JP2014010392A - Electrophotographic photoreceptor and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoreceptor having excellent cleaning property, wear resistance, and image characteristics, without causing any problem on adhesion to a support body, and to provide an image forming device using the photoreceptor.SOLUTION: An electrophotographic photoreceptor includes a photosensitive layer formed on a conductive support. The conductive support has a cylindrical shape with an outer diameter of 25 mm or less. The photosensitive layer contains copolymer polycarbonate resin including a repeated structure represented by the following general formula (1).

Description

  The present invention relates to an electrophotographic photosensitive member used for a copying machine, a printer, and the like. More particularly, the present invention relates to an electrophotographic photosensitive member that has excellent adhesion between a conductive support and a photosensitive layer, has good cleaning characteristics, and that can reduce the size of an image forming apparatus, and an image forming apparatus equipped with the electrophotographic photosensitive member. is there.

Electrophotographic technology is widely used in fields such as copiers and various printers because of its immediacy and high quality images.
As a photoreceptor which is the core of electrophotographic technology, a photoreceptor using an organic photoconductive material having advantages such as non-pollution, easy film formation, and easy manufacture is used.
As a photoreceptor using an organic photoconductive material, a so-called dispersion type photoreceptor in which a photoconductive fine powder is dispersed in a binder resin, and a laminate type photoreceptor in which a charge generation layer and a charge transport layer are laminated are known. ing. Multilayered photoreceptors can be obtained by combining highly efficient charge generating substances and charge transporting substances, so that highly sensitive photoreceptors can be obtained, and a wide range of materials can be selected and highly safe photoreceptors can be obtained. The layer can be easily formed by coating, has high productivity, and is advantageous in terms of cost. Therefore, it is the mainstream of photoreceptors, and has been developed and put into practical use.

  In recent years, electrophotographic printers and MFPs have been used for SOHO use and home use, and the demand for space saving and downsizing has increased more than ever, and the trend toward downsizing of printers has been accelerated. When the outer diameter of the electrophotographic photosensitive member is reduced, cleaning with a cleaning blade is difficult, and problems such as poor cleaning and filming are likely to occur. Particularly, this tendency is remarkable when the outer diameter of the support is 25 mm or less. Controlling the surface properties of the photosensitive layer is an important factor. Further, when the outer diameter of the photoconductor is reduced, the number of rotations of the photoconductor required for printing one print is increased, so that the surface layer of the photoconductor is also worn.

In the case of a general photoreceptor having no functional layer such as a surface protective layer, the photosensitive layer is in contact with the cleaning blade, and the photosensitive layer is also worn.
Examples of the binder resin for the photosensitive layer include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, thermoplastic resins such as polycarbonate, polyester, polysulfone, phenoxy, epoxy, and silicone resin, and various kinds of heat. A curable resin is used. Among the various binder resins, the polycarbonate resin has relatively excellent performance, and various polycarbonate resins have been developed and put into practical use.

In recent years, polycarbonate resins having excellent wear resistance have been developed (for example, Patent Document 1 and Patent Document 2).
It has also been pointed out that the adhesion between the photosensitive layer and the substrate becomes a problem when the diameter of the drum is reduced (Patent Document 3). Conventionally, there has been a method of using an electrophotographic photosensitive member having a small outer diameter in order to reduce the size of the image forming apparatus. However, the small outer diameter means that the applied photosensitive layer is heated when it is dried. This means that a large curvature is applied to the shrinkage, which is a disadvantageous direction from the viewpoint of adhesion between the photosensitive layer and the support.

JP 2011-26574 A JP 2011-26575 A JP 2012-22312 A

As described above, using an electrophotographic photosensitive member with a small outer diameter to achieve the same number of print life as an electrophotographic photosensitive member with a large outer diameter requires a lot of rotation of the photosensitive layer. But it was a disadvantage. Although the polycarbonate described in Patent Document 3 is excellent in adhesiveness, it has not been able to achieve both electrical characteristics, abrasion resistance, and image characteristics at a practical level.
Therefore, even a binder resin for a photosensitive layer having excellent cleaning characteristics may not be practically used due to problems of adhesion or wear resistance. This problem appeared when the support outer diameter was 25 mm or less, and was particularly noticeable when the support outer diameter was 22 mm or less.

  That is, the object of the present invention is excellent in cleaning characteristics, abrasion resistance and image characteristics when an electrophotographic photosensitive member having an outer diameter of a support of 25 mm or less is used, and causes no problem in adhesion to the support. The object is to provide an electrophotographic photoreceptor.

As a result of intensive studies, the present inventor uses a photoconductor containing a polycarbonate resin having a specific structure in the photosensitive layer, so that even when an electrophotographic photoconductor having a support outer diameter of 25 mm or less is used. The present inventors have found that the cleaning properties and abrasion resistance are excellent and that there is no problem with the adhesion to the support, and the present invention has been completed.
That is, the gist of the present invention is that, in an electrophotographic photosensitive member having a photosensitive layer on at least a conductive support, the conductive support has a cylindrical shape having an outer diameter of 25 mm or less, and the photosensitive layer has the following general formula ( The electrophotographic photosensitive member contains a copolymer polycarbonate resin having a repeating structure represented by 1), and an image forming apparatus equipped with the electrophotographic photosensitive member.

  Here, n / (m + n) = 0.25 to 0.47, and particularly preferably n / (m + n) = 0.35 to 0.45.

