JP4597837B2 - Image forming method, image forming apparatus, and electrophotographic cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having high durability in long-term repetitive image formation and capable of giving stable high-quality images, and to provide an electrophotographic method. <P>SOLUTION: The image forming method includes a step of forming an electric field between an image bearing member and a cleaning member by applying a voltage to the cleaning member, and a step of attracting toner on the image bearing member to the cleaning member, wherein the image bearing member has at least a photosensitive layer having a crosslinked charge transport layer in a surface, wherein the crosslinked charge transport layer is formed by curing at least a trifunctional or higher functionality radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to an electrophotographic photosensitive member having a crosslinked surface layer, a cleaning device using electrostatic force, and an image forming method using toner having a uniform particle size and high circularity.

  The electrophotographic method applied to copying machines, laser printers, etc. is a method of charging a toner image onto a transfer medium after charging, exposing, and developing a toner on an electrophotographic photosensitive member (hereinafter also referred to as an image bearing member or simply a photosensitive member). And fixing and obtaining a stable image. After the transfer, the electrophotographic photosensitive member is cleaned for residual toner on the surface and used for the next repeated use. The greatest feature of this electrophotographic method is that the photoreceptor can be used repeatedly, and no complicated plate making is required. For this reason, an image forming apparatus using an electrophotographic method has been widely used for office work. In recent years, laser printers using a small and low-cost electrophotographic method have been developed as output devices for personal computers. Furthermore, there is a demand for easily obtaining a color image, and a color laser printer with high definition and high stability is desired.

  In general, an organic photoreceptor using an organic photoconductive material is used as the photoreceptor. For example, a photoconductive polymer such as polyvinyl carbazole (PVK), a single layer type organic photoreceptor using a charge transfer complex such as PVK-TNF (2,4,7-trinitrofluorenone), and an azo pigment phthalocyanine pigment There is known a function-separated type photoreceptor in which a charge transport layer containing a charge transfer material typified by a compound having a triphenylamine structure is laminated on a charge generation layer containing a photoconductive material. This function-separated type photoconductor has become mainstream because it can use a material having high design sensitivity, low cost, easy disposal, etc., and a high sensitivity to the laser emission wavelength.

  However, such an organic photoreceptor has a weak point. For example, mechanical durability and chemical durability are poor compared to inorganic photoreceptors. When the surface layer of the photosensitive layer is a charge transfer layer, the charge transfer layer is usually formed by dispersing and mixing a charge transfer substance, which is a low molecular compound, in a polymer compound to impart film formability. Insufficient strength for repeated use. In particular, when the organophotoreceptor is exposed to a developing unit employing a two-component developer, when it is in contact with paper as a transfer medium in the transfer process, or when it is rubbed with a cleaning blade in the cleaning process Alternatively, it is known that the charge transfer layer wears due to insufficient strength when it comes into contact with the charging roller when contact charging is used in the charging step.

Moreover, usually, for use corona charging method the charging of the organic photoreceptor, ozone, charge products such as NO _X is continuously generated. These are chemically active, accumulate on or react with the surface of the organophotoreceptor, and some penetrate into the interior of the photosensitive layer and have various adverse effects on electrostatic properties or image properties. In particular, when moisture in the air is absorbed by a charged product on the surface of the photoconductor or a substance generated by a reaction between this and the material on the surface of the photoconductor at high humidity, the surface resistance decreases, image flow or image blurring, etc. It is known that an abnormal image is generated. This can be a fatal defect for high definition color images.

  Many improvements have been made to the lack of mechanical durability. For example, the cleaning blade used in the cleaning process is said to give the maximum load to the electrophotographic photosensitive member, but there is a method of using a brush with little wear even at high cost. In Patent Documents 1 to 3, there is a method of reducing the shearing force of the blade by controlling the surface friction coefficient within an appropriate range. Furthermore, a method of adding a lubricant to the toner and supplying it to the surface of the photoreceptor, a method of providing a lubricant supply source in the cleaning process and supplying the lubricant from the outside of the organic photoreceptor, and the like can be mentioned. Furthermore, there is a method of adding a lubricant to the surface of the organic photoreceptor. However, neither method is satisfactory.

Further, most of the chemical durability is caused by the aforementioned corona charging used for charging and transfer. In recent years, a contact charging method or a transfer method in which charging is performed using a contact member is used. Patent Documents 4 and 5 show a method in which a voltage is applied to a brush, roller, blade, or the like having appropriate conductivity and elasticity to bring it into contact with the surface of the photoreceptor, and charging and transfer are performed. These contact charging system, compared with the non-contact charging method, charging the photosensitive member, since the voltage at which the transfer can be reduced, a small amount of generated ozone or NO _X. As a result, there is an advantage that chemical deterioration of the photoreceptor can be reduced. As an intermediate method, a proximity charging method in which a minute gap is provided between the charging member and the photoconductor and charging is performed by applying a direct current or a direct current voltage on which an alternating current is superimposed has begun to be adopted. However, ozone also by the method of these charge, the amount of the NO _X is not nil, it was not sufficient to further increase the durability and high stabilization of the photoreceptor.

  Furthermore, in the case of a tandem high-speed color printer that forms a color image by sequentially forming four colors on a transfer medium, the amount of wear on each photoconductor is not uniform, and the sensitivity of each photoconductor changes. Color balance is lost. If even one color causes image blurring, the quality of the color image is significantly degraded. When repeated at a high speed for a long time, the amount of wear increases. As a result, the photoconductor is frequently replaced, and the convenience of the electrophotographic method becomes poor. For this reason, a protective layer has conventionally been provided on the organic photoreceptor. Various additives have been used for the photosensitive layer and the protective layer. For example, as in Patent Document 7, a fluorine-containing resin is contained or dispersed in the protective layer and the photosensitive layer, and the surface energy is controlled to improve mechanical and chemical durability. However, it is still insufficient. is there.

  On the other hand, it has been found that a toner having a small particle size and a spherical shape is an effective means for improving the image quality. Such a toner is manufactured by a polymerization method, but the toner by the polymerization method has a sharper particle size distribution than that of the pulverization method, and can easily encapsulate wax, which greatly improves the fluidity of the toner. You can also Further, the spherical toner can be easily obtained by controlling the shape.

  However, it is known that there are some problems with spherical toners with small particle sizes by polymerization. The biggest problem is in the cleaning process. It is difficult to completely remove the transfer residual toner on the surface of the photoreceptor, resulting in poor cleaning. This is because the toner is close to the closest packed state between the contact portion of the photosensitive member and the cleaning blade during cleaning, and the toner between the first layer toner and the second layer toner having strong adhesion to the photosensitive member. It is said that the first-layer toner slips and remains as a defective cleaning. Also, in high-speed image formation, the tip of the blade cannot contact the photoreceptor smoothly, and the tip of the blade is slightly turned up. As a result, it is said that the cleaning performance of this portion is lowered, and the toner having a small particle diameter slips through.

  In order to solve this problem, for example, in Patent Document 7, a conductive member is used for the cleaning blade, and an AC voltage and a DC voltage having the same polarity as the charged charge of the toner at the time of development are applied to the remaining part of the photoreceptor. A method for removing toner is shown. Further, as disclosed in Patent Document 8, a method is disclosed in which a conductive member is used for the cleaning blade and this is grounded. Alternatively, there is a method of applying a DC voltage having a polarity opposite to that of the residual toner. Alternatively, a method of applying a DC voltage having the same polarity as the residual toner is shown.

  However, since these are all cleaned by contacting the cleaning blade with the photosensitive member and scraping off the residual toner, in the case of a toner using a low melt viscosity, sharp melt polyester binder resin, Wax in the vicinity of the surface of the toner oozes out to the surface by the pressure of the cleaning blade and is rubbed against the photoreceptor, so-called wax filming occurs. It is known that the occurrence of wax filming on the photoconductor adversely affects various image characteristics depending on conditions. For example, if the coefficient of friction of the photoreceptor decreases, the adhesion between the surface of the photoreceptor and the toner decreases. As a result, the toner on the photoconductor is easily abnormally transferred to the transfer medium by discharge before the nip between the transfer medium such as paper and the photoconductor, and an abnormal image called so-called transfer dust is generated.

Not only this wax filming, but also various filming caused by foreign matter adhering to the surface of the photoreceptor, all cause deterioration in image quality, even if they differ in degree. In addition, deterioration of the surface of the photoreceptor itself that is exposed to charging for a long time is also a problem. In order to solve this problem, Patent Document 11 proposes a removal method using a polishing means that is stable over time. However, when this polishing means is applied to a soft organic photoreceptor, there is a problem that it is excessively scraped. Also, the abrasive particles of the polishing means damage the surface of the organic photoreceptor. On the other hand, a method of using a reinforced photosensitive layer containing alumina as a filler on the surface has been proposed, but it is known that there are various side effects in dispersing and containing the filler itself.
JP-A-6-342236 JP-A-8-202226 Japanese Patent Laid-Open No. 9-81001 JP-A 63-149668 Japanese Patent Laid-Open No. 7-281503 JP 7-84394 A JP-A-5-265360 JP-A-7-210053 JP 2004-117419 A

  SUMMARY OF THE INVENTION A first object of the present invention is to provide an electrophotographic method and an image forming apparatus using the same which can obtain a durable and stable high-quality image for long-term repeated image formation. A second object of the present invention is an electrophotographic method which does not cause cleaning failure when a spherical toner having a small particle diameter is used, and has a long maintenance interval in which filming such as wax filming does not occur. To provide a color image forming method, an electrophotographic apparatus, and a process cartridge.

  In order to solve the above problems, it has been found that the following embodiments are preferable.

  The first requirement is that an electrophotographic photoreceptor (also called a photoreceptor or an image carrier) has at least a crosslinkable charge transport layer (also called a surface layer or a crosslinkable surface layer) on the surface, both of which have charge transportability. A radically polymerizable monomer having at least a charge transporting structure and a radically polymerizable compound having a charge transporting structure are cured. The electrophotographic photosensitive member formed by the above method is used. This electrophotographic photosensitive member has high wear resistance, is less likely to be scratched and hardly scratches, but has the property of being scraped very slightly as image formation is repeated. As a result, the charged product generated from the charging step is not accumulated on the outermost surface, or the degenerated material in the surface area of the electrophotographic photosensitive member is removed little by little, and the surface is constantly renewed.

  In addition, because the cleaning that uses an electric field to adsorb the toner is used, or when a cleaning blade is used, the cleaning assisting means that adsorbs the toner using the electric field is also used. Never give. Also, a polishing means that actively polishes the surface of the photoreceptor can be used without causing deterioration in image quality. As a result, the electrophotographic image forming method is highly durable and highly stable over a long period of time.

  The second requirement is that when using a small-diameter spherical toner, the most difficult cleaning is achieved by applying a voltage between the cleaning means and the photosensitive member and adsorbing the transfer residual toner by the action of an electric field as described above. It is to suppress cleaning defects in the process. As a result, it is possible to obtain an image in which an image defect due to residual toner is eliminated.

  The third requirement is that the volume average particle diameter of the toner is 3 to 9 μm, and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) is 1.01 to 1.25. And a toner having an average circularity of 0.950 or more and less than 1.00.

  Thereby, a high-definition image can be formed. Furthermore, by using urea-modified polyester with highly dispersed pigment as the binder resin and using a small particle size spherical toner with a sharp particle size distribution, it has excellent fluidity, low temperature fixability, and hot offset resistance. And a glossy and highly transparent color image can be obtained.

  If it demonstrates in detail below, this invention will achieve the said subject by following (1)-(30).

  (1) An image forming method including a step of applying a voltage to the cleaning unit to form an electric field between the image carrier and the cleaning unit, and a step of adsorbing the toner on the image carrier to the cleaning unit. The image carrier has a photosensitive layer having at least a cross-linked charge transport layer on the surface, and the cross-linked charge transport layer has at least a trifunctional or higher-functional charge transporting structure and a charge. An image forming method comprising curing a radically polymerizable compound having a transporting structure.

  (2) The crosslinked charge transport layer is formed by curing at least a plurality of trifunctional or higher functional radical polymerizable monomers not having a charge transport structure and a radical polymerizable compound having a charge transport structure. The image forming method as described in (1) above, wherein

  (3) The crosslinked charge transport layer is formed by curing at least a monofunctional and trifunctional or higher radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure, Alternatively, it is formed by curing a bifunctional or trifunctional or higher radical polymerizable monomer having no charge transporting structure and a radical polymerizable compound having a charge transporting structure. Image forming method.

  (4) The crosslinked charge transport layer is formed by curing at least a radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a monofunctional charge transport structure. The image forming method according to any one of (1) to (3) above.

  (5) The image forming method as described in any one of (1) to (4) above, wherein the thickness of the crosslinked charge transport layer is from 1 μm to 20 μm.

  (6) The image forming method as described in any one of (1) to (5) above, wherein the radical polymerizable monomer has an acryloyloxy group and / or the methacryloyloxy group.

  (7) At least one of the radically polymerizable monomers having no charge transporting structure is a radically polymerizable monomer having no charge transporting structure represented by the following general formula (A): The image forming method according to 6).

（式中、Ｒ_７１、Ｒ_７２、Ｒ_７３、Ｒ_７４、Ｒ_７５、Ｒ_７６は水素又は一般式（Ｂ）で示されるグループを示し、Ｒ_７７は単結合、アルキレン基、アルキレンエーテル基、又はアルキレンオキシカルボニル基を示し、Ｒ_７８は水素又はメチル基を示す。）

(Wherein R ₇₁ , R ₇₂ , R ₇₃ , R ₇₄ , R ₇₅ , R ₇₆ represent hydrogen or a group represented by the general formula (B), and R ₇₇ represents a single bond, an alkylene group, an alkylene ether group, or Represents an alkyleneoxycarbonyl group, and R ₇₈ represents hydrogen or a methyl group.)

（８）前記Ｒ_７１、Ｒ_７２、Ｒ_７３、Ｒ_７４、Ｒ_７５、Ｒ_７６のうち、一般式（Ｂ）で示されるグループが５つ或いは６つ占め、残りを水素が占めることを特徴とする上記（７）に記載の画像形成方法。

(8) Of the R ₇₁ , R ₇₂ , R ₇₃ , R ₇₄ , R ₇₅ , and R ₇₆ , the group represented by the general formula (B) occupies 5 or 6 and the remaining is hydrogen. The image forming method according to (7) above.

  (9) The radical polymerizable functional group of the trivalent or higher functional radical polymerizable monomer having no charge transport structure and the radical polymerizable compound having a charge transport structure used in the crosslinked charge transport layer is an acryloyloxy group and / or The image forming method according to any one of (1) to (8) above, which is a methacryloyloxy group.

  (10) The image forming method according to any one of (1) to (9), wherein the cleaning unit includes a toner polarity control unit upstream of the cleaning unit.

  (11) The image forming method according to (10), wherein the cleaning unit is an elastic roller.

  (12) The cleaning unit is a brush roller, and a DC voltage having a polarity opposite to the polarity of toner, an AC voltage, or a DC on which an AC voltage is superimposed is applied to the brush roller. The image forming method described in 1.

  (13) Any one of the above (1) to (9), wherein the cleaning means includes an upstream brush roller and a downstream brush roller, and voltages having different polarities are applied to the brush roller. The image forming method described in 1.

  (14) The image forming method as described in (13) above, wherein a DC voltage having a polarity opposite to the polarity of toner, an AC voltage, or a DC on which an AC voltage is superimposed is applied to the brush roller.

  (15) The image forming method according to any one of (1) to (9), wherein the cleaning unit includes a cleaning blade and at least two cleaning auxiliary units upstream of the cleaning blade.

  (16) The image forming method as described in (15) above, wherein the cleaning auxiliary means is a plurality of rotatable brush rollers having a cleaning device.

  (17) The image forming method as described in (15) or (16) above, wherein the resistance values of the at least two cleaning auxiliary means are the same and have high resistance.

  (18) The image forming method as described in (15) above, wherein the cleaning auxiliary means is a rotatable brush roller having a cleaning device and a fixed brush.

  (19) The image forming method according to (15), wherein the cleaning auxiliary means is a rotatable brush roller having a cleaning device and a sheet-like elastic member.

  (20) The image forming method as described in any one of (15), (18), and (19) above, wherein the resistance values of the at least two cleaning assisting means are different.

  (21) The resistance value of the most upstream cleaning auxiliary means is lower than that of the downstream cleaning auxiliary means (15), (16), (18), (19), or (20 The image forming method according to any one of the above.

  (22) The image forming method as described in any one of (15) to (21) above, wherein DC voltages having different polarities are applied to the cleaning auxiliary means.

  (23) A voltage obtained by superimposing an AC voltage on a DC voltage is applied to the cleaning auxiliary means disposed on the most upstream side, and a DC voltage is applied to the other cleaning auxiliary means. (15) The image forming method according to any one of (22).

  (24) The image forming method as described in any one of (15) to (23) above, wherein an input toner amount of the cleaning blade is 0.05 mg / cm 2 or less.

  (25) The image forming method as described in any one of (15) to (24) above, wherein the cleaning blade is a polishing blade.

  (26) The volume average particle diameter of the toner is 3 μm or more and 9 μm or less, and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) of the toner is 1.01 or more and 1 The image forming method as described in any one of (1) to (25) above, wherein the toner has an average circularity of 0.950 or more and less than 1.00.

  (27) The image forming method as described in (26) above, wherein the toner contains at least a modified polyester as a toner binder, and wax is finely dispersed inside the toner.

  (28) The image forming method as described in (27) above, wherein the modified polyester is a modified polyester having a urea group.

  (29) An image forming apparatus that executes the image forming method according to any one of (1) to (28).

  (30) An electrophotographic cartridge, wherein the image forming method according to any one of (1) to (28) is executed.

  The inventors have studied an image forming method in which a spherical toner having a small particle diameter and containing a polyester-based binder resin and a wax, which can stably obtain high image quality over a long period of time and has excellent low-temperature fixability, has been studied. As a result, it was concluded that in order to obtain good cleaning performance, it is better to form an image with a considerable degree of mechanical stress in the image forming process. However, it is important to minimize the stress, and a method of applying stress to the photoreceptor without applying such stress to the toner was selected. Therefore, the first is cleaning by electrostatic force, and the second is the method of selecting a cross-linked charge transport layer that is mechanically flexible and thick and tough as the surface of the photoreceptor. did. Therefore, it is excellent in suppressing wax filming particularly in image formation using a spherical toner having a small particle diameter using the above-mentioned urea-modified polyester resin as a binder resin. A polishing blade can be employed as a polishing means for easy removal.

(1) Since the cleaning method using electrostatic force due to the electric field is employed, or because the cleaning auxiliary means for cleaning with a plurality of electrostatic forces is employed upstream of the cleaning blade, the toner or the photosensitive member is excessive. Does not give mechanical stress. As a result, wax filming caused by the seeping out of the wax dispersed in the toner is suppressed, and the wear durability of the photoreceptor is improved, so that a high-quality image stable for long-term repeated image formation can be obtained.
(2) Toner having a sharp particle size distribution with a volume average particle size Dv of 3 to 9 μm, a small particle size of Dv / Dp 1.01 to 1.25 and an average circularity of 0.950 or more and less than 1.00 Since the particles can be cleaned, a high-quality image free from image defects due to poor cleaning can be obtained.
(3) In long-term repeated image formation in a high-temperature and high-humidity environment, a high-quality image with no image flow can be obtained.
(4) Since the photoconductor is slightly worn while having a high surface strength, foreign matter polishing means such as filming can be used effectively, so that stable printout is always made in long-term repeated image formation. .
(5) Even if a polishing blade as a polishing means is employed, cracking or peeling of the photosensitive layer is suppressed.

  The present invention is described in further detail below.

  In the present invention, by applying a voltage as a cleaning unit, an electric field that is electrostatically adsorbed between the electrophotographic photosensitive member and the cleaning unit is formed, and cleaning is performed to clean the toner adhering to the electrophotographic photosensitive member. An image forming method using an apparatus, wherein the electrophotographic photosensitive member is provided with a photosensitive layer having a crosslinked charge transport layer on at least a surface thereof, and the crosslinked charge transport layer has at least a charge transport structure. By adopting an image forming method formed by crosslinking and curing a polymerizable monomer and a radical polymerizable compound having a charge transporting structure, the above-mentioned problems are solved. As the radical polymerizable monomer having no charge transporting structure, a tri- or higher functional monomer is preferable. In particular, it is preferable to use a plurality of trifunctional or higher functional groups. Furthermore, it is preferable to use a monofunctional one or a bifunctional one and a trifunctional or higher one at the same time. In the present invention, the number of functional groups of the radical polymerizable compound having a charge transporting structure is not limited, but monofunctional to trifunctional functions can be usually used. Monofunctional ones are particularly preferable.

