JP2832063B2 - Image holding member - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an image holding member for holding an electrostatic image or a toner image.

[Conventional technology]

An electrostatic image or toner image is formed by various processes. As an image holding member on which an electrostatic image or a toner image is formed, there are an image holding member having a photoconductive layer called an electrophotographic photosensitive member and an image holding member having no photoconductive layer.

The image holding member usually comprises a support and an image holding layer thereon.

The electrophotographic photosensitive member has various configurations in order to obtain predetermined characteristics or according to the type of an applied electrophotographic process. A photoreceptor in which a photoconductive layer is formed as an image holding layer on a support as a typical example of an electrophotographic photoreceptor, and a photoreceptor having a stack of a photoconductive layer and an insulating layer thereon as an image holding layer There is widely used. A photoreceptor composed of a support and a photoconductive layer is used for image formation by the most common electrophotographic processes, that is, charging, image exposure and development, and if necessary, transfer. Also, for photoreceptors with an insulating layer, this insulating layer protects the photoconductive layer, improves the mechanical strength of the photoreceptor, improves the dark attenuation characteristics,
Alternatively, it is provided for the purpose of being applied to a specific electrophotographic process described in JP-B-42-13910 and the like.

The electrophotographic photosensitive member is applied to a predetermined electrophotographic process to form an electrostatic image, and the electrostatic image is developed and visualized.

A typical configuration of an image holding member without a photoconductive layer has an insulating layer as the image holding layer, and some typical uses of the image holding member will be described below.

(1) For example, Japanese Patent Publication No. 32-7115, Japanese Patent Publication No. 32-8204
As described in JP-B-43-15559, an electrostatic image formed on an electrophotographic photosensitive member for the purpose of improving the repetitive usability of the electrophotographic photosensitive member is an image having no photoconductive layer. The toner image is transferred to a holding member for development, and then the toner image is transferred to a recording medium. (2) applying an electric signal to the multi-needle electrode to form an electrostatic image according to the electric signal on the surface of the image holding member having no photoconductive layer, This can be developed into an image. An image holding member used in such an electrophotographic process.

The image holding member is generally formed by forming an image holding layer on a conductive support, but as the conductive support,
An Al drum whose surface is mirror-finished is generally used. Mirror finishing is a process necessary for achieving uniformity of the thickness of the image holding layer and uniformity of the electrostatic properties of the support, and not deteriorating the image quality. However, the mirror finishing treatment has been a factor of cost increase, and a low-cost and high-performance support has been desired.

Therefore, in the present invention, it is possible to provide an image holding member that realizes a conductive substrate that is uniform in terms of surface roughness and electrically at low cost and does not rely on means such as mirror finishing, and obtains a good image. It is the purpose.

The present invention relates to an image holding member having a support and an image holding layer on the support, wherein the support has a base and a conductive electrodeposition coating film on the surface of the base, and the image holding layer includes An intermediate layer is provided between the support and the support.

By applying the electrodeposition coating film to the conductive support of the image holding member, (1) a uniform conductive layer can be obtained without any particular smoothing treatment even if the undercoat is rough. (2) Inexpensive plastic can be used without using a metal such as aluminum for the base material. This makes it possible to obtain a low-cost and homogeneous conductive support, which is the object of the present invention.

The electrodeposition paint used for forming the electrodeposition coating film of the present invention is generally prepared by depositing a conductive powder having an average particle size of 0.1 to 5 μm in an electrodepositable resin with respect to 100 parts by weight of the electrodepositable resin. 5 to 50 parts by weight.

A typical substrate of the present invention is a plastic material, which is subjected to a generally known plating process on plastic, that is, 3 to 10 μm by electroless plating. Next, a low-temperature curing type generally known as an electrodeposition paint, preferably an acrylic
A conductive powder is dispersed in a melamine-based, acrylic-based, epoxy-based, urethane-based, or alkyd-based resin, and can be applied to an anionic or cationic system.

In the anionic system, the substrate side is used as the anode, and in the cationic system,
A cathode, liquid temperature 20-25 ° C. range at an applied voltage 50～200V, 1-5 minutes current density 0.5~3A / dm ² processing time. Then
After washing, drain and drain in an oven at 90-100 ° C for 20-180.
Cure for a minute to complete. The amount of eutectoid in the coating film at this time was resin 10
The amount of the conductive powder is 10 to 60 parts by weight, preferably 30 to 50 parts by weight based on 0 parts by weight.

As the substrate, other than the above-mentioned plastics, metals such as aluminum, copper, and iron can be used. In this case, even if the surface is not mirror-finished, a good support can be formed by the flattening effect of the electrodeposition coating.