  According to the present invention, even when an electrophotographic photosensitive member having an outer diameter of a support of 25 mm or less is used, it has excellent cleaning characteristics, abrasion resistance and image characteristics, and adhesion between the support and an adjacent layer. An electrophotographic photosensitive member that does not cause a problem can be obtained, and a miniaturized image forming apparatus can be obtained.

1 is a schematic diagram illustrating a main configuration of an embodiment of an image forming apparatus of the present invention. It is an X-ray diffraction diagram showing a powder X-ray diffraction spectrum of oxytitanium phthalocyanine used in Examples and Comparative Examples of the present invention. It is an X-ray diffraction diagram showing a powder X-ray diffraction spectrum of oxytitanium phthalocyanine used in Examples and Comparative Examples of the present invention.

Hereinafter, the best mode for carrying out the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
For the photosensitive layer of the electrophotographic photosensitive member of the present invention, a polycarbonate resin having a specific structure is used as a binder resin for the photosensitive layer provided on the conductive support of the photosensitive member.

  As a specific structure of the photosensitive layer of the present invention, a laminate type in which a charge generation layer mainly composed of a charge generation material, a charge transport layer mainly composed of a charge transport material and a binder resin is laminated on a conductive support. Examples thereof include a dispersion type (single layer type) photoreceptor having a photosensitive layer in which a charge generation material is dispersed in a layer containing a charge transport material and a binder resin on a photoreceptor and a conductive support. In the present invention, the binder resin is preferably used in the charge transport layer of the laminated photosensitive layer.

<Polycarbonate resin>
In the present invention, the photosensitive layer contains a polycarbonate resin composed of a repeating structural unit represented by the following general formula (1) as a binder resin.

n / (m + n) is 0.25 to 0.47. n / (m + n) is preferably 0.30 or more, and more preferably 0.35 or more, from the viewpoint of ensuring wear resistance. The upper limit is preferably 0.46 or less, more preferably 0.45 or less, from the viewpoint of production stability.
The polycarbonate resin of the present invention can be produced according to the methods described in Patent Document 1 and Patent Document 2.

  In the polycarbonate resin having a repeating structure represented by the general formula (1), the viscosity average molecular weight is usually 10,000 or more, preferably 15,000 or more, more preferably 20 so as to be suitable for coating and forming a photosensitive layer. It is usually not more than 300,000, preferably not more than 200,000, more preferably not more than 100,000. If the viscosity average molecular weight is less than 10,000, the mechanical strength of the resin is lowered and is not practical, and if it is 300,000 or more, it may be difficult to form a photosensitive layer with an appropriate film thickness. is there.

The photosensitive layer of the present invention contains a polycarbonate resin composed of the repeating unit represented by the formula (1), but the polycarbonate resin composed of the repeating unit represented by the formula (1) is substantially represented by the formula (1). As long as it is composed of repeating units represented by (), other repeating structures may be used without departing from the spirit of the present invention.
Moreover, although the photosensitive layer of this invention contains the polycarbonate resin which consists of a repeating unit represented by Formula (1) based on this invention, you may contain another binder resin. Other resins used in combination include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, thermoplastic resins such as polycarbonate, polyester, polysulfone, phenoxy, epoxy, and silicone resins, and various resins. A thermosetting resin etc. are mentioned. Among these resins, polycarbonate resin or polyester resin is preferable.

  Specific examples of suitable structures of the binder resin are shown below. These specific examples are shown for illustration, and any known binder resin may be mixed and used as long as it does not contradict the gist of the present invention.

  The viscosity average molecular weight of the binder resin that may be used in combination is arbitrary as long as the effect of the present invention is not significantly impaired, but is preferably 10,000 or more, more preferably 20,000 or more, and the upper limit is It is preferably 150,000 or less, more preferably 120,000 or less, and still more preferably 100,000 or less. If the value of the viscosity average molecular weight is too small, the mechanical strength of the photoreceptor may be insufficient.If it is too large, the viscosity of the coating solution for forming the photosensitive layer may be too high and the productivity may decrease. is there.

When the layer containing the polycarbonate resin composed of the repeating unit represented by the formula (1) contains a binder resin other than the resin, the layer is added to the layer in order to maintain the mechanical properties of the electrophotographic photosensitive member of the present invention. The polycarbonate resin composed of repeating units represented by the formula (1) is preferably 50% by weight or more, more preferably 80% by weight or more, particularly preferably, based on the total binder resin contained. Only the polycarbonate resin consisting of the repeating unit represented by the formula (1) is used as the binder resin, and no binder resin other than the resin is contained.

<Conductive support>
The conductive support according to the present invention has a cylindrical shape and has an outer diameter of 25 mm or less.
In order to reduce the size of the image forming apparatus, the conductive support preferably has an outer diameter of 25 mm or less, more preferably 22 mm or less, and even more preferably 20 mm or less. On the other hand, from the viewpoint of arranging members around, it is usually 14 mm or more, preferably 16 mm or more, and more preferably 18 mm or more. The smaller the outer diameter of the conductive support, the greater the heat shrinkage when it is dried, which tends to put a burden on the photosensitive layer, etc., but when the photosensitive layer contains the polycarbonate resin, Compared to a small-diameter photoreceptor, printing durability and adhesion are improved, and the image quality is further improved. This may be because the adhesiveness at the interface between layers or between the layer and the support is improved, and the photosensitive layer is resistant to deformation.