  Although the reason for this is not clear, for example, a case where the radical polymerizable monomer having no charge transporting structure is monofunctional is considered and the effect is considered. When the crosslinked charge transport layer coating solution is applied onto the charge transport layer of the present invention to form a crosslinked charge transport layer, most of the solvent in the coating solution is volatilized, and this monomer having a boiling point higher than that of the solvent remains. It will be. This monomer is considered to provide a degree of freedom of molecular level movement or diffusion of the composition present in the crosslinked charge transport layer before curing, or to ensure microfluidity. In addition, the monofunctional monomer moderately participates in a chain reaction related to curing and contributes to an improvement in the crosslinking density. Conventionally, there are cases where residual solvents (low molecular weights that do not have radical reactivity) are preferred for crosslinking and curing. However, in practice, it is extremely difficult for production management to leave an appropriate amount of solvent during curing. The non-reactive solvent is an obstacle to the chain reaction and basically becomes an unstable factor. This is not limited to monofunctional monomers. For example, in the case of trifunctional and hexafunctional monomers, it is considered that the trifunctional monomer serves as a reactive diluent. It is expected to be common in using radically polymerizable monomers that do not have multiple charge transporting structures. In particular, it is considered that this effect is enhanced by mixing a plurality of monomers having a functional group number of 2 or more. However, in order to increase the crosslink density of the crosslinkable charge transport layer after curing, it is preferable that one monomer is hexafunctional or higher. This is different from the simple combined effect in the prior art. In other words, in the present invention, for the purpose of stable image formation for a longer period of time, a special effect is given to the object of providing a tough cross-linked charge transport layer having a thicker film thickness. Even if the film thickness is 5 μm or more, preferable results can be obtained.

  Hereinafter, the photosensitive member, toner, and cleaning device used in the electrophotographic photosensitive member, toner, image forming method, and apparatus of the present invention will be described.

(I) Photoreceptor The electrophotographic photoreceptor of the present invention has a photosensitive layer including at least a cross-linked surface layer.

The support is not particularly limited as long as it has conductivity of 10 ¹⁰ Ω · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum; tin oxide In addition, a metal oxide such as indium oxide coated on a film or cylindrical substrate by vapor deposition or sputtering, or a plate made of aluminum, aluminum alloy, nickel, stainless steel or the like and extruded or drawn by a method such as drawing. After pipe formation, pipes that have been subjected to surface treatment such as cutting, superfinishing, and polishing can be used. A conductive endless belt can also be used as a support. In addition, it is also possible to use a conductive powder dispersed on a support and dispersed in a suitable binder resin.

  Examples of the conductive powder include metal powders such as carbon black, aluminum, nickel, iron, nichrome, copper, zinc, and silver, or metal oxide powders such as conductive tin oxide and ITO. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic and curable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. The conductive layer can be provided by dispersing and applying these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

  The photosensitive layer is formed by laminating a charge generation layer, a charge transport layer, and a cross-linked charge transport layer in this order, and further includes other layers as necessary.

  The charge generation layer includes a charge generation material having a charge generation function as a main component, a binder resin, and further includes other components as necessary.

  As the charge generation material, both inorganic materials and organic materials can be used.

  Examples of the inorganic material include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compound, amorphous silicon, and the like.

  A known material can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, squaric acid methine pigments, azo pigments having a carbazole skeleton, azo pigments having a triphenylamine skeleton, azo pigments having a diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having a fluorenone skeleton, azo pigments having an oxadiazole skeleton, azo pigments having a bis-stilbene skeleton, azo pigments having a distyryl oxadiazole skeleton, azo pigments having a distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, indigo Id based pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.

  Among these, oxytitanium phthalocyanine represented by the following structural formula (1) is one of the preferable ones.

構造式（１）中、Ｘ^１、Ｘ^２、Ｘ^３、及びＸ^４は、Ｃｌ又はＢｒを表す。ｈ、ｉ、ｊ、及びｋは、０〜４の整数を表す。

In the structural formula (1), X ¹ , X ² , X ³ , and X ⁴ represent Cl or Br. h, i, j, and k represent an integer of 0 to 4.

  The crystalline form of oxytitanium phthalocyanine has strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of the black angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα. It is more preferable from the viewpoint of sensitivity characteristics that it is either oxytitanium phthalocyanine or oxytitanium phthalocyanine having strong peaks at 9.6 ° and 27.3 °.

  Examples of the binder resin include polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, and polyacrylamide. These can be used alone or as a mixture of two or more.

  Specifically, JP-A Nos. 01-009964, 04-01627, 04-175337, 05-232727, 05-310904, 06-234836. No. 6, JP-A 06-234841, JP-A 06-239049, JP-A 06-236050, JP-A 06-236051, JP-A 06-295077, JP-A 07-056374. And polymer materials described in JP-A-08-176293.

  In addition to the above, polymer charge transport materials having a charge transport function, such as polycarbonate, polyester, polyurethane, polyether, polysiloxane having arylamine skeleton, benzidine skeleton, hydrazone skeleton, carbazole skeleton, stilbene skeleton, pyrazoline skeleton, etc. In addition, a polymer material such as an acrylic resin, a polymer material having a polysilane skeleton, or the like can be used.

  Specific examples include polysilylene polymers described in JP-A 63-285552, JP-A 05-19497, JP-A 05-70595, JP-A 10-73944, and the like.

  The charge generation layer can contain a low molecular charge transport material. As the low molecular charge transport material, both a hole transport material and an electron transport material are suitable.

  As the electron transporting material, an electron accepting material is preferable, and examples thereof include chloroanil, bromanyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7- Tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophene-4- ON, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, diphenoquinone derivatives, and the like. These can be used alone or as a mixture of two or more.

  Examples of the hole transport material include known electron donating materials. For example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9- Examples include styryl anthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, and the like. These hole transport materials can be used alone or as a mixture of two or more.

  Examples of the method for forming the charge generation layer include a vacuum thin film preparation method and a casting method from a solution dispersion system. As the vacuum thin film production method, for example, a vacuum deposition method, a glow discharge decomposition method, a sputtering method, a CVD method, and the like are suitable, and the above-described inorganic materials and organic materials can be favorably formed.

  As a method of providing a charge generation layer by a casting method, for example, an inorganic or organic charge generation material is dispersed by a ball mill, an attritor, a sand mill, a bead mill or the like using a solvent together with a binder resin as necessary. Can be formed by appropriately diluting and coating. Examples of the solvent include tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclopentanone, anisole, xylene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate and the like. In addition, a leveling agent such as dimethyl silicone oil or methylphenyl silicone oil can be added to the dispersion as necessary. The application can be performed by dip coating, spray coating, bead coating, ring coating, or the like.

  The thickness of the charge generation layer is preferably from 0.01 to 5 μm, more preferably from 0.05 to 2 μm.

-Charge transport layer-
The charge transport layer is formed by dissolving or dispersing a charge transport material having a charge transport function and a binder resin in an appropriate solvent, and coating and drying the solution on the charge generation layer.

  As the charge transport material, the electron transport material, the hole transport material and the polymer charge transport material described in the charge generation layer can be used. As described above, the use of the polymer charge transport material can reduce the solubility of the lower layer when the cross-linked charge transport layer is applied, and is particularly useful.

  Examples of the binder resin include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyacetic acid. Vinyl, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, A urethane resin, a phenol resin, an alkyd resin, etc. are mentioned.

  The amount of the charge transport material added is preferably 20 to 300 parts by mass, more preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin. However, when a polymer charge transport material is used, it can be used alone or in combination with a binder resin.

  As the solvent used for coating the charge transport layer, the same solvent as the charge generation layer can be used, but a solvent that dissolves the charge transport material and the binder resin well is suitable. These solvents may be used alone or in combination of two or more. In addition, the same coating method as that for the charge generation layer can be used to form the lower layer portion of the charge transport layer.

  Moreover, a plasticizer and a leveling agent can also be added to a charge transport layer as needed.

  As the plasticizer for the resin, known plasticizers such as dibutyl phthalate and dioctyl phthalate can be used. The amount of the plasticizer used is suitably 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

  Examples of the leveling agent include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain. The amount of the leveling agent used is suitably 1 part by mass or less with respect to 100 parts by mass of the binder resin.

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

--Cross-linked charge transport layer--
On the charge transport layer, a crosslinkable charge transport layer coating liquid described below is applied and dried, and then irradiated with heat, light, or electromagnetic waves as external energy to initiate a curing reaction. It is formed.

  The crosslinkable charge transport layer is a layer having a crosslink structure having a charge transport function, and having at least one trifunctional or higher radical polymerizable monomer having no charge transportable structure and one or more functional charge transportable structures. A coating solution containing a radical polymerizable compound, other additives, and a solvent is applied on the charge transport layer, dried, and cured.

  Next, the constituent materials of the crosslinkable charge transport layer coating solution of the present invention will be described.

  The trifunctional or higher functional radical polymerizable monomer having no charge transporting property used in the present invention is a hole transporting structure such as triarylamine, hydrazone, pyrazoline, carbazole, such as condensed polycyclic quinone, diphenoquinone, cyano group. And a monomer having no electron transport structure such as an electron-withdrawing aromatic ring having a nitro group and having three or more radical polymerizable functional groups. The radical polymerizable functional group may be any group as long as it has a carbon-carbon double bond and is capable of radical polymerization. Examples of these radical polymerizable functional groups include 1-substituted ethylene functional groups and 1,1-substituted ethylene functional groups shown below.

  (1) As the 1-substituted ethylene functional group, for example, a functional group represented by the following structural formula (2) is preferably exemplified.

^{_{CH 2 = CH-X 1 -}} ··· structural formula (2)
However, in the structural formula (2), X ¹ represents an arylene group such as a phenylene group or a naphthylene group which may have a substituent, an alkenylene group which may have a substituent, a —CO— group, — COO— group, —CON (R ¹⁰ ) — group (wherein R ¹⁰ is a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, an aralkyl group such as a benzyl group, a naphthylmethyl group or a phenethyl group, a phenyl group, or a naphthyl group) Represents an aryl group such as a group) or an S-group.

  Specific examples of these substituents include a vinyl group, a styryl group, a 2-methyl-1,3-butadienyl group, a vinylcarbonyl group, an acryloyloxy group, an acryloylamide group, and a vinyl thioether group. (2) As the 1,1-substituted ethylene functional group, for example, a functional group represented by the following structural formula (3) is preferably exemplified.

_{CH 2 = C (Y) -X} 2 - ··· structural formula (3)
However, in Structural Formula (3), Y represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, a phenyl group which may have a substituent, or a naphthyl group. An aryl group such as a halogen atom, a cyano group, a nitro group, an alkoxy group such as a methoxy group or an ethoxy group, -COOR ¹¹ group (where R ¹¹ is a hydrogen atom, a methyl group optionally having substituents, Represents an alkyl group such as an ethyl group, an aralkyl group such as an optionally substituted benzyl or phenethyl group, an aryl group such as an optionally substituted phenyl group or naphthyl group, and the same or different from each other; Or CONR ¹² R ¹³ (wherein R ¹² and R ¹³ have a hydrogen atom, an alkyl group such as an optionally substituted methyl group or an ethyl group, or a substituent). Even An aralkyl group such as a benzyl group, a naphthylmethyl group, or a phenethyl group, or an aryl group such as a phenyl group or a naphthyl group that may have a substituent, which may be the same or different from each other. , X ² represents the same substituent, single bond, and alkylene group as X ^{1 in the} structural formula (2). However, Y, at least one oxycarbonyl group in X ^2, cyano, an alkenylene group, and an aromatic ring.

  Examples of these substituents include an α-acryloyloxy chloride group, a methacryloyloxy group, an α-cyanoethylene group, an α-cyanoacryloyloxy group, an α-cyanophenylene group, and a methacryloylamino group.

  In addition, examples of the substituent further substituted with the substituent for X and Y include, for example, a halogen atom, a nitro group, an alkyl group such as a cyano group, a methyl group, and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, An aryloxy group such as a phenoxy group, an aryl group such as a phenyl group and a naphthyl group, an aralkyl group such as a benzyl group and a phenethyl group, and the like.

  Among these radical polymerizable functional groups, an acryloyloxy group and a methacryloyloxy group are particularly useful, and a compound having three or more acryloyloxy groups includes, for example, a compound having three or more hydroxyl groups in the molecule. It can be obtained by an ester reaction or a transesterification reaction using acrylic acid (salt), acrylic acid halide, and acrylic ester. A compound having three or more methacryloyloxy groups can be obtained in the same manner. Further, the radical polymerizable functional groups in the monomer having three or more radical polymerizable functional groups may be the same or different.

  As a trifunctional or higher functional radical polymerizable monomer having no charge transport structure, any known monomer can be used effectively. Although it can use individually or in combination of 2 or more types, it is preferable to use 2 or more types together.

  Among these, it is preferable that at least one monomer having an acryloyloxy group or a methacryloyloxy group represented by the following general formula (A) is included as a radical polymerizable monomer having no charge transporting structure used in the present invention.

（式中、Ｒ_７１、Ｒ_７２、Ｒ_７３、Ｒ_７４、Ｒ_７５、Ｒ_７６は水素又は

(Wherein R ₇₁ , R ₇₂ , R ₇₃ , R ₇₄ , R ₇₅ , R ₇₆ are hydrogen or

を示し、Ｒ_７７は単結合、アルキレン基、アルキレンエーテル基、アルキレンオキシカルボニル基を示し、Ｒ_７８は水素およびメチル基を示す。

R ₇₇ represents a single bond, an alkylene group, an alkylene ether group or an alkyleneoxycarbonyl group, and R ₇₈ represents hydrogen and a methyl group.

  The radical polymerizable monomer having no charge transport structure represented by the general formula (A) includes a compound having 3 acryloyloxy groups and 3 hydrogen groups, 4 acryloyloxy groups and 2 hydrogen groups. A compound having 5 acryloyloxy groups and 1 hydrogen group, a compound having 6 acryloyloxy groups, a compound having 3 methacryloyloxy groups and 3 hydrogen groups, 4 methacryloyloxy Examples thereof include a compound having a group and two hydrogen groups, a compound having five methacryloyloxy groups and one hydrogen group, and a compound having six methacryloyloxy groups. Furthermore, although the following are illustrated, it is not limited to these compounds.

  Table 1-1

表１−２

Table 1-2

これらは、２種類以上を併用することが好ましい。

These are preferably used in combination of two or more.

  It can be exemplified that these monomers are produced by esterification of a polyhydric alcohol for reasons such as excellent yield, low production cost and high productivity. In addition, when two or more of these monomers are used in combination, more specifically, two, three, or four, when using a monomer having six radical polymerizable functional groups, the yield is excellent. It is preferable to use a mixture of a monomer having six radically polymerizable functional groups and a monomer having 5 or less radically polymerizable functional groups in which hydrogen groups remain without being esterified.

  Furthermore, the blending ratio of the monomer having the six radical polymerizable functional groups is preferably 20 to 99% by weight, more preferably 30 to 97% by weight, from the viewpoint that the yield is also excellent. More preferably, it is 40 to 95% by weight. For the same reason, when a monomer having five radical polymerizable functional groups is used, it is preferable to contain 20 to 99% by weight of this monomer, more preferably 30 to 97% by weight, still more preferably 40 to 95% by weight. When a monomer having four radical polymerizable functional groups is used for the same reason, it is preferable to contain 0.01 to 30% by weight of this monomer, more preferably 0.1 to 20% by weight, More preferably, it is 3 to 5% by weight. When a monomer having three radical polymerizable functional groups is used for the same reason, it is preferable to contain this monomer in an amount of 0.01 to 30% by weight, more preferably 0 to 0%. 0.1 to 20% by weight, more preferably 3 to 5% by weight.

More specifically, for the same reason, 30 to 70% by weight, preferably 40 to 60% by weight of a compound having 5 acryloyloxy groups and 1 hydrogen group, and 70 to 30% by weight of a compound having 6 acryloyloxy groups. %, Preferably a mixture containing 60 to 40% by weight, a compound having 5 acryloyloxy groups and one hydrogen group 30 to 65% by weight, preferably 40 to 55% by weight, 6 acryloyloxy groups The compound having 65 to 30% by weight, preferably 55 to 40% by weight, and one, two, three or four selected from the compounds listed below are 0.01 to 5% by weight, preferably Is a mixture containing 1-3% by weight,
-Compound having 1 acryloyloxy group and 5 hydrogen groups-Compound having 2 acryloyloxy groups and 4 hydrogen groups-Compound having 3 acryloyloxy groups and 3 hydrogen groups-4 Compounds having 1 acryloyloxy group and 2 hydrogen groups 5 methacryloyloxy groups and 1 hydrogen group 30-70 wt%, preferably 40-60 wt% and 6 methacryloyloxy groups A mixture containing 70 to 30% by weight, preferably 60 to 40% by weight of a compound having 30 to 65% by weight, preferably 40 to 55% by weight, a compound having 5 methacryloyloxy groups and one hydrogen group, 6 65 to 30% by weight, preferably 55 to 40% by weight of a compound having one methacryloyloxy group, and the compounds listed below One selected from among, two, three or four 0.01 to 5 wt%, preferably a mixture containing 1-3 wt% can be exemplified.

-Compound having 1 methacryloyloxy group and 5 hydrogen groups-Compound having 2 methacryloyloxy groups and 4 hydrogen groups-Compound having 3 methacryloyloxy groups and 3 hydrogen groups-4 Compound having 1 methacryloyloxy group and 2 hydrogen groups In addition, the proportion of the radical polymerizable monomer having no charge transporting structure represented by the general formula (A) used in the crosslinked surface layer is the total amount of the crosslinked surface layer. The content is preferably 3 to 95%, more preferably 5 to 80% by weight, and still more preferably 10 to 70% by weight. When the monomer component is 3% by weight or more, the three-dimensional cross-linking density of the cross-linked surface layer is high, and a dramatic improvement in wear resistance is achieved as compared with the case where a conventional thermoplastic binder resin is used. On the other hand, when the content is 95% by weight or less, the content of the charge transporting compound is high and the electrical characteristics are hardly deteriorated.

  The formation of the cross-linked charge transport layer of the present invention is not limited to those described above for the purpose of imparting functions such as viscosity adjustment during coating, stress relaxation during cross-linking, low surface free energy and low friction coefficient. A tetrafunctional radically polymerizable monomer and a radically polymerizable oligomer can be used in combination. By this combination, the smoothness of the coating layer is improved by reducing the viscosity of the radically polymerizable monomer itself having no charge transporting structure, or by reducing the viscosity of the coating liquid. Strain reduction is achieved, leading to improved cleaning properties and crack suppression. In particular, a combination of a trifunctional or tetrafunctional radical polymerizable monomer and a hexafunctional or higher functional polymerizable monomer is preferred. The mixing ratio of all these radically polymerizable monomers and oligomers is preferably 1 to 80% by weight, more preferably 5 to 60% by weight, still more preferably 10 to 40% by weight based on the total amount of the crosslinked surface layer. Furthermore, the viscosity of these radical polymerizable monomers used in combination is preferably 1000 mPa · s and 25 ° C. or lower, more preferably 800 mPa · s and 25 ° C. or lower.

  Examples of the monofunctional to tetrafunctional radical polymerizable monomers include the following, but are not limited to these compounds. Here, ethyleneoxy modification is abbreviated as EO, propyleneoxy modification as PO modification, epichlorohydrin modification as ECH modification, and alkylene modification as HPA modification.

  That is, examples of the radical polymerizable monomer used in the present invention include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, HPA-modified trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, and PO-modified. Trimethylolpropane triacrylate, caprolactone modified trimethylolpropane triacrylate, ECH modified trimethylolpropane triacrylate, HPA modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH modified glycerol Triacrylate, EO-modified glycerol tria Relate, PO-modified glycerol triacrylate, tris (acryloxyethyl) isocyanurate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxytetraacrylate, EO-modified Phosphoric acid triacrylate, 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol Acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyla Relate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,0-hexanediol dimethacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F di Acrylate, neopentyl glycol diacrylate, etc. Rupropane triacrylate (TMPTA), HPA-modified trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, and ECH-modified trimethylolpropane triacrylate are preferred for the reasons described above.

  Examples of the functional monomer other than the monofunctional to tetrafunctional radical polymerizable monomers include octafluoropentyl acrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, and 2-perfluoroisononylethyl acrylate. Siloxane repeating units described in JP-B-5-60503 and JP-B-6-45770: 20-70 acryloyl polydimethylsiloxane ethyl, methacryloyl polydimethylsiloxane ethyl, acryloyl polydimethylsiloxane Vinyl monomers having polysiloxane groups, such as propyl, acryloyl polydimethylsiloxane butyl, diacryloyl polydimethylsiloxane diethyl, acrylates and methacrylates Door and the like.

  The trifunctional or higher functional radical polymerizable monomer having no charge transporting structure forms a dense cross-linked bond in the cross-linked charge transport layer, and therefore the ratio of molecular weight to the number of functional groups in the monomer (molecular weight / functional group number) is 500. The following is preferred. When the ratio of the molecular weight to the number of functional groups in the monomer exceeds 500, the crosslinkable charge transport layer has increased chemical structural flexibility and wear resistance is somewhat reduced. Therefore, in the monomers exemplified above, HPA, EO In monomers having a modifying group such as PO, it is not preferable to use a monomer having an extremely long modifying group alone. It is preferable to use in combination with a monomer having a molecular weight / number of functional groups of 500 or less.

