JP4534515B2 - Image forming apparatus - Google Patents

Description

  The present invention forms an image composed of a fixed toner image on a recording medium by forming a toner image on the surface of an image carrier and finally transferring and fixing the toner image on a predetermined recording medium. The present invention relates to a forming apparatus.

  Conventionally, on a photoreceptor rotating in a predetermined direction, a toner having a charging property charged to a predetermined polarity and a magnetic material coated with a coating material having a charging polarity opposite to that of the toner in order to ensure the charging property of the toner. In an image forming apparatus of a type that forms a toner image using a developer including a carrier, in order to clean the residue remaining on the surface of the photoreceptor after the transfer of the toner image to an intermediate transfer belt or recording paper Some have a cleaning member such as a cleaning blade in contact with the photosensitive member.

  However, in an image forming apparatus that performs cleaning by bringing a cleaning member into contact with the photosensitive member, there has been a problem that wear of the photosensitive member is intensified due to friction generated between the cleaning member and the photosensitive member. .

  Therefore, a rotating brush that rubs while rotating on the surface of the photoreceptor after the transfer is provided on the upstream side of the cleaning member in the rotation direction of the photoreceptor, and an electric charge having a polarity opposite to that of the toner is applied to the rotating brush. Thus, there has been proposed that the transfer residual toner remaining on the surface of the photoreceptor after the transfer of the toner image is disturbed and electrically sucked to assist cleaning by a cleaning member (for example, see Patent Document 1). According to this proposal, it is possible to maintain the conventional cleaning performance while suppressing the intensification of wear of the photosensitive member by weakening the contact pressure of the cleaning member to the photosensitive member.

  In addition, as a means for suppressing intensification of wear of the photosensitive member, a rotating brush for supplying a lubricant to the surface of the photosensitive member after transfer of the toner image is provided upstream of the cleaning member in the rotational direction of the photosensitive member. Has been proposed.

  FIG. 1 is a view showing a rotating brush for supplying a lubricant.

  FIG. 1 shows a photoconductor 101, a charger 102 for applying a predetermined charge to the photoconductor 101, and the surface exposed to form an electrostatic latent image on the surface of the photoconductor 101 to which a predetermined charge is applied. An exposure device 103 for developing, a developing roll 104 for developing the electrostatic latent image formed on the surface of the photosensitive member 101 with toner of the developer, and an intermediate in which the toner image formed on the photosensitive member is transferred by the transfer device 105. A transfer belt 112, a rotating brush 116 for supplying a solid lubricant 111 to the surface of the photoconductor, and a blade 113b for scraping the residue remaining on the photoconductor 101 after the toner image transfer are shown. FIG. 1 also shows a state in which the solid lubricant 111 is disposed at a position in contact with the rotating brush 116 and a state in which the blade 113b is attached to the base plate 113a.

  By the way, the coating material covering the magnetic carrier can be present in the developer even when the toner and the magnetic carrier are used while being agitated and separated from the magnetic carrier. Therefore, when toner development is performed by electrostatically adhering toner to the electrostatic latent image formed on the photosensitive member, the toner is applied to a region other than the region where the electrostatic latent image is formed on the photosensitive member. In some cases, the free additive charged to a polarity opposite to that of the toner adheres, and therefore, the free additive may also be included in the residue remaining on the photoreceptor after the toner image transfer. Therefore, when the lubricant is supplied to the photosensitive member 101 by the rotating brush 116, the free additive is transferred to the rotating brush 116, and the coating material transferred to the rotating brush 116 is the rotation of the solid lubricant 111. It is known that the contact surface that comes in contact with the brush 116 is solidified by covering the contact surface, and the supply of the lubricant to the photosensitive member 101 is interrupted.

Therefore, in the above proposal, in order to prevent this, a flicking member 117 for knocking off the free additive transferred to the rotating brush 116 is provided.
Japanese Patent Laid-Open No. 03-138683

  However, since it is difficult to completely knock the free additive once transferred to the rotating brush 116 from the rotating brush 116 by the flicking member 117, this proposal suppresses the solidification of the surface of the solid lubricant 111 caused by the coating material. It is difficult.

  This solidification is not caused only by the coating material covering the magnetic carrier having a charging polarity opposite to the charging characteristics of the toner, but is opposite to the normal polarity of the toner contained in the developer. Any additive having the property of being electrically charged can be caused by any.

  SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide an image forming apparatus that is devised for stable supply of a lubricant to an image carrier.

In order to achieve the above object, an image forming apparatus of the present invention comprises:
An electrostatic latent image is formed on the surface of the image bearing member rotated in a predetermined direction and coated with a lubricant, and a developer containing a toner and an additive having a property of being charged with a polarity opposite to that of the toner is contained therein. The electrostatic latent image is developed with the toner in the developer using a held developing device to form a toner image on the surface of the image carrier, and the toner image is finally transferred onto a predetermined recording medium. And an image forming apparatus for forming an image composed of a fixed toner image on the recording medium by fixing,
A cleaning unit for scraping the surface of the image bearing member from the surface by rubbing the residue remaining on the surface after the toner image on the surface of the image carrier has been transferred elsewhere;
A solid lubricant applied to the surface of the image carrier;
It is disposed upstream of the cleaning unit in the rotation direction of the image carrier, has conductive hairs, and rotates with the hairs in contact with the solid lubricant. A brush for applying a lubricant to the surface of the image carrier;
The hair portion includes a charge imparting portion that imparts a charge having the same polarity as the predetermined polarity.

  In the image forming apparatus of the present invention, an additive such as a free carrier coating agent having a property of being charged to a polarity opposite to that of the toner contained in the developer is added to the bristle portion of the brush that supplies the lubricant to the image carrier. The charge having the same polarity as the charged polarity of the object) is applied. As a result, an electric repulsive force is generated between the free additive that may remain as a residue on the surface of the image carrier after the toner image transfer and the bristles of the brush. Therefore, according to the image forming apparatus of the present invention, since the free additive can be prevented from adhering to the bristles of the brush itself, the free additive once adhering to the bristles is knocked down by the flicking member. The lubricant can be supplied to the image carrier more stably than in the prior art.

  Here, the image forming apparatus of the present invention may be provided with a flicking member that touches the bristles and knocks off deposits adhering to the bristles as the brush rotates.

  In this way, adhesion of free additives to the solid lubricant can be suppressed more reliably.

  In addition, the image forming apparatus of the present invention generates a moment around the rotating shaft that holds the solid lubricant and is rotatably supported via a rotating shaft that is parallel to the brush. And a support member for bringing the solid lubricant held in the rotating part into contact with the brush by the moment generated in the moment generating part. .

  If it does in this way, it can contribute to the stable supply of the lubricant to an image carrier on composition.

  Here, it is also a preferable aspect that the solid lubricant is mainly composed of zinc stearate.

  According to the image forming apparatus of the present invention, it is possible to stably supply the lubricant to the image carrier.

  Hereinafter, embodiments of the present invention will be described.

  FIG. 2 is a schematic configuration diagram of a main part of the printer which is the first embodiment of the image forming apparatus of the present invention.

  As shown in FIG. 2, the printer 1 according to the present embodiment includes four image forming units 10Y, 10M, 10C, and 10K. Each image forming unit has a photosensitive element that rotates in the direction of arrow A. Bodies 11Y, 11M, 11C, 11K, chargers 13Y, 13M, 13C, 13K, exposure devices 14Y, 14M, 14C, 14K, developing rolls 12Y, 12M, 12C, 12K, primary transfer rolls 20Y, 20M, 20C, 20K, In addition, there are provided photoconductor maintenance sections 15Y, 15M, 15C, and 15K in which a rotating brush for supplying a lubricant, a cleaning blade, and a flicking member are provided. The printer 1 is capable of full-color printing, and the symbols Y, M, C, and K added to the end of each of the above components are yellow, magenta, cyan, and black images, respectively. It is a component for formation. In order to avoid complication of the drawing, in FIG. 2, a bias applying device for applying an electric charge to the rotating brush, which will be described later, is omitted. The printer 1 is also provided with an intermediate transfer belt 30, a secondary transfer roll 40, and a tension roller 31 that circulate in the direction of arrow B.

