dispersion, 20 parts of the phosphazene monomer of structural formula (a) used in Example 1, 20 parts of methyl ethyl ketone, and 10 parts of toluene were added. A paint for the intermediate layer was prepared by dispersing the mixture for 12 hours in a sand mill using glass beads having a diameter of 1 mm. Apply this paint to an aluminum cylinder (φ60mm x 26mm)
After drying at 120°C for 30 minutes, UV rays were irradiated for 3 minutes at a distance of 20cm2 under a 1.5kV high-pressure mercury lamp while rotating the cylinder at 20rpm to determine the film thickness. A 16 μm intermediate layer was formed.

The dispersibility of the paint for the intermediate layer was good, and the surface of the intermediate layer was even and uniform. Furthermore, the average particle diameter of the primary particles of the ultrafine tin oxide particles dispersed in the intermediate layer was 400 angstroms as determined by the above-mentioned measuring method.

Next, alcohol-soluble copolymerized nylon (
5 parts (weight average molecular weight: 75,000) was dissolved in 95 parts of methanol, dip coated onto the above intermediate layer, and dried at 80°C for 10 minutes to form a second intermediate layer with a film thickness of 0.3 μm. did.

Next, the structural formula

2 parts of disazo pigment of [Chemical formula 22], polyvinyl butyral (butyral)
After dispersing 1 part (with a weight average molecular weight of 72% and a weight average molecular weight of 18,000) and 30 parts of cyclohexanone for 20 hours in a sand mill using φ1 mm glass beads, 65 parts of methyl ethyl ketone was added to prepare a charge generation layer dispersion. Prepared. This dispersion was dip coated onto the second intermediate layer and
It was dried for a minute to form a charge generation layer with a thickness of 0.2 μm.

Next, the structural formula

10 parts of the hydrazone compound of formula 23 and 10 parts of polycarbonate (weight average molecular weight 46,000) were dissolved in a mixed solvent of 20 parts of dichloromethane and 40 parts of chlorobenzene, and this solution was applied on the charge generation layer. The charge transport layer was coated by dip coating and dried at 120° C. for 60 minutes to form a charge transport layer with a thickness of 21 μm.

The electrophotographic photoreceptor thus produced was charged.
It is installed in a copying machine that repeats the process of exposure, development, transfer, and cleaning in a 0.8 second cycle, and is operated at low temperature and low humidity (1
The electrophotographic properties were evaluated in an environment of 0° C. and 10% RH. As a result, the difference between the dark area potential and the bright area potential was large, and sufficient contrast was obtained. Furthermore, when 1,000 consecutive images were produced, very stable images were obtained without any rise in dark area potential. Initial VD: -655V VL: -155V After 1,000 continuous prints VD: -650V Image: Good

Example 12 An intermediate layer, a charge generation layer and a charge transport layer were formed in the same manner as in Example 11 except that the second intermediate layer was not provided, and an electrophotographic photoreceptor was manufactured. When similarly evaluated, the difference between the dark area potential and the bright area potential was large, and sufficient contrast was obtained. Furthermore, when 1,000 consecutive images were produced, very stable images were obtained with almost no increase in dark area potential. Initial VD: -700V VL: -145V After 1,000 continuous prints VL: -145V Image: Good

Comparative Examples 3 and 4 40 parts of ultrafine tin oxide particles with an average primary particle diameter of 400 angstroms before dispersion, 20 parts of phenol resin, 20 parts of methanol, and 10 parts of 2-propanol were added. Dispersed for 12 hours using a sand mill device using φ1 mm glass beads.
A paint for the intermediate layer was prepared. This paint was dip coated onto an aluminum cylinder (φ60mm x 260mm) and
It was dried at 60 degrees for 30 minutes to form an intermediate layer with a thickness of 16 μm. Electrophotographic photoreceptors corresponding to Comparative Examples 3 and 4 were produced on this intermediate layer in the same manner as in Examples 11 and 12, respectively.

The dispersibility of the paint for the intermediate layer was poor, and the surface of the intermediate layer was rough and tin oxide particles were unevenly present. Also,
The average particle diameter of the primary particles of the ultrafine tin oxide particles dispersed in the intermediate layer was 1.7 μm as determined by the above measurement method.

When this photoreceptor was evaluated in the same manner as in Example 11, it was found that in Comparative Example 3, the dark area potential increased after 1,000 sheets were continuously printed, and fog appeared on the image. In addition, in Comparative Example 4 in which a charge generation layer and a charge transport layer were provided directly on the intermediate layer, the barrier properties of the intermediate layer were insufficient, and the charge injection from the support side was large and the dark area potential was low. No potential contrast was obtained. Comparative example 3 Initial VD: -670V VL: -175V After 1,000 continuous sheets VD: -520V Image: Fogging Comparative example 4 Initial VD: -420V VL: -80V Unable to evaluate after 1,000 sheets continuously

[0066]

Effects of the Invention The electrophotographic photoreceptor of the present invention has stable potential characteristics in all environments by containing a phosphazene resin and ultrafine metal oxide particles in the intermediate layer between the conductive support and the photosensitive layer. Good images can be obtained, and because the ultrafine metal oxide particles, which are conductive particles in the intermediate layer, have excellent dispersibility, the surface of the intermediate layer is uniform and has no image defects, making it suitable for repeated use. This has the remarkable effect that stable potential characteristics and image quality can be obtained even when Furthermore, similar effects can be achieved in an electrophotographic apparatus and a facsimile equipped with the electrophotographic photoreceptor of the present invention.

[Brief explanation 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 machine using an electrophotographic device as a printer.

[Explanation of symbols]

1 Drum-type photoreceptor as an image carrier (electrophotographic photoreceptor of the present invention) 1a Shaft 2 Corona charging device 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 that has undergone image transfer Image reading section 11 Controller 12 Receiving circuit 13 Transmitting circuit 14 Telephone 15 Line 16 Image memory 17 CPU 18 Printer controller 19 Printer

Claims (5)

[Claims] 1. An electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive support via an intermediate layer, in which the intermediate layer comprises a resin obtained by polymerizing a phosphazene monomer represented by the following general formula (1) and An electrophotographic photoreceptor characterized by containing ultrafine metal oxide particles. General formula (1) embedded image In the formula, R1 represents a group having an ethylenically unsaturated bond. [Claim 2] The phosphazene monomer has the following general formula (
The electrophotographic photoreceptor according to claim 1, which is a monomer represented by 2). General formula (2) [Chemical formula 2] In the formula, R1 represents [Chemical formula 3], and in the above formula, R2 is an alkyl group, an aryl group, an alkyl-substituted aryl group, an alkylamido group, an arylamido group , a polyoxylene group, and R3 represents a hydrogen atom or a methyl group. 3. The electrophotographic photoreceptor according to claim 1, wherein the average particle diameter of the primary particles of the ultrafine metal oxide particles is 500 angstroms or less. 4. An electrophotographic apparatus comprising the electrophotographic photoreceptor according to claim 1. 5. A facsimile machine comprising an electrophotographic apparatus comprising the electrophotographic photoreceptor according to claim 1 and means for receiving image information from a remote terminal.