  In the crosslinkable charge transport layer of the present invention, a radical polymerizable compound having a charge transport structure having one or more functions can be used. Among these, a radical polymerizable compound having a monofunctional charge transporting structure is preferable. For example, it has a hole transporting structure such as triarylamine, hydrazone, pyrazoline and carbazole, for example, an electron transporting structure such as condensed polycyclic quinone, diphenoquinone, electron withdrawing aromatic ring having cyano group or nitro group And a compound having one radical polymerizable functional group. Examples of the radical polymerizable functional group include those shown in the above radical polymerizable monomer, and acryloyloxy group and methacryloyloxy group are particularly useful. In addition, as the charge transporting structure, the effect of the triarylamine structure is high, and in particular, when a compound represented by the following structural formula (4) or (5) is used, electrical characteristics such as sensitivity and residual potential are good. To last.

構造式（４）又は（５）中、Ｒ^１は水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基、置換基を有してもよいアリール基、シアノ基、ニトロ基、アルコキシ基、−ＣＯＯＲ^７（ただし、Ｒ^７は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基又は置換基を有してもよいアリール基を表す。）、ハロゲン化カルボニル基若しくはＣＯＮＲ^８Ｒ^９（ただし、Ｒ^８及びＲ^９は、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基又は置換基を有してもよいアリール基を示し、互いに同一であっても異なっていてもよい）を表す。Ａｒ_１、Ａｒ_２は、置換もしくは未置換のアリーレン基を表わし、同一であっても異なってもよい。Ａｒ_３、Ａｒ_４は、置換もしくは未置換のアリール基を表わし、同一であっても異なってもよい。Ｘは、単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表わす。Ｚは、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキレンエーテル基、アルキレンオキシカルボニル基を表わす。ｍ、ｎは０〜３の整数を表わす。

In Structural Formula (4) or (5), R ¹ may have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or a substituent. An aryl group, a cyano group, a nitro group, an alkoxy group, —COOR ⁷ (where R ⁷ represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group or a substituent which may have a substituent, Represents an aryl group which may be present), a halogenated carbonyl group or CONR ⁸ R ⁹ (wherein R ⁸ and R ⁹ are a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a substituent, Represents an aralkyl group which may have an aryl group or an aryl group which may have a substituent, which may be the same or different from each other. Ar ₁ and Ar ₂ represent a substituted or unsubstituted arylene group, and may be the same or different. Ar ₃ and Ar ₄ represent a substituted or unsubstituted aryl group, and may be the same or different. X represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group. Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether group, or an alkyleneoxycarbonyl group. m and n represent an integer of 0 to 3.

In the structural formula (4) or (5), in the substituent of R ¹ , examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. These include halogen atoms, nitro groups, cyano groups, alkyl groups such as methyl groups and ethyl groups, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, aryl groups such as phenyl groups and naphthyl groups, It may be substituted with an aralkyl group such as a benzyl group or a phenethyl group. Of the substituents for R ¹ , particularly preferred are a hydrogen atom and a methyl group.

Substituted or unsubstituted Ar ₃ and Ar ₄ are aryl groups, and examples of the aryl group include condensed polycyclic hydrocarbon groups, non-fused cyclic hydrocarbon groups, and heterocyclic groups.

  As the condensed polycyclic hydrocarbon group, preferably those having 18 or less carbon atoms forming a ring, for example, a pentanyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, an as-indacenyl group, s-indacenyl group, fluorenyl group, acenaphthylenyl group, pleyadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylyl group, pyrenyl group, Examples include a chrycenyl group and a naphthacenyl group.

  Examples of the non-condensed cyclic hydrocarbon group include monovalent groups of monocyclic hydrocarbon compounds such as benzene, diphenyl ether, polyethylene diphenyl ether, diphenyl thioether, and diphenyl sulfone, or biphenyl, polyphenyl, diphenylalkane, diphenylalkene, and diphenyl. A monovalent group of a non-condensed polycyclic hydrocarbon compound such as alkyne, triphenylmethane, distyrylbenzene, 1,1-diphenylcycloalkane, polyphenylalkane or polyphenylalkene, or a ring such as 9,9-diphenylfluorene Examples thereof include monovalent groups of aggregated hydrocarbon compounds.

Examples of the heterocyclic group include monovalent groups such as carbazole, dibenzofuran, dibenzothiophene, oxadiazole, and thiadiazole. Further, the aryl group represented by _Ar 3, Ar ₄ is, for example, may have a substituent as shown below (1) to (8).

  (1) A halogen atom, a cyano group, a nitro group, etc. are mentioned.

(2) Alkyl groups, preferably C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C ₄ linear or branched alkyl groups, further including fluorine atoms , a hydroxyl group, a cyano _group, an alkoxy group of C 1 -C _4, a phenyl group or a halogen _atom, which may have a phenyl group substituted by an alkoxy group C 1 -C ₄ alkyl or _C 1 -C ₄ Good. Specifically, methyl group, ethyl group, n-butyl group, i-propyl group, t-butyl group, s-butyl group, n-propyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-ethoxyethyl Group, 2-cyanoethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-phenylbenzyl group, and the like.

(3) An alkoxy group (—OR ₂ ), wherein R ₂ represents the alkyl group defined in (2) above. Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, benzyloxy group , A trifluoromethoxy group, and the like.

(4) An aryloxy group, and examples of the aryl group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methoxyphenoxy group, 4-methylphenoxy group, and the like.

  (5) Alkyl mercapto group or aryl mercapto group, and specific examples include methylthio group, ethylthio group, phenylthio group, p-methylphenylthio group, and the like.

  (6) The group represented by following Structural formula (6) is mentioned.

前記構造式（６）中、Ｒ_３及びＲ_４は各々独立に水素原子、前記（２）で定義したアルキル基、又はアリール基を表わす。アリール基としては、例えばフェニル基、ビフェニル基又はナフチル基が挙げられ、これらはＣ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基又はハロゲン原子を置換基として含有してもよい。Ｒ_３及びＲ_４は共同で環を形成してもよい。

In the structural formula (6), R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group defined in the above (2), or an aryl group. Examples of the aryl group include a phenyl group, biphenyl group or a naphthyl group, and these may contain an alkoxy group of C ₁ -C _4, alkyl group, or a halogen atom C ₁ -C ₄ as a substituent. R ₃ and R ₄ may form a ring together.

  Specifically, amino group, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (tolyl) amino group, dibenzylamino group, piperidino group, morpholino group And pyrrolidino group.

  (7) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.

  (8) Substituted or unsubstituted styryl group, substituted or unsubstituted β-phenylstyryl group, diphenylaminophenyl group, ditolylaminophenyl group, and the like.

The arylene group represented by Ar ₁ and Ar ₂ is a divalent group derived from the aryl group represented by Ar ₃ or Ar ₄ .

  X represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group.

The substituted or unsubstituted alkylene group is a C ₁ -C ₁₂ , preferably C ₁ -C ₈ , more preferably C ₁ -C ₄ linear or branched alkylene group, and these alkylene groups include a fluorine atom, a hydroxyl group, a cyano _group, an alkoxy group of C 1 -C _4, a phenyl group or a halogen _atom, a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C ₄ It may be. Specifically, methylene group, ethylene group, n-butylene group, i-propylene group, t-butylene group, s-butylene group, n-propylene group, trifluoromethylene group, 2-hydroxyethylene group, 2-ethoxyethylene Group, 2-cyanoethylene group, 2-methoxyethylene group, benzylidene group, phenylethylene group, 4-chlorophenylethylene group, 4-methylphenylethylene group, 4-biphenylethylene group and the like.

The substituted or unsubstituted cycloalkylene _group, a cyclic alkylene group of C 5 -C _7, these are the cyclic alkylene group fluorine atom, a hydroxyl _group, an alkyl group of C 1 -C _4, a C 1 -C ₄ It may have an alkoxy group. Specific examples include a cyclohexylidene group, a cyclohexylene group, and a 3,3-dimethylcyclohexylidene group.

  The substituted or unsubstituted alkylene ether group represents ethyleneoxy, propyleneoxy, ethylene glycol, propylene glycol, diethylene glycol, tetraethylene glycol, tripropylene glycol, alkylene ether group alkylene group is hydroxyl group, methyl group, ethyl group, etc. You may have the substituent of. As the vinylene group, a group represented by the following structural formula is preferable.

ただし、構造式中、Ｒ_５は、水素、アルキル基（（２）で定義されるアルキル基と同じ）、アリール基（Ａｒ_３、Ａｒ_４で表わされるアリール基と同じ）であり、ａは１又は２、ｂは１〜３を表わす。

However, in the structural formula, R ₅ is hydrogen, an alkyl group (the same as the alkyl group defined by (2)), an aryl group (the same as the aryl group represented by Ar ₃ or Ar ₄ ), and a is 1 Or 2, b represents 1-3.

  Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether group, or an alkyleneoxycarbonyl group.

  Examples of the substituted or unsubstituted alkylene group include the same substituents as the alkylene group for X.

  Examples of the substituted or unsubstituted alkylene ether group include the alkylene ether group represented by X.

  Examples of the alkyleneoxycarbonyl group include a caprolactone-modified group.

  Further, a radically polymerizable compound having a monofunctional charge transport structure is more preferably a compound represented by the following structural formula (7).

ただし、構造式（７）中、ｏ、ｐ、ｑはそれぞれ０又は１の整数、Ｒａは水素原子、メチル基を表わし、Ｒｂ、Ｒｃは水素原子以外の置換基で炭素数１〜６のアルキル基を表わし、複数の場合は異なってもよい。ｓ、ｔは０〜３の整数を表わす。Ｚａは単結合、メチレン基、エチレン基、又は下記構造式で表される基を表す。

In Structural Formula (7), o, p and q are each an integer of 0 or 1, Ra represents a hydrogen atom or a methyl group, Rb and Rc are substituents other than a hydrogen atom and an alkyl having 1 to 6 carbon atoms. Represents a group, and a plurality of groups may be different. s and t represent an integer of 0 to 3. Za represents a single bond, a methylene group, an ethylene group, or a group represented by the following structural formula.

ただし、構造式で表わされる化合物としては、Ｒｂ、Ｒｃの置換基として、特にメチル基、エチル基である化合物が好ましい。

However, as the compound represented by the structural formula, a compound having a methyl group or an ethyl group as a substituent for Rb and Rc is particularly preferable.

  In the radically polymerizable compound having a monofunctional charge transport structure represented by the structural formulas (4), (5) and (7), particularly the structural formula (7), the carbon-carbon double bond has both sides. In a polymer that is not opened into a terminal structure but is incorporated into a chain polymer and crosslinked by polymerization with a trifunctional or higher radical polymerizable monomer, And present in a cross-linked chain between the main chain and the main chain (in this cross-linked chain, an intermolecular cross-linked chain between one polymer and another polymer and a folded state in one polymer) In the main chain and other sites derived from the polymerized monomer at a position away from this in the main chain), but present in the main chain. The triarylamine structure suspended from the chain moiety, even if present in the bridge chain, It has at least three aryl groups arranged radially from the elementary atoms and is bulky, but it is not directly bonded to the chain part and is suspended from the chain part via a carbonyl group, etc. Since these triarylamine structures can be spatially arranged adjacent to each other in the polymer, there is little structural distortion in the molecule, and the electrophotographic photoreceptor In the case of the surface layer, it is presumed that an intramolecular structure that is relatively free from interruption of the charge transport path can be adopted.

Specific examples of the radically polymerizable compound having a monofunctional charge transporting structure of the present invention are shown below, but are not limited to the compounds having these structures.

  Table 2-1.

表２−２

Table 2-2

表２−３

Table 2-3

表２−４

Table 2-4

表２−５

Table 2-5

表２−６

Table 2-6

表２−７

Table 2-7

表２−８

Table 2-8

表２−９

Table 2-9

表２−１０

Table 2-10

表２−１１

Table 2-11

表２−１２

Table 2-12

また、好ましいものとして、２官能以上の電荷輸送性構造を有するラジカル重合性化合物が使用できる。これらは１官能の電荷輸送性構造を有するラジカル重合性化合物と比べて、立体的な位置取りの融通性に劣ること、或いはトリアリールアミン構造が重合体中で相互に程よく隣接する空間配置をとり難いこと、また分子内の構造的歪みが予想され、電荷輸送経路の確保について若干の困難さが考えられる。しかしながら、前述の電荷輸送性構造を有しない３官能以上のラジカル重合性モノマーと共に硬化し、架橋構造中に取り込むことにより、十分使用に耐える電気的特性、機械的特性を有する架橋型電荷輸送層を形成できるものである。硬化膜の形成に当たっては、前述の様に複数の電荷輸送性構造を有しない３官能以上のラジカル重合性モノマーを併用することが好ましい。２種或いは３種以上併用することが好ましい。例えば、硬化速度を上げる為に５官能或いは６官能の電荷輸送性構造を有しないラジカル重合性モノマーを使用する場合、これに１〜４官能の電荷輸送性構造を有しないラジカル重合性モノマーを併用することが好ましい。更には、３官能〜４官能の電荷輸送性構造を有しないラジカル重合性モノマーを併用することが好ましい。この理由は明確でないが、一つには架橋型電荷輸送層の化学構造として、官能基の少ないものと併用することで、上記の困難さを緩和する効果があるものと予想される。

Moreover, as a preferable thing, the radically polymerizable compound which has a charge transportable structure more than bifunctional can be used. These are inferior in flexibility of steric positioning as compared with radically polymerizable compounds having a monofunctional charge transporting structure, or have a spatial arrangement in which the triarylamine structures are adjacent to each other in the polymer. This is difficult, and structural distortion within the molecule is expected, and there are some difficulties in securing the charge transport route. However, by curing together with the above-described trifunctional or higher-functional radical polymerizable monomer having no charge transport structure and incorporating it in the cross-linked structure, a cross-linked charge transport layer having sufficient electrical and mechanical properties to withstand use can be obtained. It can be formed. In forming the cured film, it is preferable to use a trifunctional or higher functional radical polymerizable monomer having no plural charge transporting structures as described above. It is preferable to use two or more types in combination. For example, when using a radical polymerizable monomer that does not have a pentafunctional or hexafunctional charge transporting structure in order to increase the curing rate, a radical polymerizable monomer that does not have a 1-4 functional charge transporting structure is used in combination with this. It is preferable to do. Furthermore, it is preferable to use a radical polymerizable monomer having no trifunctional to tetrafunctional charge transporting structure in combination. The reason for this is not clear, but it is expected that, in part, the chemical structure of the cross-linked charge transport layer is effective in alleviating the above difficulties by using it in combination with one having few functional groups.

  Specific examples of the radical polymerizable compound having a bifunctional or higher functional charge transporting structure of the present invention are shown below, but are not limited to the compounds having these structures.

  Table 3-1.

表３−２

Table 3-2

表３−３

Table 3-3

表３−４

Table 3-4

表３−５

Table 3-5

表３−６

Table 3-6

表３−７

Table 3-7

表３−８

Table 3-8

表３−９

Table 3-9

表３−１０

Table 3-10

表３−１１

Table 3-11

表３−１２

Table 3-12

表３−１３

Table 3-13

表３−１４

Table 3-14

表３−１５

Table 3-15

表３−１６

Table 3-16

表３−１７

Table 3-17

表３−１８

Table 3-18

表３−１９

Table 3-19

表３−２０

Table 3-20

表３−２１

Table 3-21

表３−２２

Table 3-22

表３−２３

Table 3-23

表３−２４

Table 3-24

表３−２５

Table 3-25

表３−２６

Table 3-26

表３−２７

Table 3-27

表３−２８

Table 3-28

表３−２９

Table 3-29

表３−３０

Table 3-30

表３−３１

Table 3-31

表３−３２

Table 3-32

表３−３３

Table 3-33

表３−３４

Table 3-34

表３−３５

Table 3-35

表３−３６

Table 3-36

表３−３７

Table 3-37

表３−３８

Table 3-38

表３−３９

Table 3-39

表３−４０

Table 3-40

表３−４１

Table 3-41

表３−４２

Table 3-42

表３−４３

Table 3-43

表３−４４

Table 3-44

本発明の３官能の電荷輸送性構造を有するラジカル重合性化合物の具体例を以下に示すが、これらの構造の化合物に限定されるものではない。

Specific examples of the radical polymerizable compound having a trifunctional charge transporting structure of the present invention are shown below, but are not limited to the compounds having these structures.

  Table 4-1

表４−２

Table 4-2

表４−３

Table 4-3

表４−４

Table 4-4

表４−５

Table 4-5

前記２官能以上の電荷輸送性構造を有するラジカル重合性モノマーの添加量は、前記架橋型電荷輸送層に対し２０〜８０質量％が好ましく、３０〜７０質量％がより好ましい。前記添加量が２０質量％未満であると、架橋型電荷輸送層の電荷輸送性能が充分に保てず、繰り返しの使用で感度低下、残留電位上昇などの電気特性の劣化が現れることがあり、８０質量％を超えると、電荷輸送構造を有しない３官能モノマーの含有量が低下し、架橋密度の低下を招き高い耐摩耗性が発揮されないことがある。なお、使用されるプロセスによって要求される電気特性や耐摩耗性が異なり、それに伴い本感光体の架橋型電荷輸送層の膜厚も異なるため一概には言えないが、両特性のバランスを考慮すると３０〜７０質量％の範囲が最も好ましい。

The addition amount of the radical polymerizable monomer having a bifunctional or higher functional charge transporting structure is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass with respect to the cross-linked charge transporting layer. When the addition amount is less than 20% by mass, the charge transport performance of the crosslinkable charge transport layer cannot be sufficiently maintained, and deterioration of electrical characteristics such as a decrease in sensitivity and an increase in residual potential may appear due to repeated use. If it exceeds 80% by mass, the content of the trifunctional monomer having no charge transport structure is lowered, and the crosslinking density is lowered, and high wear resistance may not be exhibited. Note that the electrical characteristics and abrasion resistance required differ depending on the process used, and the thickness of the cross-linked charge transport layer of the photoconductor also varies accordingly. The range of 30-70 mass% is the most preferable.

  In forming the crosslinkable charge transport layer, a polymerization initiator may be contained in the crosslinkable charge transport layer coating solution in order to efficiently advance the curing reaction as necessary. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. These polymerization initiators may be used alone or in combination of two or more.

  Examples of the thermal polymerization initiator include 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, benzoyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5. -Di (peroxybenzoyl) hexyne-3, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, 2,2-bis (4,4-di-t-butyl Peroxycyclohexyl) propane and other peroxide initiators; azobisisobutylnitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, azobisisobutylamidine hydrochloride, 4,4′-azobis-4-cyanovaleric acid, etc. And azo initiators.

  Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 4- (2-hydroxyethoxy) phenyl. -(2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one Acetophenone-based or ketal-based photopolymerization of 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, etc. Agents: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobuty Benzoin ether photopolymerization initiators such as ether and benzoin isopropyl ether; benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone, 1 Benzophenone photopolymerization initiators such as 1,4-benzoylbenzene; thioxanthone photopolymerization such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Initiators; Other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenol Ruethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10 -Phenanthrenes, acridine compounds, triazine compounds, imidazole compounds, and the like.

  In addition, what has a photopolymerization acceleration effect can also be used individually or in combination with the said photoinitiator. Examples include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4'-dimethylaminobenzophenone, and the like.

  The content of the polymerization initiator is preferably 0.5 to 40 parts by mass and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total content having radical polymerizability.

  The crosslinkable charge transport layer coating liquid may contain additives such as various plasticizers, leveling agents, and low molecular charge transport materials that do not have radical reactivity for the purpose of stress relaxation and adhesion improvement, as necessary. .

  As the plasticizer, for example, those used in general resins such as dibutyl phthalate and dioctyl phthalate can be used.

  The amount of the plasticizer used is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the crosslinkable charge transport layer coating solution.

  Examples of the leveling agent include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain.

  The amount of the leveling agent used is preferably 3% by mass or less based on the total solid content of the crosslinkable charge transport layer coating solution.

Coating the crosslinked charge transporting layer of the present invention, which contains at least a radical polymerizable compound having a trifunctional or higher radical polymerizable monomer and one or more functional charge transport structure having no kind of charge transport structure of the It is formed by applying and curing the working liquid on the charge transport layer described later. In the case where the radically polymerizable monomer is a liquid, such a coating liquid can be applied by dissolving other components in the liquid, but if necessary, it is diluted with a solvent and applied.

  Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, and butanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; tetrahydrofuran, dioxane, Ether solvents such as propyl ether; halogen solvents such as dichloromethane, dichloroethane, trichloroethane and chlorobenzene; aromatic solvents such as benzene, toluene and xylene; cellosolv solvents such as methyl cellosolve, ethyl cellosolve and cellosolve acetate It is done. These solvents may be used alone or in combination of two or more.