  A basic image forming operation of the printer 1 will be described.

  First, toner image formation by the yellow image forming unit 10Y is started, and a predetermined charge is applied to the surface of the photoreceptor 11Y rotating in the direction of arrow A by the contact-type charger 13Y. Next, the exposure device 14Y irradiates the surface of the photoreceptor 11Y with exposure light corresponding to a yellow image to form an electrostatic latent image. The electrostatic latent image is developed with yellow toner by the developing roller 12Y to form a yellow toner image on the photoreceptor 11Y. The toner image is transferred to the intermediate transfer belt 30 by the primary transfer roll 20Y.

  Here, in the printer 1, a developer including toner and a magnetic carrier covered with an outer covering agent having a charging polarity opposite to that of the toner is used in order to ensure the charging characteristics of the toner. The development (visualization) of the electrostatic latent image is performed with the toner in the developer. In the printer 1, when the toner and the magnetic carrier are mixed, the toner is charged to the negative side, and the outer covering agent of the magnetic carrier is charged to the positive side. In addition, this outer covering agent is an example of the additive referred to in the present invention.

  The intermediate transfer belt 30 receives the magenta toner image of the next color in accordance with the timing at which the yellow toner image transferred onto the intermediate transfer belt 30 reaches the primary transfer roll 20M of the image forming unit 10M of the next color. A toner image is formed by the magenta image forming unit 10M so as to reach the primary transfer roll 20M. The magenta toner image formed in this way is transferred onto the yellow toner image on the intermediate transfer belt 30 while being superimposed on the primary transfer roll 20M.

  Subsequently, toner image formation by the cyan and black image forming units 10C and 10K is performed at the same timing as described above, and sequentially superimposed on the yellow and magenta toner images of the intermediate transfer belt 30 in the primary transfer rolls 20C and 20K. Is transcribed.

  Thus, the multicolor toner image transferred onto the intermediate transfer belt 30 is finally secondarily transferred to the paper 200 by the secondary transfer roll 40, and the multicolor toner image is conveyed together with the paper 200 in the direction of arrow C, as shown in the figure. A color image is formed on the sheet 200 by being fixed by a fixing device that does not. In the following, since the functions of the image forming units for Y, M, C, and K are the same, the Y (yellow) color image forming unit 10Y will be representatively described.

  FIG. 3 is an enlarged view of the yellow image forming unit shown in FIG.

  The photoreceptor maintenance unit 15Y, which is a component of the yellow image forming unit 10Y shown in FIG. 3, has a housing 150Y, a lubricant supply mechanism 155Y including a solid lubricant 1554Y, and a bristle portion 1521Y extending radially from its center. The rotating brush 152Y includes a bias applying device 153Y that applies a predetermined charge to the bristle portion 1521Y of the rotating brush 152Y, and a urethane rubber blade 151Y. The lubricant supply mechanism 155Y includes a rotation shaft 1551Y, a rotation arm 1552Y, a weight 1553Y, a solid lubricant 1554Y, and a rotatable cam 1555Y whose shaft is directly connected to a rotation shaft of a motor (not shown). Yes.

  The solid lubricant 1554Y contains zinc stearate as a main component, and is attached to a rotating arm 1552Y that can rotate around a rotating shaft 1551Y.

  The rotating arm 1552Y is supported by a rotating shaft 1555Y and supported by a cam 1555Y that rotates as a motor (not shown) rotates. Therefore, when the cam 1555Y rotates, the rotating brush 152Y and the solid lubricant 1554Y repeats contact and separation, and the rotating arm 1552Y has its own weight due to the solid lubricant 1554Y and the weight of the weight 1553Y attached to the opposite side of the solid lubricant 1554Y across the rotating arm 1552Y. A moment in the direction in which the solid lubricant 1554Y is pressed against the rotary brush 152 shown in FIG. Therefore, in the printer 1, the amount of lubricant supplied to the photoconductor 11Y can be controlled by changing the weight of the weight or changing the rotational speed of the cam 1555Y.

  In the printer 1, as described above, in order to ensure the charging performance of the toner that greatly affects the stability of the image quality, an external resin composed of a random copolymer of an acrylic resin and a fluororesin having a charging polarity opposite to that of the toner. A developer containing a magnetic carrier coated with a covering agent is used, and this outer covering agent can be separated from the carrier particles by the contact between the toner and the magnetic carrier and exist in the developer agent. Therefore, the outer covering agent may be electrostatically attached to a portion other than the portion where the electrostatic latent image is formed on the photoreceptor during toner development.

  The bristle portion 1521Y of the rotating brush 152Y shown in FIG. 3 is kneaded with carbon black to provide conductivity, and the bias applying device 153Y shown in FIG. 3 has a voltage of + 200V to + 400V applied to the bristle portion 1521Y of the rotating brush 152Y. Is applied. As a result, in this printer 1, the adhesion itself of the positively charged outer covering agent to the rotating brush 152Y, which solidifies on the surface of the solid lubricant 1554Y and prevents the supply of the lubricant to the photoreceptor 11Y, is electrically repelled. It is suppressed by using power.

  In this printer 1, a flicking member 154Y made of polyoxymethylene (POM) is provided, and the hair 1521Y of the rotary brush 152Y is electrically charged with a reverse polarity (here, minus side). It is also possible to deal with an outer covering adsorbed on the surface.

  Table 1 below shows setting conditions of an example performed using the printer 1 of the present embodiment.

  In Table 2 shown below, a full color print with an image density of 20% is displayed under the six types of conditions set in Table 1 from Example 1 to Example 4 and Comparative Example 1 to Comparative Example 2. Wear of the photoconductor 11Y after 300,000 sheets under high temperature and high humidity (28 ° C., 85% RH) and another 300,000 sheets under low temperature and low humidity (10 ° C., 15% RH) The results of evaluating the edge damage of the blade 151Y and the cleaning performance are shown.

In addition, Beltron B12N (manufactured by Kanebo Co., Ltd., fiber thickness 6 denier, brush hair density 50 × 10 ³ / inch ² , hair length 6.5 mm (including adhesive layer)) is used for the rotating brush 152Y. The solid lubricant 1554Y was obtained by melting zinc stearate and molding it into a bar shape of 5 mm × 5 mm × 320 mm. A blade 151Y having a blade hardness of 87 and a free length of 9 mm was set to have a blade linear pressure of 2.6 gf / mm, a setting angle of 23 °, and a blade cleaning angle of 12.6 °. The amount of biting of the flicking member 154Y into the rotating brush 152Y was set to 1.0 mm, and the amount of biting of the rotating brush 152Y into the photoreceptor 11Y was set to 1.0 mm. The toner has a volume average particle size of 5.8 μm, a shape factor of 132, a Mn—Mg ferrite carrier having an average particle size of 35 μm of the core material is used as a carrier, and methyl methacrylate / isobutyl methacrylate / methyl methacrylic acid is used as an outer covering agent. / Perfluorooctyl ethyl methacrylate obtained by random copolymerization is used.

  Regarding the wear of the photoconductor 11Y, the film thickness of the photoconductor 11Y before printing and after printing a total of 600,000 sheets was measured with an eddy current film thickness meter, and the difference was calculated. Photoreceptor scratches were evaluated by measuring 10-point average roughness (Ra) with a surface roughness meter (Surfcom 1400A manufactured by Tokyo Seimitsu Co., Ltd.), and the judgment criteria were ○ (Rz 3.0 μm or less), Δ (3. 0 <Rz <3.5 μm), x (Rz> 3.5 μm), the degree of solidification of the surface of the solid lubricant 1554Y is determined by sensory evaluation by visual observation, and the criterion is ○ (no solidification at all), Δ (some solidified), x (clearly solidified on the surface). Evaluation of the uniformity of the halftone image is made by sensory evaluation by visual observation of the print image, and the judgment criteria are ○ (no problem), Δ (slightly splattered), and x (splattered frequently).