As the conductive powder, aluminum, copper, nickel,
Metal powders such as iron, metal foils and metal short fibers; conductive metal oxides such as antimony oxide, indium oxide, and tin oxide; polymer conductive materials such as polypyrrole, polyaniline, and polymer electrolyte; carbon fiber, carbon black And graphite powder.

In the present invention, the thickness of the electrodeposition coating film is 5 to 50 μm, and particularly preferably 10 to 30 μm.

In the present invention, an intermediate layer can be provided on the electrodeposition coating film, if necessary, for example, for controlling the barrier property and the adhesion to the image holding layer.

Examples of the resin material used for the intermediate layer include copolymer nylon, N-alkoxymethylated nylon, polyurethane, polyurea, polyester, and phenol resin, in addition to the above-mentioned polyether polyamide.

The thickness of the intermediate layer is preferably 0.1 μm to 10 μm, and it can be formed by electrodeposition coating in addition to a general coating method such as immersion coating, spray coating, roll coating and the like.

When the image holding member is an electrophotographic photoreceptor, the image holding layer may be a photoconductive layer of a laminated structure in which a function is separated into a charge generation layer and a charge transport layer, or a photoconductive layer of a single layer type.

In the case of the laminated structure type photosensitive conductive layer, the charge generation layer is made of an azo pigment such as Sudan Red, Diane Blue, a quinone pigment such as pyrenequinone or anthantrone, a quinocyanine pigment, a perylene pigment, an indigo pigment such as indigo or thioindico, an azulhenium salt pigment, or copper. A charge generating substance such as a phthalocyanine pigment such as phthalocyanine is dispersed in a binder resin such as polyvinyl butyral, polystyrene, polyvinyl acetate, an acrylic resin, polyvinyl pyrrolidone, ethyl cellulose, and cellulose acetate butyrate. It can be formed by coating on the surface. The thickness of such a charge generation layer is 5 μm or less,
Preferably it is 0.05-2 μm.

The charge transport layer provided on the charge generation layer includes a polycyclic aromatic compound having a structure such as biphenylene, anthracene, pyrene, or phenanthrene in a main chain or a side chain, and a nitrogen-containing ring such as indole, carbazole, oxadiazole, or pyrazoline. It can be formed using a coating solution in which a charge transporting substance such as a formula compound, a hydrazone compound, a styryl compound, or the like is dissolved in a film-forming resin as necessary.

Examples of the resin having such a film forming property include polyester, polycarbonate, polymethacrylate, and polystyrene.

The thickness of the charge transport layer is 5 to 40 μm, preferably 10 to 30 μm.
m.

Further, the stacked structure type photoconductive layer may have a structure in which a charge generation layer is stacked on a charge transport layer.

Furthermore, in the case of a single-layer photosensitive conductive layer, the charge-generating substance and the charge-transporting substance as described above can be contained in a resin, and an organic photoconductive polymer layer such as polyvinyl carbazole and polyvinyl anthracene can be formed. A selenium deposited layer, a selenium-tellurium deposited layer, an amorphous silicon layer, and the like can also be used.

On the other hand, as the support used in the present invention, a support formed in a drum or sheet shape is generally used.

When the image holding member does not have a photoconductive layer, the image holding layer is an insulating layer. As the resin used for forming such an insulating layer, polyamide, polyester, acrylic resin, polyamino acid ester, polyvinyl acetate, polycarbonate, polyvinyl formal, polyvinyl butyral, polyvinyl alkyl ether, polyalkylene ether, polyurethane elastomer and the like Thermoplastic resins and thermosetting resins such as thermosetting polyurethane, phenolic resins, and epoxy resins are exemplified.

FIG. 1 shows a schematic configuration of a general transfer type electrophotographic apparatus using a drum type photoreceptor according to the present invention.

In FIG. 1, reference numeral 1 denotes a drum-type photosensitive member as an image carrier, which is driven to rotate at a predetermined peripheral speed in the direction of an arrow around a shaft 1a. The photoreceptor 1 is uniformly charged at a predetermined positive or negative potential on its peripheral surface by a charging means 2 during the rotation process, and then exposed at a light exposure section 3 by an image exposure means (not shown) at an exposure section 3.
(Slit exposure, laser beam scanning exposure, etc.). As a result, an electrostatic latent image corresponding to the exposure image is sequentially formed on the peripheral surface of the photoconductor.