  The dilution ratio with the solvent varies depending on the solubility of the composition, the coating method, and the target film thickness, and is arbitrary. The application can be performed by dip coating, spray coating, bead coating, ring coating, or the like.

  In the present invention, after applying such a crosslinkable charge transport layer coating solution, energy is applied from the outside and cured to form a crosslinkable charge transport layer. The external energy used at this time includes heat, light, and the like. , There is radiation. The heat energy is applied by heating from the coating surface side or the support side using a gas such as air or nitrogen, steam, various heat media, infrared rays or electromagnetic waves.

  The heating temperature is preferably 100 to 170 ° C. When the heating temperature is less than 100 ° C., the reaction rate is slow and the curing reaction may not be completed completely. When the heating temperature exceeds 170 ° C., the temperature becomes too high and the curing reaction proceeds non-uniformly to cause cross-linked charge transport. Large distortions, a large number of unreacted residues, and reaction termination ends may occur in the layer. In order to advance the curing reaction uniformly, it is also effective to complete the reaction by heating at a relatively low temperature of less than 100 ° C. and then heating to 100 ° C. or more.

As the energy of the light, a UV irradiation light source such as a high-pressure mercury lamp or a metal halide lamp having an emission wavelength mainly in ultraviolet light can be used, but the visible light source can be adjusted according to the absorption wavelength of the radical polymerizable substance or photopolymerization initiator. Selection is also possible. The irradiation light amount is preferably 50 to 1000 mW / cm ² . When the irradiation light amount is less than 50 mW / cm ² , the curing reaction may take time, and when it exceeds 1000 mW / cm ² , the progress of the reaction becomes non-uniform, and the surface of the crosslinkable charge transport layer is locally May occur, or many unreacted residues and reaction termination ends may occur. In addition, internal stress increases due to rapid crosslinking, which causes cracks and film peeling.

  Examples of the energy of the radiation include those using an electron beam.

  Among these energies, those using heat and light energy are useful because of easy reaction rate control and simple apparatus.

  The thickness of the cross-linked charge transport layer is preferably 1 to 20 μm, and more preferably 2 to 10 μm. When the film thickness exceeds 20 μm, cracks and film peeling may easily occur. When the film thickness is 10 μm or less, the margin is further improved, so that the crosslinking density can be increased, and the wear resistance is further improved. It is possible to select materials to be increased and to set curing conditions. On the other hand, the radical polymerization reaction is prone to oxygen inhibition, that is, the surface in contact with the atmosphere may not be cross-linked due to the effect of radical trapping by oxygen, and tends to be non-uniform. This effect is noticeable when the film thickness is 1 μm or less, and the crosslinkable charge transport layer having a film thickness of 1 μm or less tends to have a reduced wear resistance or uneven wear. In addition, mixing of the lower layer charge transport layer component occurs during the application of the crosslinkable charge transport layer. If the coating thickness of the crosslinkable charge transport layer is thin, contaminants spread throughout the layer, which inhibits the curing reaction and lowers the crosslink density.

  For these reasons, the cross-linked charge transport layer of the present invention has a good wear resistance and scratch resistance at a film thickness of 1 μm or more, but a portion that is locally scraped to the lower charge transport layer is formed in repeated use. And the wear of the portion increases, and the density unevenness of the halftone image is likely to occur due to the chargeability and sensitivity fluctuation. Therefore, it is desirable that the film thickness of the crosslinkable charge transport layer be 2 μm or more for a longer life and higher image quality.

  The crosslinkable charge transport layer coating solution contains other components in addition to the trifunctional or higher functional radical polymerizable compound not having the charge transportable structure and the radical polymerizable compound having a monofunctional or higher functional charge transport structure. As a binder resin having no radically polymerizable functional group, an additive such as an antioxidant and a plasticizer can be included.

  When these additives are contained in a large amount, the crosslinking density is reduced, the cured product generated by the reaction and the additive are phase-separated, and become soluble in an organic solvent. Specifically, it is important to suppress the total content to 20% by mass or less with respect to the total solid content of the coating liquid. Further, in order not to dilute the crosslinking density, the total content of monofunctional or bifunctional radically polymerizable monomers, reactive oligomers, and reactive polymers is 20% by mass or less based on the trifunctional or more functionally polymerizable monomers. Is desirable. Further, when a large amount of a radical polymerizable compound having a bifunctional or higher functional charge transporting structure is contained, a bulky structure is fixed in the crosslinked structure by a plurality of bonds, so that distortion is likely to occur. It is easy to become an aggregate. This can cause solubility in organic solvents. Although different depending on the compound structure, the content of the radical polymerizable compound having a bifunctional or higher functional charge transporting structure is preferably 10% by mass or less based on the radical polymerizable compound having a monofunctional charge transporting structure. Furthermore, in a structure in which a charge generation layer, a charge transport layer, and a crosslinkable charge transport layer are sequentially laminated, it is possible to achieve wear resistance and scratch resistance when the outermost crosslinkable charge transport layer is insoluble in an organic solvent. Is preferred.

  In the constitution of the present invention, in order to make the crosslinkable charge transport layer insoluble in the organic solvent, (i) the composition of the crosslinkable charge transport layer coating solution, adjustment of the content ratio thereof, and (ii) the crosslinkable charge transport Dilution solvent of layer coating liquid, adjustment of solid content concentration, (iii) Selection of coating method of crosslinkable charge transport layer, (iv) Control of curing condition of crosslinkable charge transport layer, and (v) Charge of lower layer Although it is important to control the poor solubility of the transport layer, it is not always achieved by one factor.

  As a diluting solvent for the crosslinkable charge transport layer coating solution, when a solvent having a low evaporation rate is used, the remaining solvent may hinder the curing, and the amount of the lower layer component may be increased. It leads to uniform curing and reduced curing density. For this reason, it tends to be soluble in organic solvents. Specifically, tetrahydrofuran, a mixed solvent of tetrahydrofuran and methanol, ethyl acetate, methyl ethyl ketone, ethyl cellosolve and the like are useful, but are selected according to the coating method. Moreover, regarding the solid content concentration, if it is too low for the same reason, it tends to be soluble in an organic solvent. On the contrary, the upper limit concentration may be restricted due to the limitation of the film thickness and the coating solution viscosity. Specifically, it is desirable to use in the range of 10 to 50% by mass.

  As the coating method of the crosslinkable charge transport layer, a method of reducing the solvent content at the time of forming the coating film and the contact time with the solvent is preferable. Specifically, the spray coating method and the amount of the coating liquid are regulated. The ring coating method is particularly preferred. In order to suppress the amount of the lower layer component mixed, it is also effective to use a polymer charge transport material as the charge transport layer and to provide an insoluble intermediate layer for the coating solvent for the cross-linked charge transport layer.

  As the curing condition of the cross-linked charge transport layer, if the energy of heating or light irradiation is low, the curing is not completely completed and the solubility in the organic solvent is increased. On the other hand, when cured with very high energy, the curing reaction becomes non-uniform, and it tends to increase the number of uncrosslinked parts and radical stopping parts and to form an aggregate of minute cured products. For this reason, it may become soluble in an organic solvent.

  In order to insolubilize in the organic solvent, the heat curing conditions are preferably 100 to 170 ° C. and 10 minutes to 3 hours, and the curing conditions by UV light irradiation are 50 to 1000 mW / cm 2 and 5 seconds to 5 minutes. In addition, it is desirable to control the temperature rise to 50 ° C. or less to suppress uneven curing reaction.

  For example, the cross-linking charge transport layer is insoluble in an organic solvent. For example, an acrylate monomer having three acryloyloxy groups and a triarylamine compound having one acryloyloxy group are used as a coating solution. In this case, the use ratio is preferably 7: 3 to 3: 7. Moreover, it is preferable to add 3-20 mass% of the said polymerization initiator with respect to these acrylate compounds whole quantity, and also add a solvent, and prepare a coating liquid. For example, in the charge transport layer that is the lower layer of the cross-linked charge transport layer, when the surface layer is formed by spray coating using a triarylamine donor as the charge transport material and polycarbonate as the binder resin, the above coating is used. As the liquid solvent, tetrahydrofuran, 2-butanone, ethyl acetate and the like are preferable. The use ratio is 3 to 10 times the total amount of the acrylate compound.

  Next, for example, the prepared coating solution is applied by spraying or the like on a photoreceptor in which an undercoat layer, a charge generation layer, and the charge transport layer are sequentially laminated on a support such as an aluminum cylinder. Thereafter, it is naturally dried or dried at a relatively low temperature for a short time (25 to 80 ° C., 1 to 10 minutes) and cured by UV irradiation or heating.

For UV irradiation, it uses a metal halide lamp, illuminance 50 mW / cm ² or more, preferably 1000 mW / cm ² or less. For example, when irradiating 200 mW / cm ² of UV light, the drum circumferential direction may be uniformly irradiated for about 30 seconds from a plurality of lamps during curing. At this time, the drum temperature is controlled so as not to exceed 50 ° C.

  In the case of thermosetting, the heating temperature is preferably 100 to 170 ° C. For example, when a blow type oven is used as the heating means and the heating temperature is 150 ° C., the heating time is 20 minutes to 3 hours.

  After the curing is completed, the electrophotographic photosensitive member of the present invention is obtained by further heating at 100 to 150 ° C. for 10 to 30 minutes to reduce the residual solvent.

  In the photoreceptor of the present invention, an intermediate layer is provided between the charge transport layer and the crosslinkable charge transport layer for the purpose of suppressing the charge transport layer component from being mixed into the crosslinkable charge transport layer or improving the adhesion between the two layers. Is possible. For this reason, as the intermediate layer, those that are insoluble or hardly soluble in the crosslinking type charge transport layer coating solution are suitable, and generally a binder resin is used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As the method for forming the intermediate layer, the coating method is employed.

  The thickness of the intermediate layer is not particularly limited and can be appropriately selected according to the purpose, and is preferably 0.05 to 2 μm.

  In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support and the photosensitive layer. The undercoat layer generally comprises a resin as a main component. However, considering that the photosensitive layer is applied with a solvent thereon, these resins are resins having a high solvent resistance with respect to general organic solvents. Is desirable. Examples of the resin include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. In order to prevent moire and reduce residual potential, the undercoat layer is added with a fine powder pigment of a metal oxide such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, or indium oxide. be able to.

For the undercoat layer, a material in which Al ₂ O ₃ is provided by anodic oxidation, an organic material such as polyparaxylylene (parylene), or an inorganic material such as SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ is vacuumed. Those provided by the thin film preparation method can also be used favorably. In addition, known ones can be used.

  The undercoat layer can be formed using an appropriate solvent and a coating method like the above-described photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention.

  There is no restriction | limiting in particular in the film thickness of the said undercoat layer, According to the objective, it can select suitably, 0-5 micrometers is preferable.

  In the present invention, for the purpose of improving the environmental resistance, in particular, for the purpose of preventing a decrease in sensitivity and an increase in residual potential, the cross-linked charge transport layer, the charge transport layer, the charge generation layer, the undercoat layer, An antioxidant can be added to each layer such as the intermediate layer.

  Examples of the antioxidant include phenolic compounds, paraphenylenediamines, hydroquinones, organic sulfur compounds, and organic phosphorus compounds. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the phenol compound include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl- 6-t-butylphenol), 4,4′-thiobis- (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1,3 Tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy Benzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis (4′-hydroxy-3 ′) -T-butylphenyl) butyric acid] cricol ester, tocopherols, and the like.

  Examples of the paraphenylenediamines include N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl- p-phenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine, and the like.

  Examples of the hydroquinones include 2,5-di-t-octyl hydroquinone, 2,6-didodecyl hydroquinone, 2-dodecyl hydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methyl. And hydroquinone and 2- (2-octadecenyl) -5-methylhydroquinone.

  Examples of the organic sulfur compounds include dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like. It is done.

  Examples of the organic phosphorus compounds include triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.

  These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.

  The addition amount of the antioxidant is preferably 0.01 to 10% by mass with respect to the total mass of the layer to be added.

(II) Toner -Toner-
--Average particle size--
The dry toner having a volume average particle diameter (Dv) of 3 to 9 μm and a ratio (Dv / Dp) to the number average particle diameter (Dp) of 1.01 to 1.25 is particularly cleanable. Will be better. In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced, When used as an agent, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.

  On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.

--Measurement method of particle size--
For the toner particle size (volume average particle size, number average particle size), Coulter Counter TA-II (manufactured by Coulter, Inc.) was used as a measuring device. This was continued in a personal computer equipped with an interface (manufactured by Nikka Ki) that outputs the number distribution and volume distribution. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using first grade sodium chloride. Alternatively, ISOTON II (manufactured by Coulter Scientific Japan) may be used. As a measurement method, 0.1 to 5 ml of a dispersant alkylbenzene sulfonate is added to 100 to 150 ml of the electrolytic aqueous solution, and then 2 to 20 mg of a measurement sample is added, followed by dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. Went. The particle size distribution of particles having a size of 2 to 40 μm was measured based on the number using a 100 μm aperture set in the Coulter counter TA-II type. The weight-based weight average particle diameter (D4) and volume average particle diameter (Dv) (the median value of each channel is a representative value for each channel) values obtained from the volume distribution were determined.

--Measurement method of circularity--
The circularity of the toner can be defined as follows.

Circularity = circumference of a circle having the same area as the projected area of the particle / contour length of the projected image of the particle As a method of measuring the circularity, the suspension containing the particle is passed through the imaging unit detection zone on the flat plate. An optical detection method that optically detects and analyzes particle images with a CCD camera is suitable. This value can be measured as an average circularity by a flow type particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. . In the present invention, this average circularity is used.

-Binder resin-
As the binder resin for the toner, resins such as polystyrene resin, polyester resin, and epoxy resin can be used. Polyester resin is preferable, and modified polyester resin is particularly preferable. Examples of the substituent related to the modification of the modified polyester resin include a urea group and a urethane group. Examples of the polyester modified with a urea bond include a reaction product of a polyester prepolymer having an isocyanate group and amines. Can be mentioned. Examples of the polyester prepolymer having an isocyanate group include a polycondensate of a polyol and a polycarboxylic acid, and a polyester obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

-Colorant-
As the colorant used in the toner of the present invention, dyes and pigments capable of obtaining toners of yellow, magenta, cyan and black colors can be used. For example, carbon black, lamp black, ultramarine blue, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, Rogmin 6G, lake, chaco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, etc. Any conventionally known dyes and pigments such as dyes and pigments can be used alone or in combination.

-Electricity control agent-
The charge control agent used in the toner of the present invention is particularly preferably a metal salt of the aforementioned salicylic acid derivative, but if necessary, a transparent or white substance that does not impair the color tone of the color toner may be added, The toner can be stably charged. Specifically, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds and the like are used, but are not limited thereto.

-External powder-
--- Specific surface area of externally added powder--
When the specific surface area of the external additive powder used in the present invention is less than 20 m ² / g, the external additive powder may be present alone without adhering to the toner surface, and the specific surface area is larger than 50 m ² / g. In some cases, the fluidity of the toner may be improved so that the cleaning property becomes insufficient.

--- Amount of external powder added-
When the amount of the external additive powder is less than 0.3 parts by weight, black streaks are likely to occur due to poor cleaning, and when the additive amount is more than 2.0 parts by weight, the external additive powder is excessively present. In some cases, the toner does not adhere to the surface of the toner and inhibits the charging stability of the toner.

--Material of external powder--
The material of the externally added powder may be any material such as silica, titanium oxide, aluminum oxide, various organic fine particles, and various metal particles, but silica and titanium oxide are preferable, and silica is particularly preferable. In addition, the silica used in the present invention is generally produced by a wet method or a dry method, and is particularly called so-called fumed silica produced by a dry method (vapor phase oxidation of a silicon halide compound). It is preferable from the viewpoint of fluidity.

  This fumed silica is manufactured by a conventionally known technique. For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction includes the following reactions.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl
In this production process, for example, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. In the present invention, it can be used as an external powder. Moreover, as a method of hydrophobizing the silica fine powder, a method of surface-treating the surface of the silica fine powder with a silane compound or the like can be mentioned.

  That is, the silane compound is reacted with the hydrogen group bonded to the silica fine powder, and the hydroxyl group is substituted with a siloxyl group, etc. Therefore, the degree of hydrophobization is the above reaction among the hydroxyl groups present before hydrophobization. Is the proportion of hydroxyl groups lost due to. The hydrophobization treatment is performed by reacting a fine silica powder with a dialkyl dihalogenated silane, a trialkyl halogenated silane, a hexaalkyldisilazane, an alkyl trihalogenated silane, or the like at a high temperature. The degree of hydrophobicity of the silica fine powder can be measured by the following method.

--Method of measuring degree of hydrophobicity--
Add 50 ml of water to a 200 ml beaker and add 0.2 g of fine silica powder. Then, while gently stirring with a magnetic stirrer, add methanol from the burette where the tip was immersed in water at the time of dropping, and the floating silica fine powder began to sink. It is obtained from the following formula.

Hydrophobic degree (%) = (ml of methanol dropped / (50 + ml of methanol dropped)) × 100
In this case, methanol acts as a surfactant, and as the silica fine powder that floats is dispersed in water via methanol as the methanol is dropped, the hydrophobicity of the silica fine powder increases as the value of the degree of hydrophobicity increases. The degree of conversion is high.

  Further, in the present invention, by further adding a lubricant as an external additive for the toner, the cleaning property of the residual toner on the photoreceptor after transfer is improved. This is presumed to be because the lubricant reduces the adhesion between the photoreceptor and the toner.

-Lubricant-
Moreover, as a lubricant used in the present invention, fatty acid metal salts, polyvinylidene fluoride, and the like may be added, but are not limited thereto.

-Other additives-
In addition to the external additive powder used in the present invention, alumina or the like may be added as an external additive for the purpose of improving the fluidity of the toner.

(Synthesis example of a compound having a monofunctional charge transporting structure)
The compound having a monofunctional charge transport structure in the present invention is synthesized, for example, by the method described in Japanese Patent No. 3164426. An example of this is shown below.

(1) Synthesis of hydroxy group-substituted triarylamine compound (the following structural formula (9)) 113.85 g (0.3 mol) of methoxy group-substituted triarylamine compound (the following structural formula (8)) and 138 g of sodium iodide ( 0.92 mol) was added 240 ml of sulfolane and heated to 60 ° C. in a nitrogen stream. In this liquid, 99 g (0.91 mol) of trimethylchlorosilane was added dropwise over 1 hour and stirred at a temperature of about 60 ° C. for 4 and a half hours to complete the reaction. About 1.5 L of toluene was added to the reaction solution, cooled to room temperature, and washed repeatedly with water and an aqueous sodium carbonate solution. Thereafter, the solvent was removed from the toluene solution and purified by column chromatography (adsorption medium: silica gel, developing solvent: toluene: ethyl acetate = 20: 1). Cyclohexane was added to the obtained pale yellow oil to precipitate crystals. In this way, 88.1 g (yield = 80.4%) of white crystals of the following structural formula (9) was obtained. The melting point is 64.0-66.0 ° C. The elemental analysis values of this compound are shown in Table 1 .

元素分析値（％）

Elemental analysis value (%)

（２）トリアリールアミノ基置換アクリレート化合物（例示化合物Ｎｏ．５４）
上記（１）で得られたヒドロキシ基置換トリアリールアミン化合物（構造式（９））８２．９ｇ（０．２２７ｍｏｌ）をテトラヒドロフラン４００ｍｌに溶解し、窒素気流中で水酸化ナトリウム水溶液（ＮａＯＨ：１２．４ｇ，水：１００ｍｌ）を滴下した。この溶液を５℃に冷却し、アクリル酸クロライド２５．２ｇ（０．２７２ｍｏｌ）を４０分かけて滴下した。その後、５℃にて３時間撹拌し反応を終了させた。この反応液を水に注ぎ、トルエンにて抽出した。この抽出液を炭酸水素ナトリウム水溶液と水で繰り返し洗浄した。その後、このトルエン溶液から溶媒を除去し、カラムクロマトグラフィー処理（吸着媒体：シリカゲル、展開溶媒：トルエン）にて精製した。得られた無色のオイルにｎ−ヘキサンを加え、結晶を析出させた。この様にして例示化合物Ｎｏ．５４の白色結晶８０．７３ｇ（収率＝８４．８％）を得た。融点は１１７．５〜１１９．０℃である。なお、この化合物の元素分析値を表２に示す。

(2) Triarylamino group-substituted acrylate compound (Exemplary Compound No. 54)
82.9 g (0.227 mol) of the hydroxy group-substituted triarylamine compound (Structural Formula (9)) obtained in the above (1) is dissolved in 400 ml of tetrahydrofuran, and an aqueous sodium hydroxide solution (NaOH: 12.2. 4 g, water: 100 ml) was added dropwise. The solution was cooled to 5 ° C., and 25.2 g (0.272 mol) of acrylic acid chloride was added dropwise over 40 minutes. Then, it stirred at 5 degreeC for 3 hours, and reaction was complete | finished. The reaction solution was poured into water and extracted with toluene. This extract was repeatedly washed with an aqueous sodium bicarbonate solution and water. Thereafter, the solvent was removed from the toluene solution and purified by column chromatography (adsorption medium: silica gel, developing solvent: toluene). N-Hexane was added to the obtained colorless oil to precipitate crystals. In this way, Exemplified Compound No. As a result, 80.73 g (yield = 84.8%) of 54 white crystals were obtained. The melting point is 117.5-119.0 ° C. The elemental analysis values of this compound are shown in Table 2 .

