JP2017194507A - Image carrier protective agent, protective layer forming device, image forming method, image forming apparatus, and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image carrier protective agent that can suppress squeaking of a blade, protects image carriers, prevents contamination of charging means, and has improved cleanability.SOLUTION: There is provided an image carrier protective agent containing a fatty acid metal salt and an inorganic lubricant, where the inorganic lubricant contains a first inorganic lubricant having a number average primary particle diameter of 1.0 μm or less and a second inorganic lubricant having a number average primary particle diameter of 2.0 μm or more. Preferable aspects include one where the inorganic lubricant is at least one selected from mica, boron nitride, molybdenum disulfide, tungsten disulfide, talc, kaolin, montmorillonite, calcium fluoride, and graphite.SELECTED DRAWING: None

Description

  The present invention relates to an image carrier protecting agent, a protective layer forming apparatus, an image forming method, an image forming apparatus, and a process cartridge.

  Conventionally, an electrophotographic image forms an electrostatic latent image by an electrostatic charge on an image carrier, and a charged toner is attached to the electrostatic latent image by a developing means to form a visible image. The visible image is transferred to a recording medium.

  The toner that has not been transferred may remain on the image carrier after the transfer of the visible image onto the recording medium, and the electrostatic latent image is formed with the toner remaining on the image carrier. When formed, there is a problem that uniform charging of the image carrier is inhibited. For this reason, after the transfer, the toner remaining on the image carrier is removed by a cleaning process and then charged. In order to prevent toner from remaining on the transferred image carrier, an image carrier protective agent containing an inorganic lubricant such as a fatty acid metal salt and boron nitride is applied to the surface of the image carrier. Things have been done.

  However, the stress due to the friction between the image carrier and the cleaning means in the cleaning step causes the image carrier to wear and scratches the image carrier, and filming of the image carrier cannot be prevented. There is a problem that the protection of the body is poor. Further, there is a problem that the charging means is contaminated, and further, toner cannot be sufficiently prevented from passing through in the cleaning process.

Therefore, it contains a fatty acid metal salt and boron nitride, and the boron nitride has a crystal grain size of 0.1 μm to 1.0 μm and a secondary particle size of 3.0 μm to 14.0 μm. An image carrier protecting agent has been proposed (see, for example, Patent Document 1).
Further, there has been proposed an image carrier protecting agent containing a fatty acid metal salt and boron nitride, wherein the oxygen content of the boron nitride is 0.4 wt% to 4.5 wt% (for example, Patent Document 2). reference).
Furthermore, a protective layer forming apparatus having a protective agent block containing a fatty acid metal salt, a core material, and a roller-shaped image carrier protective agent supply member has been proposed (for example, see Patent Document 3).

  SUMMARY OF THE INVENTION An object of the present invention is to provide an image carrier protecting agent that can suppress blade squealing and has both the protection of the image carrier, the prevention of contamination of the charging means, and the cleaning property.

  The image carrier protective agent of the present invention as a means for solving the above problems contains a fatty acid metal salt and an inorganic lubricant, and the inorganic lubricant has a number average primary particle size of 1.0 μm or less. A first inorganic lubricant and a second inorganic lubricant having a number average primary particle size of 2.0 μm or more.

  According to the present invention, it is possible to provide an image carrier protecting agent that can suppress blade squealing and has both protection of the image carrier, prevention of contamination of the charging means, and cleaning.

FIG. 1A is a schematic cross section showing an example of an open-cell foam layer. FIG. 1B is a schematic cross-sectional view showing an example of a closed cell foam layer. FIG. 2A is a side view showing an example of an image carrier protecting agent supply member. FIG. 2B is an enlarged schematic view showing an example of an exposed surface of the continuous foam type foam layer. FIG. 3 is a schematic view showing an example of the protective layer forming apparatus of the present invention. FIG. 4 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 5 is a schematic view showing an example of the process cartridge of the present invention.

(Image carrier protective agent)
The image carrier protecting agent of the present invention contains a fatty acid metal salt and an inorganic lubricant, wherein the inorganic lubricant has a number average primary particle size of 1.0 μm or less; And a second inorganic lubricant having a number average primary particle size of 0 μm or more, and further contains other components as necessary.
In the image carrier protective agent of the present invention, in the conventional image carrier protective agent and protective layer forming apparatus, vibration is generated in the cleaning process when the cleaning blade or the image carrier protective agent coating blade and the image carrier are rubbed. However, this is based on the knowledge that there is a problem that blade squeal occurs at that time.