  Examples of the material for the conductive support include a metal material such as aluminum, aluminum alloy, stainless steel, copper, and nickel, and a resin material imparted with conductivity by adding conductive powder such as metal, carbon, and tin oxide. Mainly used are resin, glass, paper, or the like obtained by depositing or coating a conductive material such as aluminum, nickel, ITO (indium-tin oxide) on the surface. As a form, a drum shape, a sheet shape, a belt shape, or the like is used regardless of the shape as long as it has a cylindrical shape. A conductive material having an appropriate resistance value may be applied on a conductive base made of a metal material for controlling conductivity, surface properties, etc., or for covering defects.

When a metal material such as an aluminum alloy is used as the conductive support, it may be used after anodizing, chemical conversion coating or the like. When the anodizing treatment is performed, it is desirable to perform a sealing treatment by a known method.
The surface of the support may be smooth, or may be roughened by using a special cutting method or performing a polishing treatment. Further, it may be roughened by mixing particles having an appropriate particle diameter with the material constituting the conductive support.

<Underlayer>
An undercoat layer may be provided between the conductive support and the photosensitive layer in order to improve adhesion and blocking properties.
As the undercoat layer, a resin, a resin in which particles such as a metal oxide are dispersed, or the like is used. Examples of metal oxide particles used for the undercoat layer include metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, titanium Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium acid and barium titanate. Only one type of particle may be used, or a plurality of types of particles may be mixed and used. Among these metal oxide particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicone. As the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. A thing of a several crystalline state may be contained.

In addition, various particle diameters of the metal oxide particles can be used. Among these, from the viewpoint of characteristics and liquid stability, the average primary particle diameter is preferably 10 nm to 100 nm, particularly preferably 10 nm to 50 nm. It is as follows.
The undercoat layer is preferably formed in a form in which metal oxide particles are dispersed in a binder resin. As binder resin used for the undercoat layer, phenoxy, epoxy, polyvinyl pyrrolidone, polyvinyl alcohol, casein, polyacrylic acid, celluloses, gelatin,
Starch, polyurethane, polyimide, polyamide and the like can be used alone or in a form cured with a curing agent. Among them, alcohol-soluble copolymerized polyamide, modified polyamide and the like are preferable because they exhibit good dispersibility and coatability.

The addition ratio of the inorganic particles to the binder resin can be arbitrarily selected, but it is preferably used in the range of 10 wt% to 500 wt% in terms of stability of the dispersion and coatability.
The thickness of the undercoat layer can be arbitrarily selected, but is preferably from 0.1 μm to 25 μm from the viewpoint of photoreceptor characteristics and applicability. Moreover, you may add a well-known antioxidant etc. to an undercoat layer.
<Charge generation layer>
When the electrophotographic photosensitive member of the present invention is a laminated type photosensitive member, examples of the charge generating material used in the charge generating layer include selenium and its alloys, cadmium sulfide, other inorganic photoconductive materials, phthalocyanine pigments, and azo pigments. Various photoconductive materials such as organic pigments such as quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone pigments, and benzimidazole pigments can be used, and organic pigments, phthalocyanine pigments, and azo pigments are particularly preferable. These fine particles are, for example, polyester resin, polyvinyl acetate, polyacrylate ester, polymethacrylate ester, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, epoxy resin, urethane resin, cellulose ester, cellulose ether. It is used in a form bound with various binder resins. The use ratio in this case is used in the range of 30 to 500 parts by mass with respect to 100 parts by mass of the binder resin, and the film thickness is usually 0.1 μm to 1 μm, preferably 0.15 μm to 0.6 μm.

When a phthalocyanine compound is used as the charge generation material, specifically, a metal such as metal-free phthalocyanine, copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, germanium, or an oxide or halide thereof. Phthalocyanines are used. Examples of the ligand to a metal atom having 3 or more valences include a hydroxyl group and an alkoxy group in addition to the oxygen atom and chlorine atom shown above. Particularly preferred are X-type, τ-type metal-free phthalocyanine, titanyl phthalocyanine such as A-type, B-type, and D-type, vanadyl phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine. Of the crystal forms of titanyl phthalocyanine mentioned here, A type and B type are described in W.W. It has been shown by Heller et al. As phase I and phase II, respectively (Zeit. Kristallogr. 159 (1982) 173), and type A is known as a stable type. The D-type is a crystal type characterized by a clear peak at a diffraction angle 2θ ± 0.2 ° of 27.3 ° in powder X-ray diffraction using CuKα rays. As the phthalocyanine compound, only a single compound may be used, or several mixed states may be used. As the mixed state that can be placed in the phthalocyanine compound or crystal state here, the respective constituent elements may be mixed and used later, or the mixed state in the production / treatment process of the phthalocyanine compound such as synthesis, pigmentation, crystallization, etc. It may be generated. As such treatment, acid paste treatment, grinding treatment, solvent treatment and the like are known. Moreover, in oxytitanium phthalocyanine, it is preferable that the chlorine content in a crystal | crystallization is 1.5 mass% or less. The chlorine content can be determined from elemental analysis. In the oxytitanium phthalocyanine crystal, the ratio of the chlorinated oxytitanium phthalocyanine represented by the following formula [L] is the mass spectral intensity ratio with respect to the unsubstituted oxytitanium phthalocyanine represented by the following formula [M]. 0.070 or less. The mass spectral intensity ratio is preferably 0.060 or less, more preferably 0.055 or less. In the production, when the dry grinding method is used for amorphization, 0.02 or more is preferable, and when the acid paste method is used for amorphization, 0.03 or less is preferable. The amount of chlorine substitution is measured based on the technique disclosed in Japanese Patent Application Laid-Open No. 2001-115054.