  From the results of Example 4 and Comparative Example 1 shown in Table 2, solidification on the surface of the solid lubricant is suppressed by applying a positive bias to the rotating brush 152Y, that is, a flicking member. It can be read that it is difficult to stably supply the lubricant only by providing 154Y. Further, from the results of Example 1, Example 2, Example 3, and Example 4, it can be read that the bias voltage to be applied is preferably in the range of +200 to +400. From the results of Comparative Example 1 and Comparative Example 2, by using the lubricant supply mechanism 155Y, the pressure for pressing the fixed lubricant 1554Y to the rotating brush 152Y is increased without using the lubricant supply mechanism 155Y. It can be read that the wear of the photoconductor is suppressed because the lubricant can be uniformly applied to the photoconductor.

  As described above, in the printer 1 of this embodiment, the same polarity as the charging polarity of the outer covering agent that coats the magnetic carrier particles on the bristles 1521Y of the rotary brush 152Y that supplies the lubricant to the surface of the photoreceptor 11Y. By applying this electric charge, it is possible to prevent the outer covering agent that has been detached from the magnetic carrier and transferred to the bristles 1521Y of the rotating brush 152Y from adhering to the surface of the solid lubricant 1554Y and solidifying. Therefore, according to the printer 1, the lubricant can be stably supplied to the photosensitive member.

  In the present exemplary embodiment, the suppression of adhesion of the magnetic carrier coating material to the rotating brush, which is charged with a polarity opposite to that of the toner, has been described as an example. However, the application of the present invention is not limited to the toner included in the developer. As long as it is a free external additive that is charged to a reverse polarity, it is not limited to an outer coating agent for a magnetic carrier.

  Further, in the present embodiment, a case where a lubricant supply mechanism is provided and the solid lubricant 1554Y is pressed against the rotating brush 52Y by the moment force generated by the rotating arm 1552Y and the weight 1553Y is described as an example. The generation of the moment force is not limited to this method. For example, the moment force may be generated by attaching a torsion spring to the rotation shaft 1551Y, and if the lubricant is supplied to the photosensitive member, such a mechanism is used. Even if the lubricant supply unit 155Y is omitted, the basic effect of the present invention is not reduced. Further, in the printer 1 of the present embodiment, the case where the flicking member 154Y is provided has been described as an example. However, even if this is omitted, the basic effect of the present invention is reduced. is not.

In the present embodiment, the case where Beltron B12N (manufactured by Kanebo Co., Ltd.) is used as the fiber material of the brush has been described as an example. However, the present invention is not limited to this, and nylon, acrylic or Polypropylene may be used, and among these, nylon is most preferable because it has excellent long-term stability. The electric resistance value of the bristle portion having conductivity is preferably 10 ² to 10 ⁵ Ωcm, and the case where zinc stearate is used as a main component as an example of the solid lubricant 1554Y will be described as an example. However, the present invention is not limited to this as long as it is a fatty acid metal salt such as magnesium stearate, or a fluorine resin such as PTFE.

  The pressing load of the solid lubricant 1554Y to the rotating brush 152Y is preferably 12 gf to 60 gf (118 mN to 588 mN), more preferably 15 gf to 40 gf (147 mN to 392 mN). By setting the load on the rotating brush 152Y within the above range, an appropriate amount of lubricating component can be supplied to the surface of the photoreceptor 11Y over a long period of time.

The rotational speed of the rotary brush 152Y is desirably controlled in a range where the speed ratio with respect to the photoreceptor 11Y is 0.5 to 1.5. When the peripheral speed ratio is lower than 0.5, the rotational brush 152Y and the photoreceptor 11Y The toner is packed in between, which causes poor cleaning and toner sticking to the photoreceptor 11Y. If the peripheral speed ratio is greater than 1.5, the surface of the photoreceptor 11Y is likely to be damaged due to the rubbing of the rotating brush 152Y. The fiber density on the surface of the rotary brush 152Y is preferably 15 × 10 ^{3 to} 120 × 10 ³ / inch ² (23.4 to 186 / mm ² ), more preferably 20 × 10 ^{3 to} 60 × 10 ^3. / Inch ² (31.0-93.0 / mm ² ). It is preferable to make the fiber density within the above range because a uniform lubricant can be applied over a long period of time. The fiber thickness of the surface of the rotating brush 152Y is preferably 2 to 20 denier, and more preferably 6 to 20 denier. By setting the fiber thickness within the above range, the solid lubricant 1554Y can be scraped off and applied to the photoreceptor 11Y. The fiber length of the surface of the rotating brush 152Y (* not including the raised adhesive layer thickness) is preferably 2.5 mm to 7 mm, more preferably 3 mm to 6.5 mm. By setting the fiber length within the above range, the solid lubricant 1554Y can be scraped off and applied to the photoreceptor 11Y. The appropriate coating amount of the solid lubricant 1554Y here is preferably a consumed weight of 2 to 20 μg per rotation of the photoreceptor 11Y. More preferably, the amount is 4 to 10 μg. When the amount is less than 2 μg, the effect of the lubricant is difficult to be exhibited.

  In the present embodiment, the case where urethane rubber is used as an example of the cleaning blade material has been described as an example. However, the present invention is not limited to this, and silicon rubber, fluorine rubber, chloroprene rubber, butadiene rubber, or the like can be used. Among them, it is preferable to use a polyurethane elastic body because of its excellent wear resistance. As the polyurethane elastic body, a polyurethane generally synthesized through an addition reaction between an isocyanate and a polyol and various hydrogen-containing compounds is used. As the polyol component, a polyether-based polyol such as polypropylene glycol or polytetramethylene glycol, Polyester polyols such as adipate polyols, polycaprolactam polyols, polycarbonate polyols are used, and polyisocyanate components include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, toluidine diisocyanate, hexa Methylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexyl It can be used aliphatic polyisocyanates such as Tan diisocyanate. As the curing agent, a dihydric alcohol such as 4-butanediol and a trihydric or higher polyhydric alcohol such as trimethylolpropane or pentaerythritol are usually used in combination.

  Examples of the blade material include hardness (JISA scale (JIS K 6301)) of 50 to 90, Young's modulus (kg / cm2) of 40 to 90, 100% modulus (kg / cm2) of 20 to 65, and 300% modulus (kg / kg). cm2) 70 to 150, tensile strength (kg / cm2) 240 to 500, elongation (%) 290 to 500, rebound resilience (%) 30 to 70, tear strength (kg / cm2) 25 to 75, permanent elongation (%) Of 4.0 or less can be used.

As a charging method used in the image forming apparatus of the present invention, a known charging method can be applied, and examples thereof include a corotron charging method and a contact charging method. In the contact charging method, a roller-shaped charging member, a blade-shaped charging member, a belt-shaped charging member, a brush-shaped charging member, a magnetic brush-shaped charging member, or the like can be applied. In particular, the roller-shaped charging member and the blade-shaped charging member may be arranged in a contact state or a non-contact state having a certain amount of gaps (100 μm or less) with respect to the photoreceptor. A roller-shaped charging member, a blade-shaped charging member, and a belt-shaped charging member are made of a material adjusted to an effective electrical resistance (10 ³ Ω to 10 ⁸ Ω) as a charging member, You may be comprised from the multilayer. The material of the charging member is mainly composed of synthetic rubber such as urethane rubber, silicon rubber, fluorine rubber, chloroprene rubber, butadiene rubber, EPDM, epichlorohydrin rubber, and elastomers such as polyolefin, polystyrene, vinyl chloride, conductive carbon, An appropriate electrical conductivity imparting agent such as a metal oxide or an ionic conductive agent can be blended in an appropriate amount so that an effective electrical resistance can be expressed and used as a charging member. Furthermore, a resin such as nylon, polyester, polystyrene, polyurethane, silicone, etc. is made into a paint, and an appropriate amount of an arbitrary conductivity imparting agent such as conductive carbon, metal oxide, ionic conductive agent, etc. is blended there, and the resulting paint is dipped. It can be used by laminating by any method such as spraying or roll coating.