The electrostatic latent image is then toner-developed by a developing unit 4 and the toner-developed image is periodically cycled by a transfer unit 5 between a photosensitive unit 1 and a transfer unit 5 from a paper supply unit (not shown). The transfer material P is sequentially transferred onto the surface of the transferred transfer material P.

The transfer material P having undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing, and is printed out as a copy (copy) outside the machine.

The surface of the photoreceptor 1 after the image transfer is cleaned by removing the untransferred toner by the cleaning means 6, and furthermore,
The charge is removed by the 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. The transfer device 5 also generally uses a corona transfer unit. An electrophotographic apparatus is configured by integrally combining a plurality of components, such as the above-described photoconductor, developing means, and cleaning means, as an apparatus unit, and this unit is configured to be detachable from the apparatus body. You may. For example, the photoconductor 1 and the cleaning means 6 may be integrated into one apparatus unit, and may be configured to be detachable using guide means such as rails of the apparatus body. At this time, the above-mentioned device unit may be provided with a charging unit and / or a developing unit.

In the case where the electrophotographic apparatus is used as a copier or a printer, the light image exposure L is performed by reflecting or transmitting light from the original, or by reading the original and converting it into a signal. This is performed by driving an array or driving a liquid crystal shutter array.

When used as a facsimile printer, the light image exposure L is 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 unit 10 and the printer 19. The entire controller 11 is controlled by the CPU 17. The read data from the image reading unit is transmitted to the partner station through the transmission 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. The printer controller 18 controls the printer 19. 14 is a telephone.

The image received from the line 15 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 12, and then the CPU 17 performs a decoding process of the image information and is sequentially stored in the image memory 16. . When the image of at least one page is stored in the memory 16, the image of the page is recorded. The CPU 17 reads out one page of image information from the memory 16 and sends out the decoded one page of image information to the printer controller 18. The printer controller 18 has a CP
When the image information of one page is received from U17, the printer 19 is controlled to record the image information of the page.

Note that the CPU 17 is receiving the next page during recording by the printer 19.

 As described above, image reception and recording are performed.

Example 1 A plastic cylinder having an outer diameter of 80φ and a wall thickness of 5 mm was set to C
Treated with an rO ₃ -H ₂ SO ₄ -H ₂ O-based etching solution for 1 minute, washed with water, and then used as a sensitizer solution stannous chloride 30 g / HCl
The mixture was treated with 20 ml / well at room temperature for 2 minutes and washed with water. Next, as an activator liquid, 0.3 g of palladium chloride /
Then, the mixture was treated with 3 ml of hydrochloric acid at room temperature for 2 minutes to make it conductive. Then, electroless copper plating solution (Okuno Pharmaceutical Co., Ltd.)
Plating using a pH of 13.0 at a bath temperature of 70 ° C for 3 minutes.
A copper thin film having a thickness of μm was formed. Next, treatment was performed at 70 ° C. for 30 seconds with an aqueous solution of 5% sodium hydroxide and 1% potassium persulfate to form a copper oxide film as a chemically colored film.

And 100 parts by weight of acrylic / melamine resin (trade name: Hanibright C-IL, manufactured by Honey Kasei Co., Ltd.)
15 parts by weight of copper particles having an average particle size of 0.07 μm
After dispersing for a time, dilute to 15% by weight with demineralized water, and further use a coating solution containing 2.0% by weight of carbon black for coloring at a bath temperature of 25 ° C. and a pH of 8 to 9 to be coated. Was electrodeposited at an applied voltage of 150 V for 3 minutes using a 0.5 t stainless steel plate as a counter electrode. After electrodeposition, wash with water, 97 ℃ ± 1
This was cured by heating in an oven at a temperature of 60 ° C. for 60 minutes to obtain a conductive coating film having a thickness of 20 μm.

The average particle size of the copper particles was calculated by the following formula as dense spheres having the same particle size (the same applies to the following average particle sizes).

Next, a four-element copolymerized nylon (average molecular weight 14,000, trade name Amiran CM-8000, Toray Industries, Inc.) 10
A part of the solution, which was dissolved in a mixed solvent of 60 parts of methanol and 30 parts of nobutanol, was dip-coated to a thickness of 1.0 μm, and dried at 60 ° C. for 30 minutes.

Next, the following structural formula Was dispersed in a sand mill using 1φ glass beads for 20 hours, and 10 parts of the disazo pigment described above, 6 parts of a cellulose acetate butyrate resin (trade name: CAB-381, manufactured by Eastman Chemical Co., Ltd.) and 60 parts of cyclohexane were dispersed. 100 parts of methyl ethyl ketone was added to this dispersion, and the resultant was applied by dip coating on the above-mentioned intermediate layer.
For 10 minutes to provide a charge generation layer having a thickness of 0.1 μm.