As the mixed state that can be placed in the phthalocyanine compound or crystal state here, the respective constituent elements may be mixed and used later, or the mixed state in the production / treatment process of the phthalocyanine compound such as synthesis, pigmentation, crystallization, etc. It may be generated. As such treatment, acid paste treatment, grinding treatment, solvent treatment and the like are known.

<Charge transport layer>
When the embodiment of the present invention is a multilayer photoreceptor, the charge transport layer contains a charge transport material and other components used as necessary, together with the binder resin containing the polycarbonate resin in the present invention. Specifically, such a charge transport layer is prepared by, for example, preparing a coating solution by dissolving or dispersing a charge transport material and a binder resin in a solvent. In addition, in the case of a reverse lamination type photosensitive layer, it can be obtained by coating and drying on a conductive support (or on the undercoat layer when an undercoat layer is provided).

The charge transport material is not particularly limited, and any material can be used. Examples of known charge transport materials include aromatic nitro compounds such as 2,4,7-trinitrofluorenone, cyano compounds such as tetracyanoquinodimethane, electron withdrawing materials such as quinone compounds such as diphenoquinone, and carbazole derivatives. , Indole derivatives, imidazole derivatives, oxazole derivatives, pyrazole derivatives, thiadiazole derivatives, heterocyclic compounds such as benzofuran derivatives, aniline derivatives, hydrazone derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives and multiple types of these compounds Or an electron donating substance such as a polymer having a group composed of these compounds in the main chain or side chain. Among these, carbazole derivatives, hydrazone derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives, and those in which a plurality of these compounds are bonded are preferable. Any one of these charge transport materials may be used alone, or two or more thereof may be used in any combination.
Specific examples of suitable structures of the charge transport material are shown below. These specific examples are shown for illustration, and any known charge transporting material may be used as long as it does not contradict the gist of the present invention.

Among these, CT-1, CT-2, CT-7, CT-13, ET-1, ET-2, and ET-3 are preferable from the viewpoint of electrical characteristics and applicability. These charge transport materials may be combined, and a combination of CT and ET is preferable.
The charge transport layer is formed in such a form that these charge transport materials are bound to the binder resin containing the polycarbonate resin of the present invention. The charge transport layer may be composed of a single layer, or may be a stack of a plurality of layers having different constituent components or composition ratios.

  As for the ratio of the binder resin to the charge transport material, the charge transport material is used in a ratio of 20 parts by mass or more with respect to 100 parts by mass of the binder resin. Among these, 30 parts by mass or more is preferable from the viewpoint of residual potential reduction, and 40 parts by mass or more is more preferable from the viewpoint of stability and charge mobility when repeatedly used. On the other hand, from the viewpoint of thermal stability of the photosensitive layer, the charge transport material is usually used at a ratio of 150 parts by mass or less. Among these, 110 parts by mass or less is preferable from the viewpoint of compatibility between the charge transport material and the binder resin, 80 parts by mass or less is more preferable from the viewpoint of printing durability, and 70 parts by mass or less is still more preferable from the viewpoint of scratch resistance.

The thickness of the charge transport layer is not particularly limited, but is usually 5 μm or more, preferably 10 μm or more, and usually 50 μm or less, preferably 45 μm or less, from the viewpoint of long life, image stability, and high resolution. Is in the range of 30 μm or less.
The charge transport layer has well-known plasticizers, antioxidants, ultraviolet absorbers, and electron withdrawing properties in order to improve film formability, flexibility, coating properties, stain resistance, gas resistance, light resistance, etc. You may contain additives, such as a compound, dye, a pigment, and a leveling agent. Examples of the antioxidant include hindered phenol compounds and hindered amine compounds. Examples of dyes and pigments include various pigment compounds and azo compounds.

<Dispersion type (single layer type) photosensitive layer>
In the case of a dispersion-type photosensitive layer, the above-described charge generating material is dispersed in the charge transport medium having the above-described blending ratio.
In this case, the particle size of the charge generating material needs to be sufficiently small, and is preferably 1 μm or less, more preferably 0.5 μm or less. If the amount of the charge generating material dispersed in the photosensitive layer is too small, sufficient sensitivity cannot be obtained, and if it is too large, there are adverse effects such as reduced chargeability and reduced sensitivity, for example, preferably 0.5 to 50 mass. %, More preferably 1 to 20% by mass.

  The film thickness of the photosensitive layer is usually 5 to 50 μm, more preferably 10 to 45 μm. Also in this case, known plasticizers for improving film formability, flexibility, mechanical strength, additives for suppressing residual potential, dispersion aids for improving dispersion stability, coatability Leveling agents and surfactants such as silicone oil, fluorine oil and other additives may be added to improve the viscosity.

A protective layer may be provided on the photosensitive layer for the purpose of preventing wear of the photosensitive layer or preventing or reducing deterioration of the photosensitive layer due to discharge products generated from a charger or the like.
Further, for the purpose of reducing frictional resistance and wear on the surface of the photoreceptor, the surface layer may contain a fluorine-based resin, a silicone resin, or the like. Moreover, the particle | grains which consist of these resin, and the particle | grains of an inorganic compound may be included.

<Method for preparing electrophotographic photoreceptor>
The method for preparing the electrophotographic photosensitive member to which the exemplary embodiment is applied is not particularly limited. Usually, each layer constituting the photosensitive member is a dip coating method, which is known as a method for forming a photosensitive layer of the electrophotographic photosensitive member, It is formed by coating on a support by a spray coating method, a nozzle coating method, a bar coating method, a roll coating method, a blade coating method or the like. Among these, the dip coating method is preferable because of its high productivity.
As a method for forming each layer, a known method such as sequentially applying a coating solution obtained by dissolving or dispersing a substance contained in a layer in a solvent can be applied.