  In the print 1 of the present embodiment, the case where the intermediate transfer belt 30 is used has been described as an example. However, the present invention is not limited to this, and a known transfer method is applicable in addition to the intermediate transfer belt method. For example, a direct transfer method using a transfer corotron, a transfer roll, or the like, or a transfer belt method in which a recording material is electrostatically adsorbed and conveyed to transfer an image on the image carrier may be used.

  The toner used in the image forming apparatus of the present invention is not particularly limited by the production method. For example, a binder resin, a colorant, a release agent, and a charge control agent as necessary are kneaded, pulverized, and classified. A kneading and pulverizing method, a method of changing the shape of particles obtained by the kneading and pulverizing method by mechanical impact force or thermal energy, emulsion polymerization of a polymerizable monomer of a binder resin, and a formed dispersion; Emulsion polymerization aggregation method for obtaining a toner by mixing a colorant, a release agent and, if necessary, a dispersion such as a charge control agent, and aggregating and heat-fusing, a polymerizable monomer for obtaining a binder resin Suspension polymerization method in which a solution of a coloring agent, a release agent, and a charge control agent, if necessary, is suspended in an aqueous solvent for polymerization, a binder resin and a colorant, a release agent, and if necessary, charge control Use a solution obtained by the suspension method in which a solution such as an agent is suspended in an aqueous solvent and granulated. It can be. In addition, a known method such as a production method in which the toner obtained by the above method is used as a core, and agglomerated particles are further adhered and heat-fused to give a core-shell structure can be used, but from the viewpoint of shape control and particle size distribution control Suspension polymerization method, emulsion polymerization aggregation method, and dissolution suspension method, which are produced from an aqueous solvent, are preferred, and emulsion polymerization aggregation method is particularly preferred.

The toner is composed of a binder resin, a colorant, a release agent, and the like. If necessary, silica or a charge control agent may be used. The volume average particle diameter is preferably in the range of 2 to 12 μm, and more preferably in the range of 3 to 9 μm. Further, by using a toner having an average shape index (ML ² / A: ML is the absolute maximum length of the toner, and A is the projected area of the toner) in the range of 100 to 140, high development, transferability, In addition, a high-quality image can be obtained.

  Binder resins used include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene, and isoprene, and vinyls such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate. Esters, α-methylene such as methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Homopolymers of aliphatic monocarboxylic acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone Examples of typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene- Examples thereof include a butadiene copolymer, a styrene-maleic anhydride copolymer, polyethylene, and polypropylene. Further examples include polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like.

  In addition, toner colorants include magnetic powders such as magnetite and ferrite, carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, and malachite green oxa. Rate, lamp black, rose bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 can be exemplified as a representative one.

  Typical examples of the release agent include low molecular polyethylene, low molecular polypropylene, Fischer-Tropsch wax, montan wax, carnauba wax, rice wax, and candelilla wax.

  In addition, a charge control agent may be added to the toner as necessary. As the charge control agent, known ones can be used, but azo metal complex compounds, metal complexes of salicylic acid, polar groups A resin type charge control agent containing can be used. When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. The toner in the present invention may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  Lubricants added to the toner used in the present invention include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids and fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene and polybutene, and have a softening point upon heating. Plant waxes such as silicones, oleic amides, erucic acid amides, ricinoleic acid amides, stearic acid amides, aliphatic amides, carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, etc. , Animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc., petroleum wax, and their modified products can be used alone. Use Or it may be used in combination.

  To the toner used in the present invention, inorganic fine particles, organic fine particles, composite fine particles obtained by adhering inorganic fine particles to the organic fine particles, and the like can be added for the purpose of removing deposits and deteriorated matters on the surface of the electrophotographic photosensitive member. Particularly preferred are inorganic fine particles having excellent polishing properties. Inorganic fine particles include silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, Various inorganic oxides such as manganese oxide, boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride, nitrides, borides, and the like are preferably used. Moreover, titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzene sulfonyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, γ- (2-amino) Ethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane Hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxy The treatment may be performed with a silane coupling agent such as silane, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, and p-methylphenyltrimethoxysilane. Further, hydrophobic treatment with a higher fatty acid metal salt such as silicone oil, aluminum stearate, zinc stearate, calcium stearate can be preferably performed.

  Examples of the organic fine particles include styrene resin particles, styrene acrylic resin particles, polyester resin particles, and urethane resin particles.

  Other inorganic oxides added to the toner are small-diameter inorganic oxides having a primary particle size of 40 nm or less for powder flowability, charge control, etc. Mention may be made of large-diameter inorganic oxides. As these inorganic oxide fine particles, known ones can be used, but in order to perform precise charge control, it is preferable to use silica and titanium oxide in combination. Further, the surface treatment of the small-diameter inorganic fine particles increases the dispersibility and increases the effect of improving the powder fluidity.

  The toner in the present invention can be produced by mixing the toner and the outer covering agent with a Henschel mixer or a V blender. Further, when the toner is manufactured by a wet method, it can be externally added by a wet method.

In the present invention, the mixing ratio of the toner and the carrier can be set as appropriate, and the core material (carrier core material) used in the carrier is not particularly limited, and iron, steel, nickel, cobalt, etc. Or a magnetic oxide such as ferrite or magnetite, glass beads, or the like. The average particle size of the carrier core material is generally 10 μm to 150 μm, and preferably 20 μm to 100 μm. Furthermore, for the purpose of low stress, a spherical core produced by a polymerization method can be used. The true specific gravity of the polymerization core is preferably 3.0 to 5.0 g / cm ³ , and the saturation magnetization is preferably 40 emu / g or more.

  The polymer of the (meth) acrylic acid alkyl ester used for the resin for forming the outer cover of the carrier is effective by using two or more types of monomers having different alkyl groups. Examples of these monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and tertiary butyl (meth) acrylate. , Isobutyl (meth) acrylate, tertiary pentyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, isohexyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Can be mentioned.

  Examples of monomers having a carboxylic acid group to be copolymerized with (meth) acrylic acid alkyl ester include (meth) acrylic acid, those having a carboxyl group in styrene such as carboxyl styrene, and those such as p-carboxyl styrene. Examples include those containing two or more carboxyl groups. A similar effect can be seen with a polymer having a carboxyl group by allowing a metal cation to act on an acrylic copolymer, such as an ionomer resin.

  The amount of carboxylic acid varies depending on the type of carboxylic acid monomer, the amount of carboxylic acid group, and the molecular weight of the monomer, but 0.1 to 15.0% by weight based on the total resin monomer is appropriate. More preferably, 0.5 to 10.0% by weight can exhibit a function with respect to adhesion and environmental stability. When the introduction amount is small, the durability effect is small, and when it is too large, the viscosity is high, it is difficult to obtain a uniform coating resin, and the environmental difference is deteriorated.

  As an example of the fluorine-containing monomer used for forming the outer coating layer of the carrier, a perfluoroacrylic monomer is preferable. Examples include fluorine-containing acrylic monomers such as tetrafluoropropyl methacrylate, pentafluoropropyl methacrylate, octafluoropentyl methacrylate, perfluorooctyl ethyl methacrylate, trifluoroethyl methacrylate, trifluoroethylene, tetrafluoroethylene, hexa Fluorine-containing monomers such as fluoropropene and perfluoroalkyl vinyl ether can also be used.

  The amount of fluorine can be selected according to the purpose. When the amount of fluorine is large, the contamination property is increased, the charging property is decreased, or the adhesion with the core material tends to be deteriorated. Depending on the monomer species, the amount of fluorine monomer is suitably 0.1 to 60.0 parts by weight, more preferably 0.5 to 50.0 parts by weight with respect to adhesion and charge level. Function can be expressed.

  The copolymerization ratio of the resin for forming the outer cover layer of the carrier can be appropriately selected according to the toner type and system suitability. Particularly, two or more kinds of (meth) acrylic acid alkyl esters can obtain desired characteristics by changing the polymerization ratio. As a copolymerization method of these monomers, a polymerization method such as random copolymerization or graft copolymerization can be used. Graft copolymerization is an excellent polymerization method in that the function can be easily expressed and the adhesion to the core can be increased.