Next, the following structural formula Was dissolved in 80 parts of toluene, and 10 parts of a hydrazone compound and 12 parts of a styrene-methyl methacrylate copolymer (trade name: MS-200, manufactured by Iron and Steel Chemical Co., Ltd.) were dissolved in 80 parts of toluene. This solution was dip-coated on the charge generation layer and dried with hot air at 100 ° C. for 1 hour to form a 20 μm thick charge transport layer.

The photoreceptor thus prepared was attached to an electrophotographic copying machine having a -5.6 KV corona charging, image exposure, dry toner development, toner transfer to plain paper, a cleaning process using a urethane rubber blade, and the like. Very good images were obtained.

In particular, a photoconductor in which a conductive layer is provided on a cylinder by dip-coating a coating material in which a carbon black is dispersed in a melamine resin, and an intermediate layer, a charge generation layer, and a charge transport layer are provided in the same manner as in Example 1 As a result, it was confirmed that the halftone image was excellent in denseness.

Example 2 An Al cylinder having an outer diameter of 80φ, a thickness of 1 mm, and a surface roughness Rz of 2.0 μm was subjected to chromate treatment in 0.1% by weight of CrO ₃ , and then an acryl / melamine resin (trade name: Honeybright C-IL, Honey Chemical Co., Ltd.) Co.) 100 parts by weight, average particle size 0.05μ
After dispersing 10 parts by weight of Ni particles in a ball mill for 30 hours,
The solution was diluted to 15% by weight with demineralized water, and further added with 2.0% by weight of carbon black for coloring.
Electrodeposition was performed at 5 ° C. and pH 8 to 9 using an object to be coated as an anode and a 0.5 t stainless steel plate as a counter electrode at an applied voltage of 150 V for 3 minutes. After electrodeposition, wash with water and heat in an oven at 97 ° C ± 1 ° C.
The coating was cured by heating for 1 minute to obtain an electrodeposition coating film.

Next, an ethanol solution (solid content: 15 wt%) of a resol type phenol resin (average molecular weight: 1,000, trade name: Plyophene 5010, manufactured by Dainippon Ink Co., Ltd.) having a thickness of 1.0 μm is formed on the conductive layer. And then dried and cured at 140 ° C. for 10 minutes.

Next, the following structural formula 10 parts of ε-type copper phthalocyanine pigment of Polyvinyl butyral resin (trade name: Esrec BM-2 Sekisui Chemical Co., Ltd.)
10 parts by weight with 120 parts by weight of cyclohexanone
The particles were dispersed for 10 hours by a sand mill using φ glass beads. To this dispersion was added 30 parts by weight of still ethyl ketone, and the mixture was applied on the intermediate layer, and dried at 100 ° C. for 10 minutes to obtain 0.15 μm.
The charge generation layer having a film thickness of 5 mm was provided.

Next, 10 parts of the same hydrazone compound as in Example 1 and 12 parts of a polycarbonate resin (molecular weight: 20,000, trade name: Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) were dissolved in 80 parts of monochlorobenzene. This solution was dip-coated on the charge generation layer and dried with hot air at 100 ° C. for 1 hour to form a 20 μm thick charge transport layer.

The photoreceptor thus prepared was attached to a laser beam printer that performs reversal development using a semiconductor laser (oscillation wavelength λ = 780 nm) as a light source, and the image was evaluated.
Very good images are obtained, especially in high temperature and high humidity environments (temperature 30
(° C, relative humidity: 85%), no black spots were observed.

Example 3 Using the same cylinder as in Example 2, chromate treatment was performed in a solution containing 1.0% by weight of CrO ₃ , and then 100 parts by weight of an acrylic melamine resin (trade name: Hanibright C-IL, manufactured by Honey Chemical Co., Ltd.) On the other hand, Cu particles 1 with an average particle diameter of 0.02 μm
After dispersing 0 parts by weight in a ball mill for 30 hours,
Using a coating liquid diluted to 5% by weight and further adding 2.0% by weight of carbon black for coloring, a bath temperature of 25 ° C. and a pH of 8 to
Under the conditions of 9, an electrodeposition was performed at an applied voltage of 150 V for 3 minutes using an object to be coated as an anode and a 0.5 t stainless plate as a counter electrode. After electrodeposition, the electrode was washed with water and heated in an oven at 97 ° C. ± 1 ° C. for 60 minutes to be cured to obtain an electrodeposited coating film.