<Image forming apparatus>
Next, an image forming apparatus used in the present invention will be described with reference to FIG. However, the embodiment is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention.
As shown in FIG. 1, the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device 2, an exposure device 3, a developing device 4, and a transfer device 5, and further includes a cleaning device 6 and a fixing device as necessary. A device 7 is provided.

The electrophotographic photoreceptor 1 is not particularly limited as long as it is an electrophotographic photoreceptor according to the present invention described above. In FIG. 1, as an example, the above-described photosensitive layer is formed on the surface of a cylindrical conductive support. A drum-shaped photoconductor is shown. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 6 are disposed along the outer peripheral surface of the electrophotographic photosensitive member 1.
The charging device 2 charges the electrophotographic photosensitive member 1 and uniformly charges the surface of the electrophotographic photosensitive member 1 to a predetermined potential. In FIG. 1, a roller-type charging device (charging roller) is shown as an example of the charging device 2, but other corona charging devices such as corotron and scorotron, and contact-type charging devices such as charging brushes are often used.

  In many cases, the electrophotographic photosensitive member 1 and the charging device 2 are designed to be removable from the main body of the image forming apparatus as a cartridge having both of them (hereinafter referred to as a photosensitive cartridge as appropriate). It is desirable to use in such a form. For example, when the electrophotographic photoreceptor 1 or the charging device 2 deteriorates, the photoreceptor cartridge can be removed from the image forming apparatus main body, and another new photosensitive cartridge can be mounted on the image forming apparatus main body. ing. Also, the toner described later is often stored in the toner cartridge and designed to be removable from the main body of the image forming apparatus. When the toner in the used toner cartridge runs out, this toner cartridge is removed. It can be removed from the main body of the image forming apparatus and another new toner cartridge can be mounted. Further, a cartridge equipped with all of the electrophotographic photosensitive member 1, the charging device 2, and the toner may be used. As will be described later, this image forming apparatus uses the toner of the present invention described above as the toner.

  The type of the exposure apparatus 3 is not particularly limited as long as it can expose the electrophotographic photoreceptor 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary. For example, the exposure may be performed using monochromatic light having a wavelength of 780 nm, monochromatic light having a wavelength slightly shorter than 600 nm to 700 nm, or monochromatic light having a wavelength shorter than 380 nm to 600 nm. .

  The type of the developing device 4 is not particularly limited, and an arbitrary device such as a dry development method such as cascade development, one-component conductive toner development, two-component magnetic brush development, or a wet development method can be used. In FIG. 2, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and has a configuration in which the toner T is stored inside the developing tank 41. . Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. The replenishing device is configured to be able to replenish toner T from a container such as a bottle or a cartridge.

The supply roller 43 is formed from a conductive sponge or the like. The developing roller 44 is made of a metal roll such as iron, stainless steel, aluminum, or nickel, or a resin roll obtained by coating such a metal roll with a silicone resin, a urethane resin, a fluorine resin, or the like. The surface of the developing roller 44 may be smoothed or roughened as necessary.
The developing roller 44 is disposed between the electrophotographic photoreceptor 1 and the supply roller 43 and is in contact with the electrophotographic photoreceptor 1 and the supply roller 43, respectively. The supply roller 43 and the developing roller 44 are
It is rotated by a rotation drive mechanism (not shown). The supply roller 43 carries the stored toner T and supplies it to the developing roller 44. The developing roller 44 carries the toner T supplied by the supply roller 43 and contacts the surface of the electrophotographic photosensitive member 1.

  The regulating member 45 is formed by a resin blade such as a silicone resin or a urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating such a metal blade with a resin. The regulating member 45 contacts the developing roller 44 and is pressed against the developing roller 44 side with a predetermined force by a spring or the like (general blade linear pressure is 0.05 to 5 N / cm). If necessary, the regulating member 45 may be provided with a function of imparting charging to the toner T by frictional charging with the toner T.

The agitator 42 is rotated by a rotation driving mechanism, and agitates the toner T and conveys the toner T to the supply roller 43 side. A plurality of agitators 42 may be provided with different blade shapes and sizes.
The type of the transfer device 5 is not particularly limited, and an apparatus using an arbitrary system such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method can be used. . Here, it is assumed that the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like that are disposed to face the electrophotographic photoreceptor 1. The transfer device 5 applies a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner T, and transfers the toner image formed on the electrophotographic photosensitive member 1 to a transfer material (paper, medium) P. Is.

  The cleaning device 6 is not particularly limited, and any cleaning device such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, or a blade cleaner can be used, but a blade cleaner is preferable from the viewpoint of effectiveness. The cleaning device 6 is for scraping off residual toner adhering to the photoreceptor 1 with a cleaning member and collecting the residual toner.

  The fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72. FIG. 1 shows an example in which a heating device 73 is provided inside the upper fixing member 71. As the upper and lower fixing members 71 and 72, known heat fixing members such as a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicon rubber, a fixing roll coated with a fluororesin, or a fixing sheet are used. be able to. Further, each of the fixing members 71 and 72 may be configured to supply a release agent such as silicone oil in order to improve releasability, or may be configured to forcibly apply pressure to each other by a spring or the like.

When the toner transferred onto the recording paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner is heated to a molten state and cooled after passing through the recording paper. Toner is fixed on P.
The type of the fixing device is not particularly limited, and a fixing device of any type such as heat roller fixing, flash fixing, oven fixing, pressure fixing, etc. can be provided including those used here.