  As a typical method for forming the outer coating layer on the surface of the carrier core material, a method using a layer forming raw material solution (including a matrix resin, resin fine particles, conductive fine powder, etc. in a solvent as appropriate) is used. Can be mentioned. Specifically, for example, a dipping method in which powder of a carrier core material or the like is immersed in a solution for forming an outer coating layer, a spray method in which a solution for forming an outer coating layer is sprayed on the surface of the carrier core material, a carrier core material, Fluidized bed method in which the outer layer forming solution is sprayed in a state of being floated by flowing air, the kneader coater method in which the carrier core material and the outer layer forming solution are mixed in the kneader coater, and then the solvent is removed. Although it is mentioned, it is not particularly limited to those using a solution, and depending on the carrier core material to be applied, an appropriate method such as a powder coating method in which the resin powder is heated and mixed can be used.

  The coating amount of the resin for forming the outer cover layer is suitably in the range of 0.05 to 5.0% by weight with respect to the carrier weight in order to achieve both image quality, secondary obstruction and chargeability. In addition, when applying to the charge imparting member, it is preferable to appropriately adjust the application amount and the application method so as to obtain an appropriate film thickness with respect to the charge amount, maintainability and the like.

  The solvent used for the outer layer forming raw material solution is not particularly limited as long as it dissolves the matrix resin. For example, aromatic hydrocarbons such as xylene and toluene, acetone, methyl ethyl ketone, and the like. Ketones, ethers such as tetrahydrofuran and dioxane, and halogen compounds such as chloroform and carbon tetrachloride can be used.

  Further, the photoreceptor used in this embodiment may have any structure such as a single layer structure, a laminated structure composed of a charge generation layer and a charge transport layer, or a structure in which a surface protective layer is provided thereon.

  The base layer, which is the deepest layer of the image carrier, may be a cylindrical (drum) shape of aluminum. In addition to aluminum, metal materials such as stainless steel and nickel, polyethylene terephthalate, polybutylene terephthalate, polypropylene , Polymer materials such as nylon, polystyrene, phenol resin, etc., conductive materials dispersed in an insulating material such as hard paper, the above insulating materials laminated with metal stays, the above insulating materials made of metal What formed the vapor deposition film etc. can be used.

  The material of the undercoat layer, which is a layer immediately above the base layer, includes organic zirconium compounds such as zirconium chelate compounds, zirconium alkoxide compounds and zirconium coupling agents, organic titanium compounds such as titanium chelate compounds, titanium alkoxide compounds and titanate coupling agents. In addition to organoaluminum compounds such as compounds, aluminum chelate compounds, aluminum coupling agents, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, Aluminum silicon alkoxide compound, aluminum titanium alkoxide compound, aluminum zirconium alk Kishido compounds such as organic metal compounds, and the like, and these organic zirconium compound among organic titanyl compound, organoaluminum compound residual potential are preferably used exhibits excellent electrophotographic characteristics lower. Also, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-amino Propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxycyclohexyl It can be used by containing a silane coupling agent such as trimethoxysilane. Furthermore, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, phenol resin, vinyl chloride- A binder resin such as a vinyl acetate copolymer, an epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, or polyacrylic acid can also be used. These mixing ratios can be appropriately set as necessary.

  Any known charge generating substance can be used as the material for the charge generating layer, which is a layer immediately above the undercoat layer. For infrared light, phthalocyanine pigments, squarylium, bisazo, trisazo, perylene, dithioketopyrrolopyrrole, for visible light, condensed polycyclic pigments, bisazo, perylene, trigonal selenium, dye-sensitized metal oxide fine particles, etc. are used. Among these, a particularly excellent performance is obtained, and a phthalocyanine pigment is used as a charge generating material that is preferably used. By using this, it is possible to obtain an electrophotographic photosensitive member having particularly high sensitivity and excellent repetitive stability. In addition, phthalocyanine pigments generally have several crystal forms, and any of these crystal forms can be used as long as it is a crystal form capable of obtaining a sensitivity suitable for the purpose. Particularly preferred charge generating materials include chlorogallium phthalocyanine, dichlorotin phthalocyanine, hydroxygallium phthalocyanine, metal-free phthalocyanine, oxytitanyl phthalocyanine, chloroindium phthalocyanine, and the like. The phthalocyanine pigment crystal is obtained by mechanically dry-grinding a phthalocyanine pigment produced by a known method with an automatic mortar, a planetary mill, a vibration mill, a CF mill, a roller mill, a sand mill, a kneader, or the like. It can manufacture by performing a wet grinding process using a ball mill, a mortar, a sand mill, a kneader, etc. with a solvent. Solvents used in the above treatment are aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), aliphatic polyvalents. Alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetic ester, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, ether (Diethyl ether, tetrahydrofuran, etc.), several mixed systems, and mixed systems of water and these organic solvents. The solvent used is used in the range of 1 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 1 part by weight of the pigment crystals. The treatment temperature is −20 ° C. to the boiling point of the solvent, preferably −10 to 60 ° C. In addition, grinding aids such as sodium chloride and sodium nitrate can be used during grinding. The grinding aid may be used 0.5 to 20 times, preferably 1 to 10 times the pigment. Further, phthalocyanine pigment crystals produced by a known method can be controlled by combining acid pasting or acid pasting with dry grinding or wet grinding as described above. As an acid used for acid pasting, sulfuric acid is preferable, and a concentration of 70 to 100% by weight, preferably 95 to 100% by weight is used, and a dissolution temperature is -20 to 100 ° C, preferably -10 to 60 ° C. Set to range. The amount of concentrated sulfuric acid is set in the range of 1 to 100 times, preferably 3 to 50 times the weight of the phthalocyanine pigment crystals. As a solvent to be precipitated, water or a mixed solvent of water and an organic solvent is used in an arbitrary amount. The temperature for precipitation is not particularly limited, but it is preferably cooled with ice or the like in order to prevent heat generation.

  The binder resin used for the charge generation layer can be selected from a wide range of insulating resins, and can be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane. You can also. Preferred binder resins include polyvinyl acetal resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin Insulating resin such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin can be used, but is not limited thereto. These binder resins can be used alone or in admixture of two or more. Of these, polyvinyl acetal resin is particularly preferably used.

  In addition, the blending ratio (weight ratio) between the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10. The solvent for adjusting the coating solution can be arbitrarily selected from known organic solvents such as alcohols, aromatics, halogenated hydrocarbons, ketones, ketone alcohols, ethers, esters, and the like. . For example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, Usual organic solvents such as methylene chloride, chloroform, chlorobenzene, and toluene can be used.

  Moreover, the solvent used for these dispersion | distribution can be used individually or in mixture of 2 or more types. When mixing, any solvent can be used as long as it can dissolve the binder resin as the mixed solvent.

  As a method of dispersing, methods such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker can be used. Furthermore, as a coating method used when providing this charge generation layer, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used. Can be used.

  In this dispersion, it is effective for high sensitivity and high stability that the particles have a particle size of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less.

  Further, the charge generating material can be subjected to a surface treatment for improving the stability of electrical characteristics and preventing image quality defects. A coupling agent or the like can be used as the surface treatment agent, but the surface treatment agent is not limited to this. Examples of coupling agents used for the surface treatment include vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- ( Examples of the silane coupling agent include aminoethyl) -γ-aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, and γ-chloropropyltrimethoxysilane. Of these, silane coupling agents that are particularly preferably used include vinyltriethoxysilane, vinyltris (2-methoxyethoxysilane), 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxy Examples of the silane coupling agent include silane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-chloropropyltrimethoxysilane.

  Zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl acetoacetate butoxide, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, zirconium naphthenate, lauric acid Organic zirconium compounds such as zirconium, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide and the like can also be used. Tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate Organic titanium compounds such as ethyl ester, titanium triethanolamate, polyhydroxytitanium stearate, aluminum isopropylate, monobutoxy aluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate) An organoaluminum compound such as can also be used.