元素分析値（％）
（２官能の電荷輸送性構造を有する化合物の合成例）
本発明における２官能の電荷輸送性構造を有する化合物ジヒドロキメチルトリフェニルアミンは、下記の方法にて製造できる。

Elemental analysis value (%)
(Synthesis example of a compound having a bifunctional charge transporting structure)
The compound dihydroxymethyltriphenylamine having a bifunctional charge transport structure in the present invention can be produced by the following method.

  First, 49 g of compound (1) represented by the following reaction formula and 184 g of phosphorus oxychloride were placed in a flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, and dissolved by heating. 117 g of dimethylformamide was gradually dropped from the dropping funnel, and then the reaction solution temperature was kept at 85 to 95 ° C., and the mixture was stirred for about 15 hours. Next, the reaction solution was gradually poured into a large excess of warm water, and then slowly cooled with stirring. Next, the precipitated crystals were filtered and dried, and then purified by silica gel or the like by impurity adsorption and recrystallization with acetonitrile to obtain compound (2). Yield was 30 g.

  30 g of the obtained compound (2) and 100 ml of ethanol were put into a flask and stirred. After gradually adding 1.9 g of sodium borohydride, the liquid temperature was kept at 40 to 60 ° C., and the mixture was stirred for about 2 hours. Next, the reaction solution was gradually poured into about 300 ml of water and stirred to precipitate crystals. After filtration, the product was sufficiently washed with water and dried to obtain compound (3). Yield was 30 g.

−感光体の製造例−
（製造例１）
モアレ防止のための切削加工を施したアルミニウムパイプ（直径３０ｍｍ×３５０ｍｍ）上にポリアミド樹脂（ＣＭ８０００、東レ株式会社製）の５質量％メタノール溶液を浸漬法で塗工し、０．３μｍの下引き層を設けた。次に、下引き層上に、ＣｕＫαの特性Ｘ線回折におけるブラッグ角（２θ±０．２°）の９．０°、１４．２°、２３．９°、及び２７．１°に強いピークを有するオキシチタニウムフタロシアニン１０部、ポリビニルブチラール（エスレックＢＭ２、積水化学工業株式会社製）１０部、及びシクロヘキサノン６０部を直径１ｍｍのガラスビーズを用いたサンドミルで２０時間分散した。この分散液にメチルエチルケトン１００部を加え、電荷発生層用塗工液を得た。

-Photoconductor production example-
(Production Example 1)
A 5 mass% methanol solution of polyamide resin (CM8000, manufactured by Toray Industries, Inc.) is applied on an aluminum pipe (diameter 30 mm x 350 mm) that has been cut to prevent moiré, and is subtracted by 0.3 μm. A layer was provided. Next, on the undercoat layer, strong peaks at 9.0 °, 14.2 °, 23.9 °, and 27.1 ° of the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα 10 parts of oxytitanium phthalocyanine having 10 parts, polyvinyl butyral (ESREC BM2, manufactured by Sekisui Chemical Co., Ltd.), and 60 parts of cyclohexanone were dispersed in a sand mill using glass beads having a diameter of 1 mm for 20 hours. 100 parts of methyl ethyl ketone was added to this dispersion to obtain a charge generation layer coating solution.

  Using this coating solution, a charge generation layer having a thickness of 0.12 μm was formed by dip-coating on the undercoat layer and drying. Next, 10 parts of a compound represented by the following structural formula was dissolved in 12 parts of polycarbonate Z resin (weight average molecular weight (Mw) = 28,000) and 60 parts of monochlorobenzene. This solution was applied onto the charge generation layer and dried to form a charge transport layer having a thickness of 20 μm.

得られた電荷輸送層上に、電荷輸送性構造を有さない３官能以上のラジカル重合性モノマーとして以下のａとｂの混合物を用い、１官能の電荷輸送性構造を有するラジカル重合性化合物（例示化合物Ｎｏ．５４）１０部、光重合開始剤としての１−ヒドロキシ−シクロヘキシル−フェニル−ケトン（イルガキュア１８４、チバ・スペシャルティ・ケミカルズ株式会社製）１部、及びテトラヒドロフラン１００部からなる組成の架橋型電荷輸送層用塗工液をスプレー塗工し、２０分間自然乾燥した後、メタルハライドランプにて距離１２０ｍｍ強度５００ｍＷ／ｃｍ^２にて６０秒間光照射し、塗布膜を硬化させた。次いで、１３０℃にて２０分乾燥を加え、架橋型電化輸送層の膜厚が５．０μｍとなるように架橋型電荷輸送層を形成し、像担持体Ｎｏ.１を製造した。

On the obtained charge transport layer, a radical polymerizable compound having a monofunctional charge transport structure (a mixture of the following a and b) is used as a trifunctional or higher functional radical polymerizable monomer having no charge transport structure ( Exemplified compound No. 54) 10 parts, 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator, and 100 parts of tetrahydrofuran The charge transport layer coating solution was spray coated and naturally dried for 20 minutes, and then light-irradiated with a metal halide lamp at a distance of 120 mm and an intensity of 500 mW / cm ^{2 for} 60 seconds to cure the coating film. Next, drying was performed at 130 ° C. for 20 minutes, a crosslinked charge transport layer was formed so that the film thickness of the crosslinked charge transport layer was 5.0 μm, and image carrier No. 1 was produced.

<Trifunctional or higher radical polymerizable monomer having no charge transporting structure>
10 parts by weight mixture of a and b below: 10 parts a: caprolactone-modified dipentaerythritol hexaacrylate (KAYARAD DPCA-120, manufactured by Nippon Kayaku Co., Ltd., 1700 mPa · s / 25 ° C., average molecular weight 1947, number of functional groups 6, molecular weight / number of functional groups = 324)

ｂ：トリメチロールプロパントリアクリレート
（ＫＡＹＡＲＡＤ ＴＭＰＴＡ、日本化薬株式会社製、１０５ｍＰａ・ｓ／25℃、分子量＝２９６、官能基数＝３官能、分子量／官能基数＝９９）

b: Trimethylolpropane triacrylate (KAYARAD TMPTA, manufactured by Nippon Kayaku Co., Ltd., 105 mPa · s / 25 ° C., molecular weight = 296, functional group number = trifunctional, molecular weight / functional group number = 99)

（製造例２〜６）
製造例１において、架橋電荷輸送層の膜厚を１．０μｍ、３．０μｍ、８．０μｍ、１０μｍ、２０μｍに形成し、夫々像担持体Ｎｏ.２〜６を製造した。

(Production Examples 2 to 6)
In Production Example 1, the thickness of the cross-linked charge transport layer was formed to be 1.0 μm, 3.0 μm, 8.0 μm, 10 μm, and 20 μm, and image carriers Nos. 2 to 6 were produced, respectively.

(Production Example 7)
In the production example of the image carrier 1, an image carrier 7 was produced in the same manner except that the following mixture of a and b was used as a radical polymerizable monomer having no charge transporting structure.

<Trifunctional or higher radical polymerizable monomer having no charge transporting structure>
10 parts by weight mixture of a and b below 10 parts a: Urethane acrylate (U-15HA, manufactured by Shin-Nakamura Chemical Co., Ltd., 45000 mPa · s / 40 ° C., average molecular weight 2300, functional group number 15, molecular weight / Number of functional groups = 153)
b: Trimethylolpropane triacrylate (previously TMPTA)
(Production Example 8)
In the production example of the image carrier 7, the image carrier 8 was produced in the same manner except that the following mixture of a and b was used as a radical polymerizable monomer having no charge transporting structure.

<Trifunctional or higher radical polymerizable monomer having no charge transporting structure>
10 parts by weight mixture of a and b below: 10 parts a: urethane acrylate (U-15HA mentioned above)
b: Ethoxylated pentaerythritol tetraacrylate (KAYARAD SR-494, manufactured by Nippon Kayaku Co., Ltd., 150 mPa · s / 25 ° C.)
(Production Example 9)
In the production example of the image carrier 1, Exemplified Compound No. 1 is used as a radical polymerizable compound having a charge transporting structure. A radical having no charge transporting structure, using the following structural formula (I) instead of 54
(I)

重合性モノマーとして以下のａとｂの混合物を用いた以外同様にして像担持体９を製造した。

An image carrier 9 was produced in the same manner except that the following mixture of a and b was used as the polymerizable monomer.

<Trifunctional or higher radical polymerizable monomer having no charge transporting structure>
10 parts by weight mixture of a and b below: 10 parts a: caprolactone-modified dipentaerythritol hexaacrylate (DPCA-120 described above)
b: Trimethylolpropane triacrylate (previously TMPTA)
Production Example 10)
An image carrier 10 was produced in the same manner as in Production Example 9 except that the following mixture of a and b was used as a radical polymerizable monomer having no charge transporting structure.

(Trifunctional or more radically polymerizable monomer having no charge transporting structure)
10 parts by weight mixture of a and b below: 10 parts a: urethane acrylate (U-15HA mentioned above)
b: EO-modified pentaerythritol tetraacrylate (KAYARAD RP-1040, manufactured by Nippon Kayaku Co., Ltd., 150 mPa · s / 25 ° C.,
Molecular weight = 528, number of functional groups = 4, molecular weight / number of functional groups = 132)
(Production Example 11)
In the production example of the image carrier 1, Exemplified Compound No. 1 is used as a radical polymerizable compound having a charge transporting structure. In place of 54, Exemplified Compound No. Using 377, the image carrier 10 was produced in the same manner except that the following mixture of a and b was used as a radical polymerizable monomer having no charge transporting structure.

<Trifunctional or higher radical polymerizable monomer having no charge transporting structure>
10 parts by weight mixture of a and b below: 10 parts a: caprolactone-modified dipentaerythritol hexaacrylate (KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd., 900 mPa · s / 25 ° C.,
(Molecular weight = 1263, number of functional groups = 4 functions, molecular weight / number of functional groups = 211)
b: Trimethylolpropane triacrylate (previously TMPTA)
(Production Example 12)
In the production example of the image carrier 11, an image carrier 12 was produced in the same manner except that the following mixture of a and b was used as a radical polymerizable monomer having no charge transporting structure.

<Trifunctional or higher radical polymerizable monomer having no charge transporting structure>
10 parts by weight mixture of a and b below: 10 parts a: urethane acrylate (U-15HA mentioned above)
b: EO-modified pentaerythritol tetraacrylate (RP-1040 described above)
(Production Example 13)
In the production example of the image carrier 1, an image carrier 13 was produced in the same manner except that only trimethylolpropane triacrylate (the above TMPTA) was used as a radical polymerizable monomer having no charge transporting structure.

(Production Example 14)
In a production example of the image carrier 9, dipentaerythritol hexaacrylate (KARAYAD DPHA, manufactured by Nippon Kayaku Co., Ltd., 6000 mPa · s / 25 ° C., molecular weight = 552, functional group as a radical polymerizable monomer having no charge transporting structure. The image bearing member 14 was produced in the same manner except that only the number of radicals = 6, molecular weight / number of functional groups = 100) was used.

(Production Example 15)
In the production example of the image carrier 12, the image carrier 15 was produced in the same manner except that only diurethane acrylate (U-15HA described above) was used as the radical polymerizable monomer having no charge transporting structure.

(Production Example 16)
In the production example of the image carrier 1, an image carrier 6 was produced in the same manner except that the following mixture of a and b was used as a radical polymerizable monomer having no charge transporting structure.

<Trifunctional or higher radical polymerizable monomer having no charge transporting structure>
Mixture of 1: 1 of weight ratio of a and b below 10 parts a: 1,6 hexanediol diacrylate (KS-HDDA, Nippon Kayaku Co., Ltd., 7 mPa · s / 25 ° C., molecular weight 226, number of functional groups 1, Molecular weight / number of functional groups = 226)
b: Urethane acrylate (the above U-15HA)
(Production Example 17)
In the production example of the image carrier 9, the image carrier 17 was produced in the same manner except that the following mixture of a and b was used as a radical polymerizable monomer having no charge transport structure.

<Trifunctional or higher radical polymerizable monomer having no charge transporting structure>
10 parts by weight mixture of a and b below: 10 parts a: caprolactone-modified dipentaerythritol hexaacrylate (DPCA-120 described above)
b: 2- (2-ethoxyethoxy) ethyl acrylate (SR-256, manufactured by Nippon Kayaku Co., Ltd., 6 mPa · s / 25 ° C., molecular weight 188, functional group number 1, molecular weight / functional group number = 188)
(Production Example 18)
In the production example of the image carrier 11, an image carrier 18 was produced in the same manner except that the following mixture of a and b was used as a radical polymerizable monomer having no charge transporting structure.

<Trifunctional or higher radical polymerizable monomer having no charge transporting structure>
10 parts by weight mixture of a and b below: 10 parts a: 1,6 hexanediol diacrylate (said KS-HDDA)
b: 2- (2-ethoxyethoxy) ethyl acrylate (previously SR-256)
(Production Example 19)
In the production example of the image carrier 1, after laminating up to the charge transport layer, 180 g of trimethoxymethylsilane, 280 ml of 1-butanol, and 106 ml of 1% by mass acetic acid aqueous solution were mixed and stirred at 60 ° C. for 2 hours. 370 ml of 1-butanol was added and stirring was continued for 48 hours. To this, 67.5 g of dihydroxymethyltriphenylamine (a compound having a bifunctional charge transporting structure), an antioxidant (Sanol LS2626, Sankyo Co., Ltd.) 1.7 g and 4.5 g of dibutyltin acetate are added and mixed, and a resin layer coating solution is applied, followed by heat curing at 120 ° C. for 1 hour, and the resin layer is formed so that the film thickness becomes 1.5 μm. Thus, an image carrier 19 was produced.

(Production Example 20)
In the photoconductor of Production Example 1, the photoconductor laminated up to the charge transport layer is referred to as an image carrier 20.

(Production Example 21)
In the same manner as in Production Example 1, except that the thickness of the charge transport layer is 5 μm, the compound is changed to Exemplified Compound No. 377 of a radical polymerizable compound having a charge transport structure, and the thickness of the cross-linked charge transport layer is 35 μm. No21 was manufactured. However, the light irradiation time of the metal halide lamp was set to 90 seconds. However, after the production, cracks occurred in the image carrier, which could not be used for image evaluation.

The manufactured image carrier is shown in Table 3 .

−トナーの製造例−
以下、トナーに係る実施例について述べる。なお、以下の記載では、部は重量部を意味する。尚、平均粒径比（体積平均粒径／個数平均粒径）をＤｖ／Ｄｐで表す。

-Example of toner production-
Examples relating to toner will be described below. In the following description, parts means parts by weight. The average particle size ratio (volume average particle size / number average particle size) is represented by Dv / Dp.

(Examples of toners A, B, and C)
(Preparation of Toner A)
100 parts of binder resin 1 (polyester resin, 1/2 outflow start temperature: 126 ° C.), 3 parts of charge control agent (salicylic acid derivative zinc compound), 2 parts of carbon black (Cabot Corporation, Regal 400R) are thoroughly mixed in a blender. Then, it melt-kneaded with the two rolls heated at 100-110 degreeC. The kneaded product was allowed to cool naturally, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and [Toner A] was obtained using an air classifier. Each physical property value was measured after the mother colored particles were immersed in hot water at 80 ° C. for 30 minutes. The average circularity: 0.940, the volume average particle diameter (Dv): 6.4 μm, the number average particle diameter ( Dp): 4.7 μm, Dv / Dp: 1.35.

(Preparation of Toner B)
Toner B was obtained by changing the classification conditions of toner A and reducing the amount of fine powder. Next, each physical property value was measured after being immersed in hot water at 80 ° C. for 30 minutes. The average circularity: 0.968, volume average particle diameter (Dv): 5.4 μm, number average particle diameter (Dp): 4 It was 0.5 μm and Dv / Dp: 1.20.

(Preparation of toners b1 to b9)
Further, by changing the classification conditions, which are toner production conditions, and the heating conditions (temperature, time) with hot water, the volume average particle diameter (Dp) is adjusted to 6.0 μm, and the average circularity is 1.05 to 1.35. And toners b1 to b9 having Dv / Dp of 0.94 to 0.98 were produced.

  (Preparation of Toner C) 240 parts of ethyl acetate / MEK solution of styrene acrylic copolymer as a toner binder in a beaker, 20 parts of pentaerythritol tetrabehenate (melting point 81 ° C., melt viscosity 25 cps), 4 parts of copper phthalocyanine blue pigment The mixture was stirred at 12000 rpm with a TK homomixer at 60 ° C., and uniformly dissolved and dispersed. This is designated as dispersion (1). In a beaker, 706 parts of ion-exchanged water, 294 parts of hydroxyapatite 10% suspension (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.2 part of sodium dodecylbenzenesulfonate were uniformly dissolved. This is designated as dispersion (2). Next, the dispersion (2) was heated to 60 ° C., and the dispersion (1) was added and stirred for 10 minutes while stirring at 12000 rpm with a TK homomixer. The mixture was then transferred to a Kolben equipped with a stirrer and a thermometer, heated to 98 ° C. to remove the solvent, filtered, washed, dried, and then classified by air to obtain [Toner C]. This [Toner C] had an average circularity: 0.988, a volume average particle diameter (Dv): 3.3 μm, a number average particle diameter (Dp): 3.1 μm, and Dv / Dp: 1.05. .

(Production example of toner D)
Among the production conditions of the toner C, the stirring conditions after the dispersion (1) was added to the dispersion (2) were changed. It was set to 9000 rpm and stirred for 20 minutes. As a result, a toner D having an average circularity of 0.980, a volume average particle diameter Dv: 8.8 μm, a number average particle diameter Dp: 8.0 μm, and Dv / Dp: 1.10.

(Developers A, B, C, and b1 to b9)
Next, 100 parts of each of toners A, B, and C are mixed with 1.5 parts of hydrophobic silica (surface area 40 m ² / g, bulk density 190 g / l) in a Henschel mixer and coated with a silicone resin. Carriers having an average particle diameter of 50 μm were mixed at a weight ratio of 5:95 to obtain developers A, B, C and b1 to b9.

(Preparation of developer D)
100 parts of toner D was mixed with 1.5 parts of hydrophobic silica (surface area 40 m ² / g, bulk density 190 g / l) and 0.2 parts of zinc stearate using a Henschel mixer and coated with a silicone resin. A spherical carrier having an average particle diameter of 50 μm was mixed at a weight ratio of 5:95 to obtain developer D.

  In the following, a toner production example using urea-modified polyester as a binder will be shown. The particle size distribution was measured using a particle size measuring device Multiriser II manufactured by Macbeth Coulter.

(1) Preparation of aqueous medium phase (aqueous phase) The following raw materials were charged into a reaction vessel in which a stir bar and a thermometer were set, and stirred at 400 rpm for 15 minutes to obtain a white emulsion.

Water 683 parts Sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30" manufactured by Sanyo Chemical Industries) 11 parts Styrene 138 parts Methacrylic acid 138 parts Ammonium persulfate 1 part.

  The obtained emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% by weight ammonium persulfate aqueous solution was added to the reaction solution, and the mixture was aged at 75 ° C. for 5 hours, and the vinyl resin (styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt co-polymerized). An aqueous dispersion (hereinafter referred to as “fine particle dispersion”) was prepared.

  The obtained “fine particle dispersion” had a volume average particle size of 0.14 μm as measured with a laser diffraction particle size distribution analyzer (“LA-920”; manufactured by Horiba, Ltd.). Further, a part of the “fine particle dispersion” was dried to isolate the resin component. The glass transition temperature (Tg) of the resin component was 52 ° C.

  Thereafter, 990 parts of water, 80 parts of the fine particle dispersion, 40 parts of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate ("Eleminol MON-7"; manufactured by Sanyo Chemical Industries Ltd.), and 90 parts of ethyl acetate are mixed. Stirring to prepare a milky white liquid (hereinafter referred to as “aqueous phase”).

(2) Synthesis of low molecular weight polyester In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 220 parts of bisphenol A ethylene oxide 2 mol adduct, 561 parts of bisphenol A propylene oxide 3 mol adduct, terephthalic acid 218 parts, 48 parts of adipic acid and 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg, and then 45 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. Molecular polyester "was synthesized.

  The obtained “low molecular weight polyester” had a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25.

(3) Synthesis of prepolymer (polymer capable of reacting with active hydrogen group-containing compound)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide were allowed to react at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15 mHg for 5 hours, and "intermediate polyester" was synthesize | combined.