In the image forming apparatus configured as described above, an image is recorded as follows. That is, first, the surface (photosensitive surface) of the photoreceptor 1 is charged to a predetermined potential (for example, −600 V) by the charging device 2. At this time, charging may be performed by a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.
Subsequently, the photosensitive surface of the charged photoreceptor 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. The developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photoreceptor 1.

The developing device 4 thins the toner T supplied by the supply roller 43 with a regulating member (developing blade) 45 and has a predetermined polarity (here, the same polarity as the charging potential of the photosensitive member 1) and the negative polarity. ), And conveyed while being carried on the developing roller 44 to be brought into contact with the surface of the photoreceptor 1.
When the charged toner T carried on the developing roller 44 comes into contact with the surface of the photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1. This toner image is transferred onto the recording paper P by the transfer device 5. Thereafter, the toner remaining on the photosensitive surface of the photoreceptor 1 without being transferred is removed by the cleaning device 6.

After the transfer of the toner image onto the recording paper P, the final image is obtained by passing the fixing device 7 and thermally fixing the toner image onto the recording paper P.
Since the image forming apparatus of the present embodiment uses the photoconductor of the present invention, it can be miniaturized and can realize high image quality of formed images without causing defective cleaning. It is.

In addition to the above-described configuration, the image forming apparatus may have a configuration capable of performing, for example, a static elimination process. The neutralization step is a step of neutralizing the electrophotographic photosensitive member by exposing the electrophotographic photosensitive member, and a fluorescent lamp, an LED, or the like is used as the neutralizing device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.
Further, the image forming apparatus may be further modified. For example, the image forming apparatus may be configured such that an auxiliary charging process or the like can be performed, offset printing may be performed, or a plurality of types of toner may be used. It is good also as a structure of a full color tandem system.

Hereinafter, the present embodiment will be described more specifically based on examples. In addition, the following examples are shown in order to describe the present invention in detail, and the present invention is not limited to the examples shown below unless it is contrary to the gist thereof. In addition, the description of “parts” in the following examples and comparative examples indicates “parts by mass” unless otherwise specified.
Here, the measurement of a viscosity average molecular weight is demonstrated.

A polycarbonate resin is dissolved in dichloromethane to prepare a solution having a concentration C of 6.00 g / L. The flow time t of the sample solution is measured in a constant temperature water bath set to 20.0 ° C. using an Ubbelohde capillary viscometer with a flow time t ₀ of the solvent (dichloromethane) of 136.16 seconds. The viscosity average molecular weight Mv is calculated according to the following formula.
a = 0.438 × η _sp +1 η _sp = t / t ₀ −1
b = 100 × η _sp / C C = 6.00 (g / L)
η = b / a
Mv = 3207 × η ^1.205

<Manufacture of photosensitive drum>
Example 1
A slurry obtained by mixing a rutile type titanium oxide having an average primary particle size of 40 nm (“TTO55N” manufactured by Ishihara Sangyo Co., Ltd.) and 3% by mass of methyldimethoxysilane with respect to the titanium oxide in a ball mill is dried, and further methanol is added. The hydrophobically treated titanium oxide obtained by washing and drying in (1) was dispersed in a methanol / 1-propanol mixed solvent by a ball mill to form a hydrophobized titanium oxide dispersion slurry, and the dispersed slurry, methanol / 1-propanol / toluene (mass ratio 7/1/2) mixed solvent and ε-caprolactam / bis (4-amino-3-methylcyclohexyl) methane / hexamethylenediamine / decamethylenedicarboxylic acid / octadecamethylene Copolymerization polymer comprising dicarboxylic acid (composition mol% 75 / 9.5 / 3 / 9.5 / 3) After stirring and mixing with the amide pellets while heating to dissolve the polyamide pellets, an ultrasonic dispersion treatment is performed to obtain a solid content containing hydrophobically treated titanium oxide / copolymerized polyamide at a mass ratio of 3/1. A dispersion having a concentration of 18.0% was obtained.

The undercoat layer-forming coating solution thus obtained is dip-coated on an aluminum cylinder having an outer diameter of 20 mm, a length of 246 mm, and a wall thickness of 0.80 mm, and the film thickness after drying becomes 2.0 μm. As a result, an undercoat layer was obtained.
Next, a coating solution for forming a charge generation layer was prepared as follows. As a charge generation substance, 20 parts of oxytitanium phthalocyanine shown in the X-ray diffraction spectrum of FIG. 2 and 280 parts of 1,2-dimethoxyethane were mixed, and pulverized with a sand grind mill for 1 hour for atomization dispersion treatment. Subsequently, 10 parts of polyvinyl butyral (trade name “Denkabutyral” # 6000C, manufactured by Denki Kagaku Kogyo Co., Ltd.) were added to 255 parts of 1,2-dimethoxyethane and 4-methoxy-4-. A binder solution obtained by dissolving in 85 parts of a mixture of methyl-2-pentanone and 230 parts of 1,2-dimethoxyethane were mixed to prepare a coating solution A for forming a charge generation layer.

  Further, as a charge generation material, 20 parts of oxytitanium phthalocyanine and 280 parts of 1,2-dimethoxyethane shown in the X-ray diffraction spectrum of FIG. It was. Subsequently, 10 parts of polyvinyl butyral (trade name “Denkabutyral” # 6000C, manufactured by Denki Kagaku Kogyo Co., Ltd.) were added to 255 parts of 1,2-dimethoxyethane and 4-methoxy-4-. A binder solution obtained by dissolving in 85 parts of a mixture of methyl-2-pentanone and 230 parts of 1,2-dimethoxyethane were mixed to prepare a coating solution B for forming a charge generation layer.