  Furthermore, various additives can be added to the coating solution for charge generation layer in order to improve electrical characteristics and image quality. Additives include quinone compounds such as chloranil, bromoanil and anthraquinone, tetracyanoquinodimethane compounds, fluorenones such as 2,4,7-trinitrofluorenone and 2,4,5,7-tetranitro-9-fluorenone Compounds, 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole and 2,5-bis (4-naphthyl) -1,3,4-oxadi Azoles, oxadiazole compounds such as 2,5-bis (4-diethylaminophenyl) 1,3,4 oxadiazole, xanthone compounds, thiophene compounds, 3,3 ′, 5,5 ′ tetra-t-butyl Electron transporting substances such as diphenoquinone compounds such as diphenoquinone, electron transporting pigments such as polycyclic condensation systems and azo systems, zirconium chelate compounds, tita Umukireto compounds, aluminum chelate compounds, titanium alkoxide compounds, organic titanium compounds, there can be used a known material such as a silane coupling agent. Examples of silane coupling agents include vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltri Methoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)- γ-aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, and the like. Examples of zirconium chelate compounds include zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl zirconium acetoacetate, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, naphthene. Zirconate, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide and the like.

  Examples of titanium chelate compounds include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, Examples include titanium lactate, titanium lactate ethyl ester, titanium triethanolamate, and polyhydroxytitanium stearate.

  Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxy aluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate) and the like.

  These compounds can be used alone or as a mixture or polycondensate of a plurality of compounds.

  Furthermore, as a coating method used when providing this charge generation layer, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used. Can be used.

  Any known material can be used as the charge transport material contained in the charge transport layer immediately above the charge generation layer, and the following can be exemplified. Oxadiazole derivatives such as 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1,3,5-triphenyl-pyrazoline, 1- [pyridyl- (2)]-3 Pyrazoline derivatives such as-(p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline, triphenylamine, tri (P-methyl) phenylamine, N, N'-bis (3,4-dimethylphenyl) biphenyl Aromatic tertiary amino compounds such as -4-amine, dibenzylaniline, 9,9-dimethyl-N, N′-di (p-tolyl) fluoren-2-amine, N, N′-diphenyl-N, Aromatic tertiary diamino compounds such as N′-bis (3-methylphenyl)-[1,1-biphenyl] -4,4′-diamine, 3- (4′dimethyla 1,2,4-triazine derivatives such as nophenyl) -5,6-di- (4′-methoxyphenyl) -1,2,4-triazine, 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, 4-diphenyl Hydrazone derivatives such as aminobenzaldehyde-1,1-diphenylhydrazone, [p- (diethylamino) phenyl] (1-naphthyl) phenylhydrazone, quinazoline derivatives such as 2-phenyl-4-styryl-quinazoline, 6-hydroxy-2, Benzofuran derivatives such as 3-di (p-methoxyphenyl) -benzofuran, α-stilbene derivatives such as p- (2,2-diphenylvinyl) -N, N′-diphenylaniline, enamine derivatives, N-ethylcarbazole, etc. Carbazole derivatives, poly-N-vinylcarba Hole transport materials such as sol and its derivatives. Quinone compounds such as chloranil, bromoanil, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2- ( 4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,5-bis (4-naphthyl) -1,3,4-oxadiazole, 2,5 -Oxadiazole compounds such as bis (4-diethylaminophenyl) 1,3,4 oxadiazole, xanthone compounds, thiophene compounds, 3,3 ′, 5,5′tetra-t-butyldiphenoquinone, etc. Examples thereof include an electron transport material such as a diphenoquinone compound, or a polymer having a group comprising the above compound in the main chain or side chain. These charge transport materials can be used alone or in combination of two or more.

  Any known binder resin can be used for the charge transport layer, but an electric insulating film-forming resin is preferred. For example, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-acetic acid Vinyl copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin. Silicon-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-carbazole, polyvinyl butyral, polyvinyl formal, polysulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, phenol resin, polyamide, carboxymethyl cellulose, vinylidene chloride Examples include, but are not limited to, polymer wax and polyurethane. These binder resins are used singly or in combination of two or more. In particular, polycarbonate resins, polyester resins, methacrylic resins, and acrylic resins are compatible with charge transport materials, soluble in solvents, and strong. Excellent and preferably used. The blending ratio (weight ratio) between the binder resin and the charge transport material can be arbitrarily set in any case, but attention must be paid to a decrease in electrical characteristics and a decrease in film strength. The thickness of the charge transport layer is 5 to 50 μm, preferably 10 to 40 μm. Furthermore, as a coating method used when providing this charge transport layer, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used. Can be used. As a solvent used for coating, usual organic solvents such as dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene and toluene can be used alone or in admixture of two or more.

  Additives such as antioxidants and light stabilizers to the photoreceptors formed with multiple layers as described above for the purpose of preventing deterioration due to ozone, oxidizing gas, or light and heat. Can do.

  For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and their derivatives, organic sulfur compounds, and organic phosphorus compounds.

  Specific examples of antioxidants include phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di). -T-butyl 4'-hydroxyphenyl) -propionate, 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl) -5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-tert-butyl-phenol), 4,4'-thio-bis -(3-methyl 6-tert-butylphenol), 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetrakis- [methyle -3- (3 ', 5'-di-t-butyl-4'-hydroxy-phenyl) propionate] -methane, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy- 5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane. Among hindered amine compounds, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2, 2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4, -Benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine heavy succinate Compound, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diimyl} {(2,2,6,6-tetramethyl- 4-piperidyl) imino} hexamethylene {(2,3,6,6-tetramethyl-4-piperidyl) imino}], 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2- n-Butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N— (1,2,2,6,6, -pentamethyl-4piperidyl) amino] -6-chloro-1,3,5-triazine condensate and the like. Dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis- ( β-lauryl-thiopropionate), ditridecyl-3,3′-thiodipropionate, 2-mercaptobenzimidazole and the like. Examples of organophosphorus antioxidants include trisnonylphenyl phosfete, triphenyl phosfeft, and tris (2,4-di-t-butylphenyl) -phosfte.

  Organic sulfur-based and organic phosphorus-based antioxidants are referred to as secondary antioxidants, and a synergistic effect can be obtained by using them together with primary antioxidants such as phenols or amines.

  Examples of the light stabilizer include benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine derivatives. Examples of the benzophenone light stabilizer include 2-hydroxy-4-methoxy benzophenone, 2-hydroxy-4-octoxy benzophenone, and 2,2'-di-hydroxy-4-methoxy benzophenone. 2-(-2′-hydroxy-5′methyl phenyl-)-benzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″) as a benzotriazole-based light stabilizer , 6 ″ -tetra-hydrophthalimido-methyl) -5′-methylphenyl] -benzotriazole, 2-(-2′-hydroxy-3′-t-butyl 5′-methylphenyl-)-5-chlorobenzo Triazole, 2- (2′-hydroxy-3′-t-butyl 5′-methylphenyl-)-5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl-) -Benzotriazole, 2- (2'-hydroxy-5'-t-octyl phenyl) -benzotriazole, 2- (2'-hydroxy 3 ', 5'-di-t-amyl phenyl) -)-Benzotriazole and the like. Other compounds include 2,4, di-t-butylphenyl 3 ', 5'-di-t-butyl-4'-hydroxybenzoate, nickel dibutyl-dithiocarbamate and the like.

Further, at least one kind of electron accepting substance can be included for the purpose of improving sensitivity, reducing residual potential, reducing fatigue during repeated use, and the like. Examples of the electron accepting substance that can be used in the photoreceptor of the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o -Dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and the like can be mentioned. Of these, fluorenone-based, quinone-based, and benzene derivatives having electron-withdrawing substituents such as Cl, CN, NO ₂ are particularly preferable.

  The charge transport layer can also contain fine particles such as silica and fluorine resin. The content of the fluororesin in the charge transport layer is suitably from 0.1 to 40% by weight, particularly preferably from 1 to 30% by weight, based on the total amount of the charge transport layer. If the content is less than 1% by weight, the modification effect due to the dispersion of the fluororesin particles is not sufficient. On the other hand, if the content exceeds 40% by weight, the light transmission property is lowered and the residual potential is increased by repeated use. .