  The obtained “intermediate polyester” has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, a hydroxyl group The value was 51. Then, 411 parts of “intermediate polyester”, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were charged in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Prepolymer 1 was synthesized.

  The free isocyanate content of the obtained prepolymer was 1.53% by weight.

(4) Synthesis of ketimine compound (active hydrogen group-containing compound) 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged in a reaction vessel equipped with a stirrer and a thermometer, and reacted at 50 ° C for 5 hours. 1 was synthesized. The amine value of the obtained ketimine compound (active hydrogen group-containing compound) was 418.

(5) Preparation of masterbatch (MB) 40 parts of carbon black (manufactured by Cabot, Regal 400R), binder resin (polyester resin: Sanyo Chemical Industries, RS-801, acid value = 10, weight average molecular weight ( Mw) = 20000, Tg = 64 ° C.) 60 parts and water 30 parts were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. The mixture was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., and then pulverized to a size of 1 mm in diameter with a perparizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch 1.

(6) Preparation of organic solvent phase (oil phase) In a reaction vessel equipped with a stir bar and a thermometer, 378 parts of the above-mentioned “low molecular polyester”, 110 parts of carnauba wax, CCA (“salicylic acid metal complex E-84”; (Orient Chemical Co., Ltd.) 22 parts and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of a “master batch” and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a “raw material solution”.

  1324 parts of the obtained “raw material solution” was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm. The carbon black and carnauba wax of the “raw material solution” were dispersed in 3 passes under the condition of 80% by volume of zirconia beads. Next, 1324 parts of a 65 wt% ethyl acetate solution of “low molecular polyester” was added to the dispersion. One pass was performed in a bead mill under the same conditions as described above, and the mixture was dispersed to prepare an “organic solvent phase”. The solid content concentration of the obtained organic solvent phase was 50% by weight.

(7) Emulsification / dispersion In a reaction vessel, 648 parts of “organic solvent phase”, 154 parts of “prepolymer”, and 6.6 parts of “ketimine compound” were charged. K. After mixing at 5,000 rpm for 1 minute using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 1200 parts of “water phase” was added to the reaction vessel. K. Using a homomixer, mixing was carried out at a rotational speed of 13,000 rpm for 20 minutes to carry out emulsification and dispersion to prepare an “emulsified slurry”.

  Next, an “emulsified slurry” was charged into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours. Thereafter, the “emulsified slurry” was aged at 45 ° C. for 4 hours. The obtained “emulsified slurry” had a volume average particle size of 5.95 μm and a number average particle size of 5.45 μm.

(8) Washing and drying After 100 parts of the “emulsified slurry” after aging were filtered under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake. K. After mixing with a homomixer (10 minutes at 12,000 rpm), the mixture was filtered. 100 parts of a 10 wt% aqueous sodium hydroxide solution was added to the filter cake obtained here, and T.C. K. After mixing with a homomixer (rotating at 12,000 rpm for 30 minutes), an operation of filtration under reduced pressure (hereinafter referred to as “ultrasonic alkali cleaning”) was performed twice. 100 parts of 10% by mass hydrochloric acid was added to the filter cake obtained here, and T.W. K. After mixing with a homomixer (10 minutes at 12,000 rpm), the mixture was filtered. To the filter cake obtained here, 300 parts of ion exchange water was added. K. The operation of mixing with a homomixer (rotating at 12,000 rpm for 10 minutes) and then filtering was performed twice to obtain a “filter cake”. The “filter cake” obtained here was dried at 45 ° C. for 48 hours with a circulating drier and sieved with a mesh of 75 μm to obtain “Toner E1” by a polymerization method.

  This toner E1 had an average circularity: 0.995, a volume average particle diameter Dv: 6.2 μm, a number average particle diameter Dp: 6.13 μm, and Dv / Dp: 1.01.

  E2 and E3 polymerization toners were produced under different toner E production conditions.

(Toner E2)
Average circularity: 0.962, volume average particle diameter Dv: 6.1 μm, number average particle diameter Dp: 5.0, Dv / Dp: 1.20.

(Toner E3)
Average circularity: 0.950, volume average particle diameter Dv: 6.0 μm, number average particle diameter Dp: Dv / Dp: 1.25.

(Production of developers E1, E2, E3)
100 parts of each of toners E1, E2, and E3 were mixed with 1.5 parts of hydrophobic silica (surface area 40 m ² / g, bulk density 190 g / l) and zinc stearate 0.2 parts in a Henschel mixer, Developers E1, E2, and E3 were obtained by mixing silicone resin-coated spheres having an average particle diameter of 50 μm in a weight ratio of 5:95.

  Next, the cleaning device and the image forming apparatus according to the present invention will be described.

( Reference form 1)
FIG. 1 is a schematic view of a cleaning device (also called a roller cleaning device) according to Reference Embodiment 1 . The image carrier No. 1 is attached to the image carrier 101. 1 was used.

The cleaning device has a cleaning member 102, a scraper blade member 103, and a conveying coil 104. For example, the cleaning member 102 is provided with a conductive elastic layer (for example, a layer formed of conductive rubber) having a rubber hardness of 15 ° to 80 ° and a volume resistance of 10 ⁵ to 10 ¹⁵ (Ωcm) around the metal shaft portion. It is a thing. Further, for example, a tube or a coating layer made of a conductive fluororesin having a volume resistance of 10 ⁶ to 10 ¹⁶ (Ωcm) may be provided around the rubber layer.

The cleaning member 102 is pressed against the surface of the image carrier 101 by a pressure member (not shown) with a force of 300 to 700 (gf), and bites 0.1 to 1.0 (mm) with respect to the surface of the image carrier. Installed in a position with quantity. The roughness of the surface of the cleaning member 102 is R _Z ≦ 5 (μm).

In this reference embodiment , a conductive elastic body having a rubber hardness of 70 ° and a volume resistance of 10 ⁹ (Ωcm) around the core metal 105 is used as the cleaning member 102, and a force of 500 (gf) is applied by a spring. It pressed against the surface of the image carrier 101 and installed at a position having a biting amount of 0.3 (mm) with respect to the image carrier 101. In addition, the driving means (not shown) of the cleaning member 102 is rotated at the same speed as the rotation speed of the image carrier 101. As the cleaning member 102 rotates, the residual toner adhering to the cleaning member 102 from the image carrier 101 reaches the contact portion of the scraper blade member 103 made of sheet-like polyurethane held by the blade holder, and the scraper blade member 103. Is peeled off from the surface of the cleaning member 102, falls on the rotating transport coil 104, and is discharged out of the cleaning device by the transport coil 104.

  FIG. 2 is a schematic view of an image forming apparatus using the cleaning device. The image forming apparatus includes an image carrier 201 that rotates in the direction of arrow A in FIG. 2, and a charging device 207, an exposure device 208, a developing device 209, a transfer device 210, a cleaning device 211, and a charge removal device 212 are disposed around the image carrier 201. Is arranged. Although not shown, a fixing device for fixing the toner image on the transfer material transferred from the image carrier 201 is disposed.

  The charging device 207 is disposed in contact with the image carrier 201, and charges the image carrier 201 to a predetermined polarity and a predetermined potential by applying a predetermined voltage.

  In FIG. 2, a charging roller is used to uniformly charge the image carrier 201 to a negative polarity. As the charging device 207, a scorotron charging device composed of an electrode wire and a grid electrode arranged in non-contact with the image carrier 201 may be used. The exposure device 208 uses an LD as a light emitting element, and forms an electrostatic latent image by irradiating the image carrier 201 with light based on image data. Although an LD is used in FIG. 2, a light emitting element such as an LED may be used.

  The developing device 209 includes a rotatable developer carrying member having a magnet roller fixed inside to hold the developer, and a stirring and conveying screw for conveying the developer while stirring. In FIG. 2, a two-component magnetic brush development system using a two-component developer composed of toner and a magnetic carrier is used as the developer. A one-component development system that does not require a carrier may be used.

  A voltage is applied from a developing bias power source to the developer carrying member, and the electrostatic latent image is adhered to the electrostatic latent image in the developing region for development. The transfer device 210 contacts the surface of the image carrier 201 with a predetermined pressing force at the time of transfer, and a voltage is applied from a power source (not shown), whereby a transfer nip portion between the image carrier 201 and the transfer device 210 is transferred. The toner image on the surface of the image carrier 201 is transferred to a transfer material. In FIG. 2, transfer is performed using a transfer roller, but a transfer device such as a corotron or a transfer belt may be used. The neutralization device 212 neutralizes residual charges on the image carrier 201 and uses an LED. The rotating speed of the image carrier 201 is 200 (mm / sec).

  After the development when a solid image was formed on the image carrier of the image forming apparatus shown in FIG. 2, the charge amount per unit weight of toner after transfer (hereinafter referred to as Q / M) was measured.

Specifically, a solid image latent image is formed on the image carrier using developer A (average circularity 0.94), and the main switch of the image forming apparatus is turned on after development, transfer, cleaning, and the like. Turned off. Next, the toner image formed on the image carrier 201 is sucked with an air pump, and the charge amount of the toner is measured with a coulomb meter (Electrometer 611 manufactured by Kessley), and the Q / M (μC) is calculated from the toner weight and the charge amount. / G) was calculated. The results are shown in Table 4 .

表４に示すように、（２）転写電圧が変動すると（３）転写残トナーのＱ／Ｍが変動する。これは、転写材の種類、画像形成装置の使用環境や使用モード、又経時変動などの様々な変動因子による転写効率の変化があっても、最良の画像が得られるように転写装置２１０の転写電圧が制御された結果を示している。

As shown in Table 4 , (2) when the transfer voltage varies, (3) the Q / M of the untransferred toner varies. This is because the transfer of the transfer device 210 is performed so that the best image can be obtained even if there is a change in transfer efficiency due to various transfer factors such as the type of transfer material, the use environment and use mode of the image forming apparatus, and variations over time. The results show that the voltage is controlled.

  Since the transfer residual toner has a negative polarity, when a positive DC voltage is applied from the power source 206 to the cored bar 205 of the cleaning member 202, the toner is cleaned by the electric field formed between the cleaning member 202 and the image carrier 201. The image carrier 201 adheres to the member 202 and is cleaned.

In the present embodiment , the image carrier 201 and the cleaning member 202 are applied with +700 (V) to the core metal 205 of the cleaning member 202 so that the linear velocity is the same. Under these conditions, the residual toner was transferred to the tape, and the reflectance (ID) was measured to be 0.02. It should be noted that not only this condition but also good cleaning performance was obtained at +400 to +800 (V). However, the appropriate bias varies depending on the environmental conditions, the resistance value of the cleaning member to be used, the thickness, and the like.

Further, the average circularity of the toner was changed and compared. Table 5 shows residual toner IDs when toner A (average circularity 0.94), toner B (average circularity 0.96), and toner C (average circularity 0.98) are mounted. Compared to toner A, toners B and C are cleaned better.

  The method for measuring the remaining toner ID is as follows. The cleaning residual toner on the image carrier 201 after the addition of the cleaning member 202 is transferred to a tape using a transparent tape (Nitto Denko Printac), and the image density (Image Density) is measured by an image densitometer (X-Rite 938). ), And the reflectance was measured to obtain a residual toner ID. The image density of the tape when no toner is present is measured and used as a reference ID, and the reference ID is subtracted from the remaining toner ID to obtain the cleaning residual toner ID.

さらに、トナーの平均円形度、粒径分布を示すＤｖ／Ｄｐを変えたトナーｂ１〜ｂ９を用いて残トナーＩＤを調べた。表６に示すように、Ｄｖ／Ｄｐが小さいトナーほどクリーニング性が良好であった。

Further, the residual toner ID was examined using toners b1 to b9 in which Dv / Dp indicating the average circularity and particle size distribution of the toner was changed. As shown in Table 6 , the smaller the Dv / Dp, the better the cleaning property.

次に、クリーニング部材２０２が像担持体２０１との間に周速差（表面の移動速度の差、線速差とも呼ぶ）をもつようにした。クリーニング部材２０２は駆動装置により像担持体２０１の回転速度に対して周速差をもつように回転駆動されている。また、上述したトナーＡ、Ｃを用い、クリーニング部材２０２の芯金２０５にトナーＡに対して＋５００（Ｖ）、トナーＣに対して＋６００（Ｖ）印加した。

Next, the cleaning member 202 has a peripheral speed difference (also referred to as a surface moving speed difference or a linear speed difference) with the image carrier 201. The cleaning member 202 is rotationally driven by a driving device so as to have a peripheral speed difference with respect to the rotational speed of the image carrier 201. Further, using the toners A and C described above, +500 (V) with respect to the toner A and +600 (V) with respect to the toner C were applied to the core metal 205 of the cleaning member 202.

  As a result, the removal efficiency of residual toner from the surface of the image carrier 201 was improved as shown in FIG.

  However, when the rotation direction of the cleaning member 202 is set to the counter direction (the negative direction in FIG. 3) with respect to the image carrier 201, an effect of mechanically scraping off the toner of the cleaning member 202 is obtained. However, in this configuration, when the amount of toner is small, the surface of the cleaning member 202 and the surface of the image carrier 201 are rubbed with a large peripheral speed difference, so that the surface of the soft cleaning member 202 is more worn than the image carrier. . It is preferable in terms of durability that the peripheral speed difference is eliminated by setting the trailing direction to be 10% or less of the peripheral speed of the image carrier 201.

  Next, the static friction coefficient μ of the cleaning member 202 was changed, and the cleaning performance was examined by providing a peripheral speed difference between the cleaning member 202 and the image carrier 201. The static friction coefficient μOPC of the image carrier 201 and the static friction coefficient μR of the cleaning member 202 were measured by the “Euler belt type” shown in FIG. NBS RICOH type 6200 paper was used as a test member in contact with the image carrier 201, and the static friction coefficient was measured with a load of 100 g. Further, the image forming apparatus shown in FIG. 2 was modified so that rod-shaped zinc stearate can be brought into contact with the image carrier 201, and μOPC was controlled. ΜR was controlled by changing the material of the cleaning member.

The experimental conditions are as follows.
(1) Speed difference, counter direction: -207 (mm / sec)
Image carrier speed: 94 (mm / sec)
・ Speed of cleaning member: 113 (mm / sec)
(2) μOPC: 0.375
(3) μR: 0.27 to 0.65
(4) Cleaning roller bias: 0 (V)
As a result, the cleaning property was good when μR> μOPC. This relationship was maintained even when a bias of +400 V to +800 V was applied. If there is a speed difference between the cleaning member 202 and the image carrier 201, the durability of the cleaning member is lowered. However, it is possible to minimize the peripheral speed difference by applying an appropriate bias.

The transfer efficiency is controlled by increasing the transfer voltage in response to environmental fluctuations and deterioration over time. At this time, as shown in Table 7 (3), when the transfer voltage is increased, the charged polarity of the transfer residual toner is reversed to positive. Therefore, the polarity control means 513 is arranged as shown in FIG. 5 to clean the positive polarity toner.

In this reference embodiment , corona discharge is used as the polarity control means 513. By applying AC 100 (μA) and DC-60 (μA) from the power source 514 to the tungsten wire, negative charges were imparted to the image carrier 501 and the residual toner. The Q / M of the residual toner after passing through the polarity control means 513 is as shown in (4) of Table 7 .

転写残トナーは極性制御手段５１３を通過しマイナス極性にそろえられた後クリーニング部材５０２との対向部に達する。ここで、クリーニング部材５０２の芯金５０５に電源５０６より直流電圧を印加すると、クリーニング部材５０２と像担持体５０１との間で形成する電界により、トナーがクリーニング部材５０２に付着し、像担持体５０１はクリーニングされやすくなる。

The transfer residual toner passes through the polarity control means 513 and is made to have a negative polarity, and then reaches a portion facing the cleaning member 502. Here, when a DC voltage is applied from the power source 506 to the metal core 505 of the cleaning member 502, the toner adheres to the cleaning member 502 due to an electric field formed between the cleaning member 502 and the image carrier 501, and the image carrier 501. Is easier to clean.

( Reference form 2)
FIG. 6 is a schematic view of a cleaning device according to the second embodiment . The image carrier 601 includes an image carrier No. 1 in Production Example 1. 1 was used.

  The toner 615 remaining on the image carrier 601 is conveyed in the CW (clockwise) direction, and is mechanically peeled off from the image carrier 601 by the brush roller 616 rotating in the same direction. The toner that does not fall off the brush roller 616 and remains attached to the roller is knocked off by the bias roller 617. The bias roller 617 may be rotating or fixed. The toner dropped from the brush roller 616 and the bias roller 617 is collected in the developing tank by a collecting roller 619 in the cleaning unit 618 and reused. In order to stabilize the system, it may be collected in a waste toner bottle and discarded.

  When cleaning from the image carrier 601, there are cases where the transfer residual toner has a polarity. By applying a bias from the transfer bias power source 620 to the bias roller 617 and applying it to the brush tip of the brush roller 616, an electrostatic force is applied simultaneously with the mechanical force of the brush, and the cleaning property is further improved.

  In this example, a bias voltage is applied via the bias roller 617, but it may be applied directly to the core of the brush roller 616. As a bias from the transfer bias power source 620, a DC voltage or an AC voltage opposite to the polarity of the toner, or both a DC voltage and an AC voltage may be superimposed. Toners having different polarities are adsorbed by the brush, or toners having polarity are erased by application of an AC voltage, and are knocked off from the image carrier 601 by the mechanical force of the brush.

In particular, when the hair transplantation intervals of the brush are alternately planted for each row, the toner between the hair transplantations can be reliably cleaned by the brush. Moreover, it is preferable that the fiber diameter (d) of flocking and the pitch (P) between flocking adjoining and the number of rows flocked alternately have the following relationship. By defining the flocking configuration, it is possible to eliminate toner that leaks from both sides of the brush.
d ≧ P / n (d: fiber diameter of flocking, P: flocking axial direction pitch, n: number of rows in the flocking rotation direction)
Further, since the brush fiber (raw yarn) is composed of a main branch and a sub-branch, it is possible to reliably clean the toner that leaks. This flocked state will be described in detail below.

( Reference form 3)
In the transfer process, the toner on the image carrier is electrostatically transferred to an intermediate transfer medium used for recording paper or color by applying a high voltage, but a discharge phenomenon occurs between the image carrier and the transfer electrode. In some cases, toner with a small charge amount or toner with an abnormal polarity is inverted in polarity by discharge. For this reason, the transfer residual toner has non-uniform polarity. In other words, a state in which positive polarity toner is mixed in negative polarity toner is generated by development. This state is shown in FIG.

  In order to prevent this, there is a method in which a pre-treatment charging step is provided before cleaning, and the polarity of the transfer residual toner is made uniform. However, the charging process using a high voltage generates ozone and nitrogen oxides, has an influence on the environment and the human body, or causes image deterioration of the image carrier.

  Therefore, it is preferable to collect transfer residual toners having different polarities by applying a bias voltage corresponding to the polarity of each toner without homogenizing the polarity by the pretreatment charging process. Specifically, a positive polarity bias is applied to the brush roller 721 shown in FIG. 7, and a brush roller 716 is further provided on the downstream side. Cleaning is possible.

  FIG. 8 shows a cleaning state diagram of residual toner on the image carrier 801 as viewed from the side.

The brush roller is configured by winding a brush 823 planted on a base fabric around the surface of a core metal 824 on a spiral. The base fabric is generally a polyester nylon material. The brush 823 is straight hair or a loop shape, and the density is 50,000 to 150,000 (lines / inch ² ), and the hair pitch is 0.7 to 0.9 (mm). ~ 50 yarn bundles are implanted. The raw yarn is composed of carbon-containing acrylic fibers having a thickness of 15 to 30 (μm). Since the fibers are set in a state where the fibers bite into the photosensitive member by about 0.5 (mm), the fibers are in a buckled state. Here, FIG. 9 shows a state in which FIG. 8 is observed from the B viewing direction.

  The cleaning toner 925 is captured at the tip where the brush exists. However, the non-cleaning toner 926 passes between the flocks where the brush is not flocked. In order to improve this, in the next line as shown in FIG. 10, the toner that has come off by flocking between the flocks of the previous line is captured, and the image carrier is cleaned.

  FIG. 11 shows a conventional flocked state. The flocks are arranged in a grid pattern at a constant pitch in both rows and columns. The planted base fabric is manufactured by winding a fabric having a constant pile width (15 to 20 mm), but the pitch between the planted hairs is not filled. Therefore, as shown in FIG. 12, when the pitch P in the column direction and the flocking diameter d and the number of rows in which the flocks are located at the same place in the row direction are n, the relation of d ≧ P / n is established. As a result, the slip-through toner comes into contact with the brush, and the residual toner is reliably captured or scraped off.