The charge generation layer forming coating solution A and the charge generation layer forming coating solution B were mixed at a ratio of 1: 1 to prepare a charge generation layer forming coating solution.
The charge generation layer coating formation dispersion was dip coated with a cylinder on which an undercoat layer had previously been formed, and a charge generation layer was formed so that the thickness after drying was about 0.4 μm.
Next, 50 parts of a charge transport material composed of an isomer mainly composed of the following structure shown in JP-A-2002-80432, a repeating unit (1- 1) 100 parts of the polycarbonate resin according to the present invention (viscosity average molecular weight 50,000), 3,5-di-t-butyl-4-hydroxytoluene 8 parts as an antioxidant, 0.1 part of tribenzylamine, As a leveling agent, 0.05 part of silicone oil was mixed with 640 parts of a mixed solvent of tetrahydrofuran and toluene (tetrahydrofuran 80 mass%, toluene 20 mass%) to prepare a coating solution for forming a charge transport layer.

The cylinder on which the charge generation layer was previously formed was dip coated on this charge transport layer forming coating solution to form a 17 μm thick charge transport layer after drying. The photoreceptor drum thus obtained is referred to as a photoreceptor A1.
Example 2
The polycarbonate resin composed of the repeating unit (1-1) used in the coating liquid for forming the charge transport layer of Example 1 was converted to a polycarbonate resin composed of the repeating unit (1-2) having the following structure (viscosity average molecular weight 50,000). Except for the above, a photoconductive drum was produced in the same manner as the photoconductor 1. The photoreceptor drum thus obtained is referred to as a photoreceptor B1.

Comparative Example 1
The photosensitive drum was prepared in the same manner as in Example 1 except that the resin used in the coating solution for forming the charge transport layer was a resin (viscosity average molecular weight 50,000) represented by a repeating unit (bisphenol Z) having the following structure. Was made. The photoreceptor drum thus obtained is referred to as a photoreceptor C1.

Comparative Example 2
A photosensitive drum was produced in the same manner as in Example 1 except that the resin used for the coating solution for forming the charge transport layer was a resin (viscosity average molecular weight 50,000) represented by the following structural formula (2). . The photoreceptor drum thus obtained is referred to as a photoreceptor D1.

Comparative Example 3
A photosensitive drum was produced in the same manner as in Example 1 except that the resin used for the coating solution for forming the charge transport layer was a resin (viscosity average molecular weight 22,000) represented by the following structural formula (3). . The photoreceptor drum thus obtained is referred to as a photoreceptor E1.

Comparative Example 4
A photoconductor drum was produced in the same manner as in Example 1 except that the resin used for the coating liquid for forming the charge transport layer was a resin represented by the following structural formula (4) (viscosity average molecular weight 50,200). . The photoreceptor drum thus obtained is referred to as a photoreceptor F1.

The manufactured photoreceptor drums A1 to F1 were subjected to the following electrical property test, adhesion test, and image property test (including wear test). These results are summarized in Table 1.
<Electrical characteristics test>
Using an electrophotographic characteristic evaluation apparatus manufactured in accordance with the Japan Imaging Society measurement standard (basic and applied electrophotographic technology, edited by the Japan Imaging Society, Corona, page 404-405), the photosensitive drum is rotated at a constant speed. It was rotated at 120 rpm, and an electrical property evaluation test was performed by a cycle of charging, exposure, potential measurement, and static elimination. At that time, the surface after 100 ms is obtained when the photosensitive member is charged so that the initial surface potential is −700 V, and the light of the halogen lamp is exposed to 780 nm monochromatic light with an interference filter at 2.0 μJ / cm ^2. The potential (hereinafter sometimes referred to as VL) was measured. The measurement environment was a temperature of 25 ° C. and a relative humidity of 50%. The smaller the value of VL, the better.

<Adhesion test>
On the photosensitive drum, using an NT cutter, 11 pieces were cut at intervals of 1 mm in both the circumferential direction and the axial direction to produce 10 × 10 100 squares. Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.) was applied from above, and the adhesiveness of the photosensitive layer was tested by pulling it up to 45 °. The number of cells of the photosensitive layer remaining on the support is evaluated, and the larger the number of cells remaining, the better.

<Image characteristics test>
A flange was attached to the photosensitive drum, and it was set on a monochrome printer ML-1630 (adopting a blade cleaning method) manufactured by Samsung, 2000 continuous printing was performed, and then a halftone image was output. If the cleaning is not successful due to the printing of 2000 sheets, the image smears due to toner slipping.

  Further, the film thickness of the photosensitive layer worn by printing 2000 sheets was measured.

Example 3
A photoconductive drum was produced in the same manner as in Example 1 except that the aluminum cylinder used had an outer diameter of 24 mm, a length of 248 mm, and a wall thickness of 0.75 mm. The photoreceptor drum thus obtained is referred to as a photoreceptor A2.
Example 4
A photosensitive drum was produced in the same manner as in Example 2, except that the aluminum cylinder used had an outer diameter of 24 mm, a length of 248 mm, and a wall thickness of 0.75 mm. The photoreceptor drum thus obtained is referred to as a photoreceptor B2.