  Examples of the fluororesin particles used in the present invention include a tetrafluoroethylene resin, a trifluorinated ethylene resin, a hexafluoropropylene resin, a vinyl fluoride resin, a vinylidene fluoride resin, a difluorodiethylene chloride resin, and their It is desirable to appropriately select one or two or more types from among the copolymers, but tetrafluoroethylene resin and vinylidene fluoride resin are particularly preferable.

  A small amount of silicone oil can be added to the coating solution as a leveling agent for improving the smoothness of the coating film.

  In addition, a high-strength surface layer can be provided in order to provide resistance to abrasion and scratches on the surface layer. As this high-strength surface layer, conductive fine particles dispersed in a binder resin, lubricating fine particles such as fluororesin and acrylic resin dispersed in an ordinary charge transport layer material, silicon and acrylic hard A coating agent can be used, but from the viewpoint of strength, electrical properties, image quality maintenance, and the like, those comprising a siloxane-based resin having a charge transporting property and having a crosslinked structure are preferable. The structure represented by I) is preferred because of its strength and stability. F in the general formula (I) has a structure having photocarrier transport properties, such as triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds. And quinone compounds, fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, ethylene compounds, and the like.

GDF: general formula (I)
G: Inorganic glassy network subgroup D: Flexible organic subunit F: Charge transporting subunit G in general formula (I), particularly preferably reactive Si groups, undergo a crosslinking reaction with each other to form a three-dimensional structure. To form a typical Si—O—Si bond, ie, an inorganic glassy network.

D in the general formula (I) is for connecting F for imparting charge transporting properties directly to a three-dimensional inorganic glassy network. In addition, the inorganic glassy network, which has firmness but is brittle, is imparted with appropriate flexibility and has an effect of improving the strength as a film. The group capable of binding to the compound represented by the general formula (I) means a group capable of binding to a silanol group generated when the compound represented by the general formula (I) is hydrolyzed. , Si (R ₁ ) _(3-a) Q _a means an epoxy group, an isocyanate group, a carboxyl group, a hydroxy group, a halogen or the like. Among these, a compound represented by a group represented by Si (R ₁ ) _(3-a) Q _a , an epoxy group, or an isocyanate group is preferable because it has higher mechanical strength. Furthermore, those having two or more of these groups in the molecule are preferable because the crosslinked structure of the cured film becomes three-dimensional and has higher mechanical strength.

  For the purpose of adjusting the film formability and flexibility of the film, it may be used by mixing with other coupling agents and fluorine compounds. As such a compound, various silane coupling agents and commercially available silicon-based hard coat agents can be used. As silane coupling agents, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane, Dimethyldimethoxysilane and the like can be used. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), and AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning). Can be used. In addition, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- ( Heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoro Fluorine-containing compounds such as octyltriethoxysilane may be added. The silane coupling agent can be used in an arbitrary amount, but the amount of the fluorine-containing compound is desirably 0.25 or less by weight with respect to the compound not containing fluorine. Beyond this, there may be a problem with the film formability of the crosslinked film.

In order to improve the strength of the film, it is more preferable to simultaneously use a compound having two or more substituted silicon groups having a hydrolyzable group represented by Si (R ₁ ) _(3-a) Q _a. preferable.

  These coating solutions are prepared without solvent or, if necessary, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, diethyl ether and dioxane. Although it can be used, it preferably has a boiling point of 100 ° C. or less, and can be used by arbitrarily mixing. The amount of the solvent can be arbitrarily set, but if it is too small, the compound represented by the general formula (I) is likely to be precipitated, so 0.5 to 30 parts by weight with respect to 1 part by weight of the compound represented by the general formula (I), Preferably, it is used at 1 to 20 parts by weight. While the reaction temperature and time vary depending on the type of raw material, it is usually 0 to 100 ° C., preferably 10 to 70 ° C., particularly preferably 50 to 150 ° C. Although there is no restriction | limiting in particular in reaction time, Since it will become easy to produce gelation when reaction time becomes long, it is preferable to carry out in 10 minutes to 100 hours.

  Further, examples of the curing catalyst include the following.

  Protic acids such as hydrochloric acid, acetic acid, phosphoric acid and sulfuric acid, bases such as ammonia and triethylamine, organotin compounds such as dibutyltin diacetate, dibutyltin dioctoate and stannous oxalate, tetra-n-butyl titanate, tetraisopropyl titanate Organic titanium compounds such as aluminum tributoxide, aluminum triacetylacetonate, etc., organic carboxylic acid iron salts, manganese salts, cobalt salts, zinc salts, zirconium salts, etc. A metal compound is preferable, and further, metal acetylacetonate or acetylacetate is preferable, and aluminum triacetylacetonate is particularly preferable. The amount of the curing catalyst used can be arbitrarily set, but is preferably 0.1 to 20% by weight with respect to the total amount of materials containing hydrolyzable silicon substituents in terms of storage stability, characteristics, strength, etc. More preferably, it is 3 to 10% by weight. The curing temperature can be arbitrarily set, but is set to 60 ° C. or higher, more preferably 80 ° C. or higher in order to obtain a desired strength. Although hardening time can be arbitrarily set as needed, 10 minutes-5 hours are preferable. It is also effective to stabilize the characteristics after the curing reaction by maintaining a high humidity state. Furthermore, depending on the application, it can be hydrophobized by surface treatment with hexamethyldisilazane, trimethylchlorosilane, or the like.

  An antioxidant is preferably added to the surface cross-linked cured film of the photoreceptor for the purpose of preventing deterioration due to an oxidizing gas such as ozone generated by a charger. When the mechanical strength of the surface of the photoconductor is increased and the photoconductor has a long life, the photoconductor is in contact with the oxidizing gas for a long time, and therefore, stronger oxidation resistance is required than before. Antioxidants are preferably hindered phenols or hindered amines, organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, benzimidazole antioxidants. , Etc., may be used. The addition amount of the antioxidant is preferably 20% by weight or less, and more preferably 10% by weight or less. Examples of the hindered phenol antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, N, N′-hexamethylene bis (3,5-di). -T-butyl-4-hydroxyhydrocinnamide, 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 2,4-bis [(octylthio) methyl] -o-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol) 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,5-di-t-amylhydroquinone, 2-t-butyl-6- (3-butyl-2- Dorokishi-5-methylbenzyl) -4-methylphenyl acrylate, 4,4'-butylidene bis (3-methyl -6-t-butylphenol), and the like.

  Also, a resin that dissolves in alcohol can be added for the purposes of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life extension, and the like. Examples of resins soluble in alcohol solvents include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal or acetoacetal (for example, manufactured by Sekisui Chemical Co., Ltd.) ESREC B, K, etc.), polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics. The molecular weight of the resin is preferably 2000-100000, more preferably 5000-50000. If the molecular weight is less than 2000, the desired effect cannot be obtained. If the molecular weight is more than 100,000, the solubility becomes low and the addition amount is limited, or the film formation is poor at the time of coating. The addition amount is preferably 1 to 40%, more preferably 1 to 30%, and most preferably 5 to 20%. When it is less than 1%, it is difficult to obtain a desired effect, and when it is more than 40%, image blurring under high temperature and high humidity tends to occur.

  Furthermore, various fine particles can be added in order to improve the contamination resistance adhesion and lubricity on the surface of the photoreceptor. They can be used alone or in combination. Examples of the fine particles include silicon-containing fine particles. The silicon-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles. The colloidal silica used as the silicon-containing fine particles is selected from those dispersed in an acidic or alkaline aqueous dispersion having an average particle diameter of 1 to 100 nm, preferably 10 to 30, or an organic solvent such as alcohol, ketone and ester. A commercially available product can be used. The solid content of colloidal silica in the outermost surface layer is not particularly limited, but is 0.1 to 50% by weight in the total solid content of the outermost surface layer in terms of film forming properties, electrical characteristics, and strength. Is used, preferably in the range of 0.1 to 30% by weight. Silicone fine particles used as silicon-containing fine particles are spherical and have an average particle diameter of 1 to 500 nm, preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and are generally commercially available. Can be used. Silicone fine particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain sufficient characteristics is low, the electron does not hinder the crosslinking reaction, The surface properties of the photographic photoreceptor can be improved. In other words, it is possible to improve the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly incorporated into a strong cross-linked structure, and to maintain good wear resistance and adherence to contaminants over a long period of time. it can. The content of the silicone fine particles in the outermost surface layer in the electrophotographic photosensitive member of the present invention is in the range of 0.1 to 30% by weight, preferably 0.5 to 10% by weight in the total solid content of the outermost surface layer. Range.