  As shown in FIG. 13, the brush roller is formed by bundling raw yarns and has a bristle length of about 5 (mm). This raw yarn is a straight fiber as shown in FIG. 14, and if it is only in contact with a spherical toner, it slips through and causes poor cleaning. In order to prevent this, as shown in FIG. 15, a capture sub-branch 1528 is provided on the main branch 1527 planted on a straight line. The length of the sub-branch 1528 is 0.05 to 0.1 (mm), and a slight branch-like protrusion is provided to eliminate the toner that leaks from the brush and reliably contacts the brush to clean the residual toner. .

( Reference form 4)
Reference form 4 will be described. The image carrier 1601 includes an image carrier No. 1 in Production Example 1. 1 and developer C were used.

Figure 16 is a schematic schematic representation of a cleaning device according to the reference embodiment 4. FIG. 17 is a schematic view of an image forming apparatus using a cleaning device.

  This will be described with reference to FIG. Since the cleaning brush 1629 is disposed so as to rub against both the image carrier 1601 and the cleaning roller 1630, the amount of residual toner arriving at the cleaning roller 1630 due to the primary cleaning effect by the cleaning brush 1629 is greatly reduced, and Since toner scraping from the cleaning roller 1630 can be realized without adding a scraper or a dedicated cleaning brush, a cleaning means utilizing the high-performance cleaning roller 1630 can be realized in a small size and at low cost.

  When the rotation direction of the cleaning roller 1630 is set to the counter direction with respect to the image carrier 1601, the toner that has not been scraped off from the cleaning roller 1630 by the cleaning brush 1629 is moved to the wedge-shaped region on the downstream side of the cleaning roller 1630. . At this time, if the toner adheres to the image carrier 1601 side by electrostatic or mechanical action within the wedge-shaped region, it passes through the charging means as it is. Since the present invention is in the trailing direction, the toner that has not been scraped off moves again to the upstream side of the cleaning roller 1630, so that it is once again subjected to the cleaning action of the cleaning roller 1630, thereby reducing the cleaning performance. Absent.

  When the rotation direction of the cleaning roller 1630 is set to the counter direction with respect to the image carrier 1601, the mechanical working force of the cleaning roller 1630 is increased, and an effect of mechanically scraping off the toner can be obtained. However, with such a configuration, when the amount of toner is small, the surface of the cleaning roller 1630 and the surface of the image carrier 1601 are rubbed with a large peripheral speed difference, so that polishing wear progresses and durability is lowered.

  The present invention not only eliminates the peripheral speed difference by setting the trailing direction, but also gives the cleaning roller 1630 the effect of mechanical scraping by providing the peripheral speed difference to 10% or less of the image carrier 1601 speed. It is possible to achieve both improved cleaning performance and durability. According to experiments conducted by the inventors, it has been found that the effect of mechanically scraping is improved by giving only a few percent. Therefore, considering the durability, in order to establish the apparatus with as little peripheral speed difference as possible, it is set to 10% or less.

  In the present invention, since the cleaning brush 1629 is used for scraping off the toner of the image carrier 1601 and the cleaning roller 1630, the amount of toner adhering is reduced by passing through the flip cover 1631 and the tip of the brush whose cleaning ability is restored is By effectively rubbing against the cleaning roller 1630 on which a small amount of cleaned toner is adhered, the scraping ability is effectively exhibited. Furthermore, since the toner adhering to a relatively large amount on the image carrier 1601 is scraped off after a slight increase in the amount of adhering toner, the cleaning performance is excellent.

  Further, according to FIG. 16, since the cleaning brush 1629 is in the counter direction and the cleaning roller 1630 is in the trailing direction with respect to the image carrier 1601, the distance between the cleaning brush 1629 and the cleaning roller 1630 is in the trailing direction, and the rubbing speed is Obtained by the difference in roller speed.

  The surface hardness of the image carrier 1601 is much higher than that of the cleaning roller 1630 made of hydrin rubber or the like. Therefore, when the cleaning brush 1629 is rubbed, the image carrier 1601 is rubbed at a high speed with priority on improving the cleaning performance, and the cleaning roller 1630 is rubbed at a low speed in consideration of the strength of the material. desirable. As described above, since the cleaning roller 1630 and the cleaning brush 1629 are in the trailing direction, in this configuration, even if the cleaning brush 1629 is used for both scraping off the image carrier 1601 and scraping from the cleaning roller 1630, the cleaning roller The durability of 1630 is not impaired.

  The cleaning roller 1630 is configured such that an electric field in a direction in which toner is attracted by a biasing unit (not shown) is generated at a contact portion with the image carrier 1601, and the toner is imaged mainly by electrostatic attraction force. An action of adsorbing from the carrier 1601 onto the cleaning roller 1630 is performed. Since such an acting force is exerted regardless of the toner shape, even the spherical dry toner of this embodiment can be easily cleaned.

  Therefore, although it is difficult to clean the spherical toner with the conventional blade cleaning method, the present invention has realized the spherical toner cleaning method with a small and low cost configuration instead of the blade cleaning method. A low-cost and high-quality image forming apparatus can be established.

( Reference form 5)
Figure 18 is a schematic schematic representation of a cleaning device according to the reference embodiment 5. The image carrier 1801 includes an image carrier No. 1 in Production Example 1. 1 and developer E1.

In this reference embodiment, the cleaning means is composed of a conductive cleaning roller 1832 having elasticity, and also serves as a charging device for the image carrier 1801. The charging / cleaning roller 1832 is disposed in contact with the image carrier 1801 and rotates in the direction of arrow C. The charging / cleaning roller 1832 applies a voltage from the power source 1833 to charge the image carrier 1801 to a predetermined polarity and a predetermined potential. In this reference embodiment , the image carrier 1801 is uniformly charged to a negative polarity.

  When cleaning small particle size spherical toner with a blade, it is necessary to increase the abutting force in order to prevent poor cleaning, but a large stress is applied to the toner in the portion where the cleaning blade and the image carrier 1801 are in contact with each other, The wax inside the toner may ooze out and adhere to the image carrier 1801, and wax filming may occur.

Therefore, the cleaning device of the present embodiment ensures the wax fill from the image carrier 1801 even when using toner using a sharp-melt polyester-based toner binder having a spherical shape with a small particle size and a lower melt viscosity than conventional toners. The cleaning is performed by applying a voltage using an elastic roller so that the cleaning can be performed without mingling. Further, the cleaning roller is configured to charge the surface of the image carrier 1801.

  The cleaning roller 1832 is an elastic material in which conductive fine particles made of an oxide of metal such as carbon black, titanium, and aluminum, an ionic conductive agent, etc. are dispersed in an elastic material such as polyurethane rubber, silicon rubber, and braziene rubber with a cored bar 1834 as a center. It has a conductive layer.

Further, an intermediate resistance layer is provided on the surface of the cleaning roller 1832 in order to prevent leakage of bias current due to a pinhole on the surface of the image carrier 1801. In some cases, a surface protective layer may be further provided to prevent the surface of the cleaning roller 1832 from being soiled. In the present embodiment , a roller adjusted so that the volume resistivity is 10 ⁶ to 10 ¹² (Ωcm) is used.

  A power source 1833 is connected to the cored bar 1834, a voltage is applied from the power source 1833 to the cleaning roller 1832, and residual toner on the image carrier 1801 is attracted to the cleaning roller side by electrostatic force, and the cleaning roller Cleaning can be performed by rotating 1832.

  FIG. 19 shows a series of processes. This is a reversal development method in which the image carrier 1901 is negatively charged and the negatively charged toner adheres to the exposed portion. The toner deposited on the image carrier 1901 after development has a negative polarity. Accordingly, a positive voltage or current is applied to the transfer device to transfer the negative polarity toner onto the transfer material. As a result, the transfer residual toner on the image carrier 1901 is inverted due to the influence of the transfer bias, and becomes a positively charged toner. Accordingly, by applying a negative voltage to the cleaning roller 1932, the positive transfer residual toner on the image carrier 1901 is cleaned.

  Specifically, by applying a voltage of −1300 V from the power source 1933 to the metal core 1934 of the cleaning roller 1932, the image carrier 1901 is uniformly charged to −700 V by discharge. Then, writing is performed by the image exposure device 1935, and the surface potential of the image carrier 1901 after exposure is set to -100V. The formed latent image is developed by applying a voltage of −400 V to the developing roller of the developing device 1936 holding the developer to attach a negative polarity toner. The developed toner is transferred to a transfer material 1938 by a transfer roller 1937 to which a voltage of +1500 V is applied, and a transfer residual toner having a positive polarity remains on the image carrier 1901.

  Although the surface potential of the image carrier 1901 is affected by the transfer, the surface potential becomes 0 V due to the static elimination light of the static elimination device 1939. Next, the positive transfer residual toner is electrostatically cleaned by the cleaning roller 1932 to which −1300 V is applied in the cleaning process, and the image carrier 1901 can be charged to −700 V again.

( Embodiment 6)
Embodiment 6 will be described with reference to FIG. The image carrier 1801 includes an image carrier No. 1 in Production Example 1. 1 and developer E2.

In the sixth embodiment , two electrostatic cleaning auxiliary means are provided upstream of the cleaning blade. Although referred to as cleaning assisting means, this is a factor that substantially determines the cleaning ability of the entire cleaning means. For image formation, reverse development and a non-contact charging roller system are used. A brush roller is used as a cleaning auxiliary means, and a metal roller is provided as a cleaning device for cleaning the surface of the brush roller.

  When image formation is started, a predetermined voltage or current is sequentially applied to the non-contact charging roller 3, the developing roller 8, the transfer roller 15, the upper recovery roller 24, the lower recovery roller 28, and the static elimination lamp 2 at predetermined timings. Almost simultaneously, the photosensitive member 1, the non-contact charging roller 3, the transfer roller 15, the developing roller 8, the left screw 9, the right screw 10, the upper cleaning brush 23, the upper recovery roller 24, the lower cleaning brush 27, the lower recovery roller 28, and the toner discharge The screw 19 rotates in a predetermined direction. The photoreceptor 1 is uniformly negatively charged (-900 V) by a non-contact charging roller 3 arranged in a non-contact manner, and a latent image is formed by the laser beam 4 (black solid potential is -150 V). The latent image is developed by a magnetic brush formed by the developing roller 8 (development bias is −600 V) to form a toner image.

  Then, the toner image is fed between the photosensitive member 1 and the transfer roller 15 from a paper feeding mechanism (not shown), and is transferred onto the transfer paper supplied in synchronization with the leading edge of the image by the upper registration roller 12 and the lower registration roller 11. The toner image is transferred (+10 μA applied). The transfer paper is separated from the photoreceptor 1 by the separation claw 16 and is discharged as a copy image through a fixing device (not shown).

  The untransferred toner on the photoreceptor 1 after the transfer is in a state where “+ polarity” and “−polarity” are mixed as shown in FIG. 27 described above. (The charge amount distribution of the untransferred toner varies depending on environmental conditions, transfer conditions, etc. as shown in FIGS. 28, 29, and 30). In this state, the toner is transferred to the position of the lower cleaning brush 27. DC + 200V is applied to the lower collection roller 28, and a potential gradient corresponding to the brush resistance is formed on the lower cleaning brush 27, thereby electrostatically adsorbing the “−polar” toner of the transfer residual toner. As shown in FIG. 31, only the “+ polarity” toner remains after the lower cleaning brush 27, and is transferred to the position of the upper cleaning brush 23. DC-200V is applied to the upper collection roller 24, and the remaining “+ polarity” toner is electrostatically adsorbed.

  The method of electrostatically cleaning the transfer residual toner in which toners having different polarities are mixed in this way is effective, but actually, a small amount of toner remains after the upper cleaning brush 23. This small amount of toner is preferably input to the cleaning blade 22 in a stable manner, and it is convenient because the cleaning blade 22 does not get involved due to the lubricating effect of the toner.

  However, there is still room for improvement in this electrostatic cleaning. The problem is the presence of nonpolar toner, the problem of charge injection into the toner, or the case where there is no toner input to the cleaning blade stably after electrostatic cleaning in an unsteady state such as a jam.

  First, the toner is injected by applying a voltage for cleaning. At this time, the charge amount is shifted to the applied voltage side, and is not attracted to the cleaning brush, and is attached to the photosensitive member 1 again. Since the upper collection roller 24 and the lower collection roller 28 shown in FIG. 20 are made of metal, when the transfer residual toner is cleaned from the photoreceptor 1 with the cleaning brush and transferred to the collection roller, the contact between the cleaning brush and the collection roller Charge is injected at the portion, and a part of the toner on the cleaning brush has the same polarity as the applied voltage, remains on the cleaning brush, and is exposed to the electric field generated by the photosensitive member 1 and the cleaning brush when coming into contact with the photosensitive member 1 again. It will be transferred to the body 1.

Table 8 shows the results of this analysis. That is, in FIG. 21-1, which is a conventional example, the cleaning brush 22 and the cleaning brush 27 are configured, and the transfer portion is removed and the developed toner (all-polarity) is sent to the cleaning portion as it is. Is analyzed.

表８（ａ）に示すように、回収ローラ２８の印加電圧が増加すると、クリーニングブラシ２７後の残ＩＤは＋１００Ｖから一旦減少し、＋２００Ｖを過ぎて再び増加している。印加電圧＋１００Ｖにおいてクリーニング不足でＩＤが大きいが、＋１００Ｖでは電荷注入が殆ど無く、クリーニングブラシ２７後のトナーの帯電量分布は現像後と同じであった。又、印加電圧が＋２００Ｖ過ぎて残トナーＩＤが増加しているのは、クリーニングブラシ２７と回収ローラ２８の接触部でトナーが電荷注入され、印加電圧極性に反転して再付着したものである（このときのトナー帯電量は殆ど「＋極性」であった）。

As shown in Table 8 (a), when the applied voltage of the collection roller 28 increases, the remaining ID after the cleaning brush 27 once decreases from + 100V, increases again after + 200V. Although the ID was large due to insufficient cleaning at an applied voltage of +100 V, there was almost no charge injection at +100 V, and the toner charge amount distribution after the cleaning brush 27 was the same as that after development. The reason why the residual toner ID increases because the applied voltage exceeds + 200V is that the toner is injected at the contact portion between the cleaning brush 27 and the collection roller 28, and reversely adheres to the applied voltage polarity. The toner charge amount at this time was almost “+ polarity”).

Further, when the collecting roller 28 is removed and the applied voltage is directly applied to the cleaning brush 27 in the configuration shown in FIG. 21B, the remaining ID becomes almost “0” as shown in Table 8 (b), and the cleaning is completely performed. It had been. From this result, it was found that toner charge injection occurred between the cleaning brush 27 and the collection roller.

Also, toner charge injection occurs between the cleaning brush and the photoreceptor. The degree varies depending on the resistance value of the brush, and decreases as the brush resistance increases. In the present invention, the cleaning brushes 23 and 27 having a resistance of 10 ⁸ to ⁹ Ω · cm are used. Therefore, in this configuration, a small amount of toner is always input to the cleaning blade.

  Further, when the spherical toner is cleaned by the cleaning blade 22, if the amount of input toner increases, a streaky or belt-like cleaning defect occurs. This is said to occur because the spherical toner rotates and enters the cleaning blade 22 while rotating.

In the conventional configuration shown in FIG. 21A, in normal image formation, the post-development toner adhesion amount (hereinafter referred to as M / A) is about 0.5 mg / cm ² . Assuming that the transfer rate is 90%, the amount of residual toner after transfer is 0.05 mg / cm ² . The toner charge amount distribution is approximately half of plus and minus. Therefore, the amount of toner input to the cleaning blade 22 is 0.025 mg / cm ² and should be able to be cleaned. However, cleaning becomes difficult when the amount of residual toner changes over time or under various image forming conditions. Typically, there are cases where the environment has changed or toner has been replenished.

When the temperature and humidity become high, as shown in FIG. 29, the charge amount distribution of the developed toner changes, and as a result, the input amount to the cleaning blade changes. Also, the toner of the developer immediately after replenishing the toner is insufficient in frictional charge with the carrier and the toner charge amount is low, and the charge amount distribution is the same as in the case of this high temperature and high humidity. appear. It is said that most “+ polarity” toners are related to background smudges. However, since this smudge toner is added to the transfer residual toner amount and input, the amount of toner input to the cleaning blade 22 increases. To do. As described above, when the amount of input to the cleaning blade 22 increases and exceeds a certain amount (typically 0.05 mg / cm ² ), a cleaning failure occurs.

  Further, since the transfer is not performed when the jam occurs, the amount of toner input to the cleaning blade 22 becomes the amount of toner after development, which greatly increases, resulting in a cleaning failure. When there is one conventional cleaning auxiliary means, a voltage in the direction of cleaning the toner after development is applied (because it is a negative polarity toner, the applied voltage becomes a positive polarity). On the other hand, most of the scumming toner is a + polar toner and cannot be cleaned by the voltage applied by the cleaning assisting means.

Therefore, in order to clean the spherical toner, it is possible to electrostatically clean both + and -polar toners with two cleaning auxiliary means as in the present invention, and the amount of input to the cleaning blade 22 is small. It is preferable to maintain it at about 0.05 mg / cm ² or less. In the present invention, while cleaning toner having a polarity opposite to the applied voltage with each cleaning brush, charge is injected into the toner at the contact portion between the cleaning brush and the collection roller, and a small amount of toner is applied to the photoreceptor 1 after passing through each brush. The toner is adhered. As a result, the spherical toner can be cleaned without any trouble such as a cleaning blade being caught.

As described above, when the cleaning brushes 23 and 27 have a resistance of 10 ⁸ to ⁹ Ω · cm, it is one of the preferred embodiments that both cleaning brushes have the same and high resistance. is there. Further, the resistance of the cleaning brush 23 can be 10 ⁸ to ⁹ Ω · cm, and the cleaning brush 27 can be 10 ⁵ to ⁶ Ω · cm. The resistance of the most upstream cleaning brush can be reduced to the downstream cleaning. A lower resistance than the brush is also a preferred embodiment. In the present invention, it is more preferable that the transfer residual toner having mixed polarities is aligned with one polarity by one brush and cleaned with one brush.

  The plurality of cleaning assisting means having the above functions may be a rubber roller made of an elastic body in addition to the brush roller, or a rubber roller having a surface layer to increase the hardness. It may be a rotating magnetic brush utilizing the rising of magnetic particles. Further, one of the plurality of cleaning auxiliary means may be a fixed one that does not rotate. For example, there are a fixed brush, a sheet-like elastic body, etc. subjected to conductive treatment. At least the cleaning auxiliary means arranged downstream is rotating, and it is preferable to have a cleaning device for cleaning the cleaning auxiliary means for maintaining the function of the cleaning auxiliary means.

  In addition, the cleaning blade of the present invention can be used with known materials and shapes under known conditions. Since a plurality of electrostatic cleaning auxiliary means are provided upstream of the cleaning blade, the cleaning blade is not used in the overload state seen in cleaning of a small particle size and spherical toner. At the same time, since the image is formed using the photoconductor having the cross-linked charge transport layer of the present invention, the wear of the photoconductor can be reduced and maintained to a preferable state.

  The term “abrasion” as used herein refers to wear that causes the surface of the photoreceptor to decrease in film thickness on average. The preferred state of wear refers to those which are not preferable for image formation such as deterioration of the surface of the photoconductor that occurs during image formation, deposition of charged products, adhesion of toner components, etc. This is a state in which filming substances, substances causing image flow, and the like are removed by slight abrasion of the surface of the photoreceptor. The ability to maintain a favorable wear state is close to the meaning of wear control. According to the present invention, this wear control has a great effect on cleaning of a small particle size and spherical toner.

  Therefore, for example, it is possible to harden the cleaning blade and control the wear with a large contact pressure in a preferable state. In addition, it is possible to use the cleaning blade by adding an abrasive to give a polishing function in a preferable state, and a cleaning blade including a known abrasive can be preferably used. As a result, the surface of the photoreceptor is always used for image formation in a state of being updated.

  Conventionally, there has been an embodiment in which the surface of the organic photoreceptor is polished to remove foreign matter. However, polishing a photosensitive layer made of a soft organic material often promotes film abrasion and damages. I was dissatisfied for that. In some embodiments, the photosensitive member provided with a hard protective layer using an organic or inorganic material was polished. However, a preferable polishing amount could not be maintained, and foreign matter remained on the surface, which was also unsatisfactory.

( Embodiment 7)
Embodiment 7 according to the present invention will be described. The image carrier 1801 includes an image carrier No. 1 in Production Example 1. 1 and developer E3.

The operation when the cleaning auxiliary means arranged at the most upstream shown in FIG. 22 is a fixed brush and does not have a cleaning device will be described. The fixed brush 32 is of low resistance and has a resistance value of 10 ^{5 to 6} Ω · cm. The resistance value of the upper cleaning brush is 10 ^{8 to 9} Ω · cm. Further, auxiliary means such as a sheet-like elastic member may be about 10 ^{5 to 6} Ω · cm. For example, when a voltage of “+ 200V” is applied, the transfer residual toner has a charge amount distribution in which “+ polarity” and “−polarity” are mixed as shown in FIG. 27, but the fixed brush 32 is low. Due to the resistance, part of the transfer residual toner is effectively electrostatically adsorbed to the fixed brush 32, and part of the toner charging polarity is inverted by charge injection to become the polarity of the applied voltage (+ polarity). Pass through. The amount that passes through the fixed brush 32 differs depending on the magnitude of the applied voltage. When the applied voltage is increased, charge injection increases, and the amount that passes through the fixed brush 32 increases. Since there is no cleaning device, the toner that is electrostatically attracted to the fixed brush 32 accumulates due to continuous toner input, and the charge injection performance deteriorates when the brush becomes dirty, but the charge is gradually injected over time and the polarity is reversed. Then, it is transferred onto the photoreceptor 1. Then, after a certain number of copies, the toner input amount, output amount, and accumulation amount reach equilibrium.