Comparative Example 5
A photoconductive drum was produced in the same manner except that the aluminum cylinder used in Comparative Example 3 had an outer diameter of 24 mm, a length of 248 mm, and a wall thickness of 0.75 mm. The photoreceptor drum thus obtained is referred to as a photoreceptor C2.
Comparative Example 6
A photoconductive drum was produced in the same manner except that the aluminum cylinder used in Comparative Example 4 had an outer diameter of 24 mm, a length of 248 mm, and a wall thickness of 0.75 mm. The photoreceptor drum thus obtained is referred to as a photoreceptor D2.

Comparative Example 7
The aluminum cylinder used in Comparative Example 5 has an outer diameter of 24 mm, a length of 248 mm, and a wall thickness of 0.
. A photoconductor drum was produced in the same manner except that a 75 mm one was used. The photoreceptor drum thus obtained is referred to as a photoreceptor E2.
Comparative Example 8
A photoconductive drum was produced in the same manner except that the aluminum cylinder used in Comparative Example 6 had an outer diameter of 24 mm, a length of 248 mm, and a wall thickness of 0.75 mm. The photoreceptor drum thus obtained is referred to as a photoreceptor F2.
The manufactured photoreceptor drums A2 to F2 were subjected to the following electrical property test, adhesion test, and image property test (including wear test). These results are summarized in Table 2.

<Electrical characteristics test>
It implemented by the method similar to Example 1, 2 and Comparative Examples 1-4.
<Adhesion test>
It implemented by the method similar to Example 1, 2 and Comparative Examples 1-4.

<Image characteristics test>
The same procedure as in Examples 1 and 2 and Comparative Examples 1 to 4 was performed except that the printer used was a monochrome printer ML-1610 manufactured by Samsung (adopting a blade cleaning method) and the number of prints was 3000.

Reference example 1
A photosensitive drum was produced in the same manner as in Example 1 except that the aluminum cylinder used had an outer diameter of 30 mm, a length of 248 mm, and a wall thickness of 0.75 mm. The photoreceptor drum thus obtained is referred to as a photoreceptor A3.
Reference example 2
A photosensitive drum was produced in the same manner as in Example 2, except that the aluminum cylinder used had an outer diameter of 30 mm, a length of 248 mm, and a wall thickness of 0.75 mm. The photoreceptor drum thus obtained is referred to as a photoreceptor B3.

Reference example 3
A photoconductive drum was produced in the same manner except that the aluminum cylinder used in Comparative Example 1 had an outer diameter of 30 mm, a length of 248 mm, and a wall thickness of 0.75 mm. The photoreceptor drum thus obtained is referred to as a photoreceptor C3.
Reference example 4
A photoconductive drum was produced in the same manner except that the aluminum cylinder used in Comparative Example 2 had an outer diameter of 30 mm, a length of 248 mm, and a wall thickness of 0.75 mm. The photoreceptor drum thus obtained is referred to as a photoreceptor D3.

Reference Example 5
A photoconductive drum was produced in the same manner except that the aluminum cylinder used in Comparative Example 3 had an outer diameter of 30 mm, a length of 248 mm, and a wall thickness of 0.75 mm. The photoreceptor drum thus obtained is referred to as a photoreceptor E3.
Reference Example 6
A photoconductive drum was produced in the same manner except that the aluminum cylinder used in Comparative Example 4 had an outer diameter of 30 mm, a length of 248 mm, and a wall thickness of 0.75 mm. The photoreceptor drum thus obtained is designated as a photoreceptor F3.
The manufactured photoreceptor drums A3 to F3 were subjected to the following electrical property test, adhesion test, and image property test. These results are summarized in Table 3.

<Electrical characteristics test>
It implemented by the method similar to Example 1, 2 and Comparative Examples 1-4.
<Adhesion test>
It implemented by the method similar to Example 1, 2 and Comparative Examples 1-4.

<Image characteristics test>
The same procedure as in Examples 1 and 2 and Comparative Examples 1 to 4 was performed except that the printer used was a monochrome printer ML-6040 (adopting a blade cleaning method) manufactured by Samsung.

As can be seen from Table-3, when using a photosensitive drum with an outer diameter of 30 mm, the structure of the resin used for the photosensitive layer is not affected at all by the adhesiveness to the support and improves image contamination due to poor cleaning. There is a wide range of resin choices to do.
However, as can be seen from the results of the outer diameter of 20 mm in Table-1 and the results of the outer diameter of 24 mm in Table-2, the smaller the outer diameter, the tighter the adhesiveness, and the selectable resins are limited. .

In the past, downsizing of printers has not attracted attention, so photoconductors with an outer diameter of 30 mm have been the mainstream. However, space saving in offices and the like has become important recently, and the outer diameter should be 25 mm or less. Has become important. There is no sufficient knowledge about this new problem, and no resin has been found that can improve adhesiveness while maintaining good electrical characteristics, cleanability, and abrasion resistance. Abrasion and adhesion can be compatible.

  In particular, in order to improve the abrasion resistance, it was thought that only the polyarylate resin could be solved after sacrificing the adhesiveness. It has been found that it is possible to improve the abrasion resistance while maintaining it and to obtain a photoreceptor having good cleaning characteristics.

Claims (4)

An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the conductive support has a cylindrical shape having an outer diameter of 25 mm or less, and the photosensitive layer is represented by the following general formula (1) An electrophotographic photoreceptor comprising a copolymer polycarbonate resin containing

The electrophotographic photosensitive member according to claim 1, wherein the component of the polycarbonate resin satisfies the following relational expression.
n / (m + n) = 0.35-0.45   The electrophotographic photosensitive member according to claim 1, wherein an outer diameter of the conductive support is 22 mm or less.   An image forming apparatus on which the electrophotographic photosensitive member according to any one of claims 1 to 3 is mounted.

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