As other fine particles, fluorine fine particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and the 8th Polymer Materials Forum Lecture Proceedings p89. Fine particles comprising a resin obtained by copolymerizing the fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , ZnO— Examples thereof include semiconductive metal oxides such as TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. For the same purpose, an oil such as silicone oil can be added. Examples of silicone oil include silicone oil such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3, 5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylsilane Cyclomethylphenylcyclosiloxanes such as rhotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane, and cyclic phenylcyclo such as hexaphenylcyclotrisiloxane Hydrosilyl group-containing cyclosiloxanes such as siloxanes, fluorine-containing cyclosiloxanes such as 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane, methylhydrosiloxane mixtures, pentamethylcyclopentasiloxane and phenylhydrocyclosiloxanes And cyclic siloxanes such as vinyl group-containing cyclosiloxanes such as pentavinylpentamethylcyclopentasiloxane.

  A siloxane-based resin having a charge transporting property and having a crosslinked structure has excellent mechanical strength and sufficient photoelectric properties, so that it can be used as it is as a charge transport layer of a multilayer photoreceptor. In that case, usual methods such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method can be used. However, when a required film thickness cannot be obtained by a single application, the necessary film thickness can be obtained by applying a plurality of times. In the case where a plurality of times of overcoating are performed, the heat treatment may be performed every time the coating is applied, or may be performed after a plurality of times of overcoating.

In the case of a single-layer type photosensitive layer, it is formed containing the charge generating material and a binder resin. As the binder resin, the same binder resins as those used for the charge generation layer and the charge transport layer can be used. The content of the charge generating substance in the single-layer type photosensitive layer is about 10 to 85% by weight, preferably 20 to 50% by weight. A charge transport material or a polymer charge transport material may be added to the single-layer type photosensitive layer for the purpose of improving photoelectric characteristics. The addition amount is preferably 5 to 50% by weight. Moreover, you may add the compound shown by general formula (I). The solvent and coating method used for coating can be the same as described above. The film thickness is preferably about 5 to 50 μm, more preferably 10 to 40 μm.

  Furthermore, the surface layer of the photoreceptor can be coated with an aqueous dispersion of a modified resin containing a fluorine-based resin as an essential component, or can be dipped. This is preferable because the torque can be further reduced and the transfer efficiency can be improved.

  An aqueous dispersion of a modified resin containing a fluorine-based resin for treating the surface layer of the photoreceptor as an essential component will be described.

  Fluorocarbon resins include tetrafluoroethylene homopolymers or copolymers of tetrafluoroethylene and olefins, fluorine-containing olefins, perfluoroolefins, fluoroalkyl vinyl ethers, vinylidene fluoride homopolymers or vinylidene fluoride and olefins, fluorine-containing Copolymers with olefins, perfluoroolefins, fluoroalkyl vinyl ethers, homopolymers of chlorotrifluoroethylene or copolymers of chlorotrifluoroethylene with olefins, fluorine-containing olefins, perfluoroolefins, fluoroalkyl vinyl ethers, etc. , Tetrafluoroethylene homopolymers or copolymers are preferred, and tetrafluoroethylene homopolymers and various The polymer in a weight ratio of 95: 5 to 10: it is also preferable to use a mixture with 90.

  The modified resin containing a fluororesin as an essential component is used as an aqueous dispersion, and the aqueous dispersion may further contain a wax and / or silicone. By containing wax or silicone, it is preferable to promote the penetration of the fluororesin into the blade. Here, examples of the wax include paraffin wax, microcrystalline wax, and perotratam. Examples of the silicone include silicone oil, silicone grease, oil compound, and silicone varnish.

  For aqueous dispersions of modified resins containing fluorine resin as an essential component, fluorine-based or other nonionic, cationic, anionic or amphoteric surfactants, pH adjusters, solvents, polyhydric alcohols, flexible An agent, a viscosity modifier, a light stabilizer, an antioxidant and the like can also be mixed.

  The permeation layer can be formed by immersing it in an aqueous dispersion of a modified resin containing a fluororesin as an essential component, but it can also be performed under reduced pressure to promote permeation of the fluororesin. it can. The pressure at this time is 0.9 atm or less, preferably 0.8 atm or less, more preferably 0.7 atm or less. In addition, heating the aqueous dispersion to 40 ° C. or higher, preferably 50 ° C. or higher is effective in promoting penetration. Furthermore, it is also effective to perform the treatment at 0.1 atm or higher, preferably 0.2 atm or higher, more preferably 0.3 atm or higher, and it is also effective to combine decompression, pressurization and heat treatment. is there. Moreover, after making it adhere by spraying or the apply | coating method, it can heat to 40 degreeC or more, Preferably it is 50 degreeC or more, and an osmosis | permeation layer can also be formed. After the aqueous dispersion of the modified resin containing a fluorine-based resin as an essential component is attached, it can be wiped off or washed before or after heat drying.

  In this embodiment, a case where a tandem system in which a plurality of image carriers and developing devices are arranged is described as an example, but a single method in which a plurality of developers are arranged around the image carrier. May be adopted.

It is a figure which shows the rotating brush for supplying a lubricant. 1 is a schematic configuration diagram of a main part of a printer that is a first embodiment of an image forming apparatus of the present invention; FIG. 3 is an enlarged view of a yellow image forming unit shown in FIG. 2.

Explanation of symbols

1 Printer 10Y, 10M, 10C, 10K Image forming unit 11Y, 11M, 11C, 11K Photoconductor 12Y, 12M, 12C, 12K Developing roll 13Y, 13M, 13C, 13K Charger 14Y, 14M, 14C, 14K Exposure unit 15Y, 15M, 15C, 15K Photoconductor maintenance unit 150Y Housing 151Y Blade 152Y Rotating brush 153Y Bias applying device 154Y Flicking member 155Y Lubricant supply mechanism 30 Intermediate transfer belt 31 Tension roller 40 Secondary transfer roll

Claims (2)

Includes an additive having a property of rotating in a predetermined direction and forming an electrostatic latent image on the surface of the image carrier having a lubricant applied to the surface, and charging the toner to a polarity opposite to the normal charging polarity of the toner The electrostatic latent image is developed with toner in the developer using a developing device that holds the developer inside to form a toner image on the surface of the image carrier, and the toner image is finally In an image forming apparatus for forming an image composed of a fixed toner image on a recording medium by transferring and fixing the recording medium on the recording medium,
A cleaning unit that scrapes off the residue remaining on the surface after the toner image on the surface of the image carrier is transferred to the surface by rubbing against the surface;
A solid lubricant mainly composed of zinc stearate applied to the surface of the image carrier;
It is arranged upstream of the cleaning unit in the rotation direction of the image carrier, has conductive hairs, and rotates while the hairs are in contact with the solid lubricant. A brush for applying a lubricant to the surface of the image carrier;
A charge imparting portion that imparts a charge having a polarity opposite to the normal charge polarity of the toner to the hair portion;
An image forming apparatus comprising: a flicking member that comes into contact with the bristles and knocks off deposits attached to the bristles as the brush rotates.   It has a rotating portion that holds the solid lubricant and is rotatably supported via a rotating shaft parallel to the brush, and a moment generating portion that generates a moment around the rotating shaft. The image forming apparatus according to claim 1, further comprising a support member that makes the solid lubricant held by the rotating portion contact the brush by a moment generated by the moment generating portion.

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