  In addition, the input amount of the transfer residual toner increases at high temperature and high humidity, and when the toner having the charge amount distribution as shown in FIG. 29 is input to the fixed brush 32, the charge injection performance is deteriorated when the toner accumulates on the fixed brush 32. The toner accumulated in the fixed brush 32 must be transferred with a polarity (in this case, + polarity) that can be cleaned by the next upper cleaning brush 23. In such a case, when a non-image is formed after a certain number of sheets, after a certain period of time, etc., a voltage higher than usual is applied to the fixed brush 32 to inject electric charge, and the toner on the fixed brush 32 is transferred to the photoreceptor 1 to transfer the fixed brush. What is necessary is just to add the cleaning mode on 32. This is the same in other embodiments such as a sheet-like member.

  20, 22, 23, and 24, the case where “AC + DC” is applied to the most upstream cleaning auxiliary means will be described with the configuration of FIG. 20. As shown in FIG. 31, the toner charge amount distribution after the lower cleaning brush 27 when the DC voltage is applied to the lower recovery roller 28 is broad with a distribution of “+ polarity”. Toner with a high charge amount has a large electrostatic force with respect to the photoreceptor 1, and the upper cleaning brush is difficult to remove with an electrostatic force. It becomes difficult to remove even with the cleaning blade 22 and causes filming. Therefore, “AC + DC” is applied to the lower collection roller. The toner charge amount distribution after the lower cleaning brush 27 is made sharp and low, so that the upper cleaning brush 23 can easily remove the charge amount distribution. Specifically, when AC is 1.5 kHz, Vpp: 200 V sine wave, and DC component is +100 V, the toner charge amount distribution after the lower cleaning brush 27 is sharp and the charge amount is low as shown in FIG. Easy cleaning with the upper cleaning brush 23. The AC and DC components are not limited to the above conditions.

(Adaptation to other image forming devices)
A description will be given of a reference embodiment in which the electrostatic cleaning device of the present invention, an image carrier having a spherical toner and a cross-linked surface layer are applied to other image forming apparatuses. Figure 25 uses a cleaning apparatus 2051 described in Reference Embodiment 1 is a tandem color image forming apparatus of the type juxtaposing four image forming units 2050 along the transfer belt 2056 extending horizontally.

  The image forming unit 2050 includes an image carrier 2055, a charging device 2052, an exposure device 2053, a developing device 2054, a roller cleaning device 2051, and a charge eliminating device 2058. The image forming unit 2050 is for each color of yellow, magenta, cyan, and black. Are arranged in four. The development toner developed in each image forming unit 50 is transferred to a transfer material 2057 by a transfer belt 2056 to which a transfer voltage extending horizontally is applied. In this way, images of yellow, magenta, cyan and black are formed, transferred onto a transfer material, and fixed by a fixing device (not shown). Although described in the order of yellow, magenta, cyan, and black, they are not specified in this order, and may be arranged in any order.

  The untransferred toner remaining on the image carrier without being transferred is cleaned by a roller cleaning device 2051. However, when the cleaning blade is used as a main cleaning capability, the image is particularly formed by wax filming on the image carrier. The coefficient of friction of the carrier decreases, and the adhesion between the image carrier and the toner decreases. Therefore, the toner on the image carrier is easily transferred to the transfer material 2057 by discharge before the nip between the transfer material 2057 and the image carrier, and an abnormal image called so-called transfer dust occurs.

By using the torque cleaning apparatus 2051 by the present reference embodiment, since there is no wax filming to the image bearing member, toner scattering does not occur. Furthermore, no image flow occurs in a high temperature and high humidity environment. Therefore, in a color image forming apparatus that requires four times of transfer in each image forming unit as in this reference embodiment , a particularly good image can be obtained over a long period of time.

In this reference embodiment has been described with reference to cleaning device of Reference Embodiment 1, Reference Embodiment 2, reference embodiment 3, reference embodiment 4, reference embodiment 5, embodiment 6, and also by using the cleaning apparatus of Embodiment 7 Similar effects can be obtained. Further, FIG. 26 is a schematic diagram using a plurality of developing devices 2159 to 2162 using the cleaning device described in the first embodiment and a color image forming apparatus having an intermediate transfer member.

The color image forming apparatus according to the present embodiment forms a single color image on an image carrier by a plurality of developing devices 2159 to 2162, and forms a full color image by superimposing the single color image on the intermediate transfer member 2164. This is a full-color image forming apparatus that employs a system in which images are collectively transferred onto a transfer material 2165 by a transfer device 2166.

  The full-color image forming apparatus includes a photosensitive member 2163, a charging device 2168, an exposure device 2169, four developing devices 2159 to 2162, a cleaning device 2167, and a charge eliminating device 2170. The developing devices 2159 to 2162 are yellow, magenta, cyan, and black. Four are arranged for each color. In this case, development is performed in the order of yellow, magenta, cyan, and black, and the image is transferred to the intermediate transfer member 2164. Finally, a four-color full-color image is formed on the intermediate transfer member, and transferred onto the transfer material 2165 at once. And is fixed by a fixing device (not shown). Although described in the order of yellow, magenta, cyan, and black, they are not specified in this order, and may be arranged in any order.

Transfer residual toner remaining on the image bearing member without being transferred is being cleaned by cleaning apparatus described in Reference Embodiment 1, the case of using a cleaning blade as a primary cleaning performance, to an image bearing member Wax filming occurs, and the wax also transfers to the intermediate transfer member, reducing the friction coefficient of both the image carrier and the intermediate transfer member, and the adhesion between the image carrier and the toner, and the intermediate transfer member and the toner. Is reduced. For this reason, as described above, an abnormal image called transfer dust due to discharge occurs. The amount of dust toner increases due to transfer to the intermediate transfer member 2164 (primary transfer) and transfer from the intermediate transfer member 2164 to the transfer material (secondary transfer).

In this reference embodiment , since there is no wax filming on the image carrier, transfer dust does not occur. Image flow does not occur in a high temperature and high humidity environment. Therefore, as in this reference embodiment , primary transfer of each of the four colors from the image carrier to the intermediate transfer member and secondary transfer of the four-color superimposed image from the intermediate transfer member 2164 to the transfer material 2165 are performed five times in total. In a color image forming apparatus that requires a transfer having a process, it is possible to obtain a good image with no dust and no image flow.

(Durability test)
The photoconductor and developer were combined and mounted on an image forming apparatus, and a long-term durability test was conducted. The results are shown in Table 9, Table 10, and Table 11 . In addition, each evaluation item and its method are as follows.

<Evaluation equipment>
The cleaning apparatus shown in FIGS. 5, 6, 7, 16, 18, 20, and 22 of the present invention was incorporated into the digital color printer shown in FIG. 25 (Ricoh Co., Ltd., Epsio 8200 modified machine). Further, in the case of only the cleaning blade as a conventional example, the brush roller was removed from the cleaning device shown in FIG. The cleaning blade 22 is a urethane rubber plate and has a biting amount of 1.05 (mm), a Young's modulus of 0.45, and a free length of 8 (mm). The blade was set in a blade holder, and contacted in the counter direction with respect to the photosensitive member rotation at an initial contact angle of 79 ° and a pressure contact force of 80 g / cm. Further, instead of the cleaning blade 22 of the cleaning device of FIG. 20, a polishing blade having the same shape polishing function was attached.

The polishing blade used was a two-layer construction comprising a urethane rubber base layer and a polishing layer containing 30% by weight of alumina fine particles, and the back was reinforced with a metal plate. The portion in contact with the photoconductor is chamfered into a curved surface so that it is in smooth contact with the photoconductor. The contact pressure is 20 gf / cm. Further, the cleaning device was modified to provide a contact / separation mechanism that can be intermittently contacted / separated from the swing mechanism, and a polishing operation of rotating the photosensitive member 30 was performed for every 5000 sheets of image formation. The results are shown in Table 11 . As the cleaning device, Embodiment 6 shown in FIG. 20 was used. The developer is all E1, and the image carrier is No. 7-No. 20. The contents of the evaluation are the same as in the examples of Tables 9 and 10 . Among the obtained results, the image density and fog density were good.

<Durability evaluation>
Using character image data (A4 width) with a printing rate of 7%, stop each time one sheet is printed under high temperature and high humidity of 35 ° C-80% RH, and then print 100,000 sheets again in the intermittent mode. Is printed. Each 10,000 sheets were left for 12 hours.

<Image quality evaluation>
As the image quality evaluation, a halftone, a solid white image, and a solid black image were output at the end of 10,000 sheets and after being left for 12 hours, and the maximum image density, fogging, and presence / absence of image flow were evaluated. Further, as the cleaning property evaluation, the presence or absence of image defects (streaks having a diameter of 0.3 mm or more, white spots, black spots, etc.) and the residual toner ID were evaluated.

  The image density was measured with a reflection densitometer X-Light 938 (manufactured by X Light). That is, the solid black image was measured at five locations and averaged. Further, the fog density was measured by setting the reflection density of the paper to “0”, measuring 10 solid white images, and indicating the maximum density as the relative reflection density.

<Measurement of wear>
In the durability evaluation, the difference between the initial film thickness of the photoreceptor and the film thickness after printing 100,000 sheets was measured. The amount of wear is an average value at 10 locations in the longitudinal direction of the photoreceptor.

<Abnormal photoconductor>
In the durability evaluation, every 10,000 sheets, the photoreceptor was visually checked for abnormalities such as scratches, peeling, and cracks.

From the results of Table 9, Table 10 and Table 11 , in the output test of 100,000 sheets using the photoreceptor and developer of the present invention, the image quality such as density and fog is good even under high temperature and high humidity conditions, In addition, an excellent image was obtained due to improved image flow, transfer scattering, and poor cleaning of the spherical toner with a small particle size. Further, when the polishing blade was mounted on the cleaning device of the present invention, the photosensitive member was stably polished without peeling or cracking caused by the polishing means.

It is the schematic of the cleaning apparatus by the reference form 1 . It is a schematic view of an image forming apparatus using the cleaning equipment of FIG. 5 is a graph showing the removal efficiency of residual toner from the surface of an image carrier. It is a figure explaining the measurement of a static friction coefficient. It is a figure explaining a polarity control means. It is the schematic of the cleaning apparatus by the reference form 2 . It is a schematic schematic representation of a cleaning device according to Reference Embodiment 3. FIG. 3 is a cleaning state diagram of residual toner on the image carrier 1 from the side. It is a figure which shows schematically the state which observed FIG. 8 from A viewing direction. FIG. 10 is a diagram schematically showing another state of FIG. 9. It is a figure which shows the conventional flocked state roughly. It is a figure which shows roughly the one aspect | mode which concerns on a flocked state. It is an aspect which concerns on a brush roller. FIG. 14 is an enlarged view of FIG. 13. It is another aspect of FIG. It is a schematic schematic representation of a cleaning device according to the reference embodiment 4. 1 is a schematic view of an image forming apparatus using a cleaning device. It is a schematic schematic illustration of a cleaning device according to the reference embodiment 5. 10 is a diagram schematically showing a series of cleaning processes according to Reference Embodiment 5. FIG. It is a figure which shows the Example which provided the cleaning brush which has a cleaning blade and two cleaning apparatuses in the upstream by non-contact charge. It is a figure which shows the conventional structure which provided the conventional cleaning blade and one auxiliary | assistant means with the cleaning apparatus upstream. It is a figure which shows the conventional structure which provided the conventional cleaning blade and the one auxiliary means which does not have a cleaning apparatus in the upstream. It is a figure which shows the Example which provided the cleaning brush which has the cleaning blade by the non-contact charge, the cleaning device upstream, and the fixed brush which does not have the cleaning device. It is a figure which shows the Example which provided the sheet-like elastic member which does not have a cleaning blade and the cleaning brush which has the cleaning blade in the non-contact charge, and the upstream, and the cleaning device. It is a figure which shows the Example which provided the cleaning brush which has a cleaning blade and the cleaning device in the upstream with non-contact charge, and the cleaning brush which does not have a cleaning device. It is a figure which shows roughly the example which applied the cleaning apparatus by the reference form 1 to one image forming apparatus. FIG. 10 is a diagram schematically showing an example in which the cleaning device according to the first embodiment is applied to another image forming apparatus. It is a figure which shows the toner charge amount distribution of the toner after general development, and the toner after transfer. It is a figure which shows the toner charge amount distribution of the toner after image development in each environment. FIG. 6 is a diagram illustrating toner charge amount distributions of a developed toner and a transferred toner at high temperature and high humidity. FIG. 6 is a graph showing toner charge amount distributions of a developed toner and a transferred toner at low temperature and low humidity. FIG. 10 is a diagram illustrating a toner charge amount distribution on a photosensitive drum after auxiliary means when a + polarity voltage is applied to the auxiliary means used conventionally. It is a figure which shows the toner charge amount distribution on the photoconductive drum after an auxiliary | assistant means when + DC voltage with which AC was superimposed on the auxiliary | assistant means currently used is applied.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Image carrier 102 Cleaning member 103 Scraper blade member 104 Conveying coil 105 Core metal 106 Power supply 201 Image carrier 202 Cleaning member 203 Scraper blade member 204 Conveying coil 205 Core metal 206 Power source 207 Charging device 208 Exposure device 209 Developing device 210 Transfer device 211 Cleaning device 212 Static elimination device 501 Image carrier 502 Cleaning member 503 Scraper blade member 505 Core metal 506 Power source 511 Cleaning device 513 Polarity control means 514 Power source 601 Image carrier 615 Toner 616 Brush roller 617 Bias roller 618 Cleaning unit 619 Recovery roller 620 Transfer bias power source 701 Image carrier 715 Toner 716 Brush roller 717 Bias roller 718 Cleaning unit 719 Collection roller 721 Brush roller 801 Image carrier 823 Brush 824 Core metal 825 Cleaning toner 826 Non-cleaning toner 925 Cleaning toner 926 Non-cleaning toner 1323 Brush 1423 Brush 1527 Main branch 1528 Sub-branch 1601 Image carrier 1629 Cleaning brush 1630 Cleaning roller 1631 Flipping cover 1801 Image carrier 1832 Cleaning roller 1833 Power supply 1833 Core metal 1901 Image carrier 1932 Cleaning roller 1933 Power supply 1934 Core metal 1935 Exposure device 1936 Developing device 1937 Transfer roller 1938 Transfer material 1939 Discharge device 2050 Image forming unit 2051 Roller Cleaning device 2052 Charging device 2 53 Exposure device 2054 Development device 2055 Image carrier 2056 Transfer belt 2057 Transfer material 2058 Static elimination device 2116 Roller 2159 Development device 2160 Development device 2161 Development device 2162 Development device 2163 Photosensitive body 2164 Intermediate transfer body 2165 Transfer material 2166 Transfer device 2167 Cleaning device 2167 Charging device 2169 Exposure device 2170 Static elimination device

Claims (22)

By applying a voltage to two or more auxiliary cleaning means, a step of causing adsorbed step and the two or more cleaning aid the toner on the image bearing member to form an electric field between the image bearing member, An image forming method comprising a step of polishing an image carrier on which the toner is adsorbed on the two or more cleaning auxiliary means with a polishing blade ,
It said image bearing member has a photosensitive layer crosslinked charge transporting layer on the front surface is formed,
The crosslinked charge transport layer is formed by curing a composition comprising a radical polymerizable monomer having no tri- or higher functional charge transport structure and a radical polymerizable compound having a charge transport structure. Image forming method. The composition, image forming method according to claim 1, characterized in that it comprises a tri- or more functional radical polymerizing monomer having no charge transport structure multiple. The composition, image forming method according to claim 1 or 2, further comprising a radical polymerizable monomer monofunctional or officer capacity having no charge transport structure. The image forming method according to any one of claims 1 to 3, wherein the radical polymerizable compound having a charge transport structure is a monofunctional.   5. The image forming method according to claim 1, wherein the cross-linked charge transport layer has a thickness of 1 μm to 20 μm. Radical polymerizable monomer not having trifunctional or more charge transport structure, the acryloyloxy group and / or according to any one of claims 1 to 5, characterized in that it has a main Taku Leroy oxy group Image forming method. Radical polymerizable monomers over not having trifunctional or more charge transporting structure, General Formula

Wherein R ₇₁ , R ₇₂ , R ₇₃ , R ₇₄ , R ₇₅ and R ₇₆ are each independently a hydrogen atom or a general formula

(Wherein R ₇₇ represents a single bond, an alkylene group, an alkylene ether group or an alkyleneoxycarbonyl group, and R ₇₈ represents a hydrogen atom or a methyl group.)
It is group shown by these. )
The image forming method according to claim 6, wherein the compound is represented by the formula: 8. The image formation according to claim 7, wherein five or six of the R ₇₁ , R ₇₂ , R ₇₃ , R ₇₄ , R ₇₅ and R ₇₆ are groups represented by the general formula (B). Method. The radical polymerizable compound having a charge transport structure is an acryloyloxy group and / or methacryloyl image forming method according to any one of claims 1 to 8, characterized in that it has a group. Wherein two or more auxiliary cleaning means, image forming method according to any one of claims 1 to 9, characterized in that it consists rotatable blanking Rashirora to have a two cleaning device. The volume resistivity of the previous SL two brush rollers are identical, the image forming method according to claim 10, characterized in that a ^{1 × 10 8 ~1 × 10 9} Ω · cm. Wherein two or more auxiliary cleaning means comprises a rotatable brush roller to have a cleaning device comprise a stationary brush,
The fixed brush, with respect to the brush roller, the image forming method according to any one of claims 1 to 9, characterized in that it is located upstream. Wherein two or more auxiliary cleaning means comprises a rotatable brush roller to have a cleaning device made of a sheet-like elastic member,
The sheet-like elastic member, relative to the brush roller, the image forming method according to any one of claims 1 to 9, characterized in that it is located upstream. The volume resistivity of the auxiliary cleaning means arranged on the upper stream is ^{1 × 10 5 ~1 × 10 6} Ω · cm, the volume resistivity of said cleaning auxiliary means arranged downstream is 1 × 10 ⁸ The image forming method according to claim 10, wherein the image forming method is ˜1 × 10 ⁹ Ω · cm . The image forming method according to any one of claims 10 to 14 different polarities of the DC voltage to two of the cleaning auxiliary means, characterized in that it is applied. The auxiliary cleaning means located most upstream, DC voltage A C voltage superimposed is applied,
Other of the auxiliary cleaning means, image forming method according to any one of claims 1 to 14, characterized in that the DC voltage is applied. The image forming method according to any one of claims 1 to 16, wherein the input toner amount of the abrasive blade is 0.05 mg / cm ² or less. The toner is less 9μm volume average particle diameter of 3μm or more, and the ratio of the volume average particle diameter to number average particle diameter of 1.01 to 1.25, average circularity of flat is 0.950 or more 1. the image forming method according to any one of claims 1 to 17 and less than 00. The toner modified polyester having free, image forming method according to any one of claims 1 to 18 wax in the inner portion, characterized in that it is dispersed minute. The image forming method according to claim 19, wherein the benzalkonium which have a pre-Symbol denatured polyester Gow rare group. An electric field is formed between the image carrier, the two or more cleaning auxiliary means for adsorbing the toner on the image carrier, and the two or more cleaning auxiliary means to apply a voltage to the image carrier. An image forming apparatus comprising: a voltage applying unit that performs polishing; and a polishing blade that polishes the image carrier on which the toner is adsorbed to the two or more cleaning auxiliary units.
The image carrier has a photosensitive layer having a crosslinked charge transport layer formed on the surface,
The crosslinked charge transport layer is formed by curing a composition comprising a radical polymerizable monomer having no tri- or higher functional charge transport structure and a radical polymerizable compound having a charge transport structure. Image forming apparatus. An electric field is formed between the image carrier, the two or more cleaning auxiliary means for adsorbing the toner on the image carrier, and the two or more cleaning auxiliary means to apply a voltage to the image carrier. An electrophotographic cartridge having a voltage applying means for polishing, and a polishing blade for polishing the image carrier on which the toner is adsorbed to the two or more cleaning auxiliary means,
The image carrier has a photosensitive layer having a crosslinked charge transport layer formed on the surface,
The crosslinked charge transport layer is formed by curing a composition comprising a radical polymerizable monomer having no tri- or higher functional charge transport structure and a radical polymerizable compound having a charge transport structure. A cartridge for electrophotography.

Images