Next, a solution prepared by dissolving 10 parts of methoxymethylated nylon (trade name: Toresin EF-30T, manufactured by Teikoku Chemical Co., Ltd.) in a mixed solvent of 60 parts of methanol and 30 parts of nobutanol was coated on the conductive layer. Dip coating to a thickness of 1.0μ, 60 ℃
For 30 minutes.

Next, the following structural formula And 10 parts of a polyvinyl butyral resin (trade name: Eslect BL-S, manufactured by Sekisui Chemical Co., Ltd.) were dispersed together with 120 parts of cyclohexane in a sand mill using 1φ glass beads for 10 hours. To this dispersion, 100 parts of methyl ethyl ketone was added, and the resultant was dip-coated on the intermediate layer, and dried at 100 ° C. for 10 minutes to form a 0.1 μm-thick charge generation layer.

Next, 10 parts of a styryl compound having the following structure and a polycarbonate resin (molecular weight: 20,000, trade name Iupilon Z)
-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was dissolved in 12 parts of monochlorobenzene. This solution was dip-coated on the charge generation layer and dried with hot air at 100 ° C. for 1 hour to form a 20 μm thick charge transport layer.

The photoreceptor thus prepared was attached to the same electrophotographic copying machine as in Example 1 and the image was evaluated. As a result, a very good image was obtained.

Example 4 The same cylinder as in Example 2 was subjected to a chromate treatment with a 0.1 wt% solution of CrO ₃ , and then 100 weight of an acrylic / melamine resin (trade name: Hanibright C-IL, manufactured by Honey Chemical Co., Ltd.) Parts, the average particle size of 0.02μm Cu
After dispersing 10 parts by weight of the particles in a ball mill for 30 hours, the mixture was diluted to 15% by weight with demineralized water, and further added with 2.0% by weight of carbon black for coloring.
Under the conditions of H8 ~ 9, the object to be coated is the anode and 0.5t as the counter electrode
Electrodeposition was performed at an applied voltage of 120 V for 3 minutes using a stainless steel plate. After electrodeposition, the electrode was washed with water and heated in an oven at 97 ° C. ± 1 ° C. for 60 minutes to be cured to obtain an electrodeposited coating film.

Next, a 10 μm-thick intermediate layer made of the same methoxymethylated nylon as in Example 3 was provided on the conductive layer.

Next, the following structural formula 4 parts of quinone pigment, 40 parts of the polycarbonate resin, 10 parts of the low molecular weight tetrafluoroethylene resin powder, and the following structural formula Of biphenyl compound is mixed with monochlorobenzene
The mixture was dispersed for 10 hours with a sand mill using 1φ glass beads together with 150 parts. To this dispersion, 50 parts of dichloromethane was added, dip-coated on the above-mentioned intermediate layer, and dried at 100 ° C. for 1 hour to provide a 20 μm photosensitive layer.

The primary charge and transfer charge of the electrophotographic copying machine using the photoreceptor thus prepared in Examples 1 and 3 were modified to polarities, and the image was evaluated using a polarity-compatible electrophotographic copying machine using a negative toner. As a result, a very uniform and good image was obtained.

[Brief description of the drawings]

FIG. 1 is a schematic structural view of a general transfer type electrophotographic apparatus using an image holding member according to the present invention. FIG. 2 is a block diagram of a facsimile using an electrophotographic apparatus using the image holding member according to the present invention as a printer. 1 .... Drum type photoreceptor

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-39053 (JP, A) JP-A-59-74569 (JP, A) JP-A-60-140358 (JP, A) JP-A Sho 51- 114132 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) G03G 5/14

Claims (5)

(57) [Claims] 1. An image holding member having a support and an image holding layer on the support, wherein the support has a substrate and a conductive electrodeposition coating film on the surface of the substrate. An image holding member having an intermediate layer between a layer and a support. 2. The image holding member according to claim 1, wherein said image holding layer is a photoconductive layer. 3. The image holding member according to claim 1, wherein the intermediate layer is a resin layer selected from polyether polyamide, copolymerized nylon, N-alkoxymethylated nylon, polyurethane, polyester and phenol resin. 4. A support having an image holding layer on the support, the support having a base material and a conductive electrodeposition coating film on the surface of the base material, wherein the image holding layer and the support An electrophotographic apparatus comprising an electrophotographic photoreceptor having an intermediate layer therebetween. 5. A support having an image holding layer on the support, the support having a base and a conductive electrodeposition coating film on the surface of the base, and A facsimile, comprising: an electrophotographic apparatus provided with an electrophotographic photosensitive member having an intermediate layer therebetween; and a receiving means for receiving image information from a remote terminal.