<Fatty acid metal salt>
There is no restriction | limiting in particular as said fatty acid metal salt, According to the objective, it can select suitably.

  The fatty acid metal salt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, barium stearate, lead stearate, iron stearate, nickel stearate, cobalt stearate, copper stearate, stearin Strontium acid, calcium stearate, cadmium stearate, magnesium stearate, zinc stearate, zinc oleate, magnesium oleate, iron oleate, cobalt oleate, copper oleate, lead oleate, manganese oleate, zinc palmitate, Cobalt palmitate, lead palmitate, magnesium palmitate, aluminum palmitate, calcium palmitate, lead caprylate, lead caprate, zinc linolenate, cobalt linolenate, calcium linolenate, ricino Le zinc, cadmium ricinoleate, zinc laurate, cobalt laurate, lauric, lead and the like magnesium laurate. These may be used individually by 1 type and may use 2 or more types together. Among these, zinc stearate, calcium stearate, and zinc laurate are preferable because they are excellent in cleaning properties and image carrier protection, inexpensive, and very hydrophobic. Zinc is more preferred.

  There is no restriction | limiting in particular as a structure of the said fatty-acid metal salt, According to the objective, it can select suitably, For example, a lamellar crystal structure etc. are mentioned.

  There is no restriction | limiting in particular as said fatty acid metal salt, According to the objective, it can select suitably, A commercial item can be used. As said commercial item, it can obtain from Wako Pure Chemical Industries Ltd. etc., for example.

  There is no restriction | limiting in particular as content of the said fatty-acid metal salt, Although it can select suitably according to the objective, 70 to 98 mass% is preferable with respect to the said image carrier protective agent whole quantity, 75 More preferably, it is at least 95% by mass. When the content is 70% by mass or more and 98% by mass or less, the protection performance of the image carrier, the prevention of contamination of the charging means, the cleaning property, and the moldability of the image carrier protection agent are improved.

<Inorganic lubricant>
The inorganic lubricant includes a first inorganic lubricant and a second inorganic lubricant.
By using the first inorganic lubricant and the second inorganic lubricant in combination, it is possible to improve the prevention of contamination of the charging means, the protection of the image carrier, and the cleaning performance by taking advantage of both. Can be achieved at the same time.
The inorganic lubricant means a compound in which the layers are bonded with a weak van der Waals force and the compound itself is cleaved and lubricated or causes internal slip.

The inorganic lubricant (first inorganic lubricant and second inorganic lubricant) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, mica, boron nitride, molybdenum disulfide, Examples include tungsten disulfide, talc, kaolin, montmorillonite, calcium fluoride, and graphite. These may be used individually by 1 type and may use 2 or more types together.
Among these, as the first inorganic lubricant, boron nitride and talc are preferable, and hexagonal mesh surfaces in which atoms are firmly combined overlap with each other at a wide interval, and only a weak van der Waals force connects the layers. Therefore, boron nitride is more preferable because the interlayer is easily cleaved and lubricated.
Further, as the second inorganic lubricant, boron nitride is preferable.

The number average primary particle size of the first inorganic lubricant is 1.0 μm or less, preferably 0.8 μm or less, more preferably 0.1 μm or more and 0.8 μm or less, and 0.1 μm or more and 0.5 μm or less. Is particularly preferred. When the number average primary particle size is 1.0 μm or less, the fluidity of the particles tends to be low and the cohesiveness tends to be strong, and the particles can be laminated at the edge of the blade. Can stabilize the behavior of the blade and suppress blade noise.
The number average primary particle size of the second inorganic lubricant is 2.0 μm or more, preferably 2.0 μm or more and 15.0 μm or less, more preferably 2.0 μm or more and 12.0 μm or less, and 2.0 μm or more. 8.0 μm or less is particularly preferable. When the number average primary particle size is 2.0 μm or more, the fluidity of the particles is high, the lubricity can be improved, and the film formation efficiency on the image carrier can be improved. Thereby, a high lubrication effect can be obtained, contamination prevention of the charging means, and cleaning properties can be improved.
Examples of the number average primary particle size of the inorganic lubricant include, for example, an image observed with a scanning electron microscope (SEM) (thermal F-SEM, manufactured by Zeiss, ULTRA55), image analysis / measurement software (Image-pro plus). 4.0j, manufactured by Media Cybernetics), and can be obtained by averaging the 10 samples.

The first inorganic lubricant is not particularly limited as long as the number average primary particle size is 1.0 μm or less, and a commercially available product can be used. As said commercial item, for example, boron nitride, trade name: HCV (made by Momentive Performance Materials Japan G.K., number average primary particle size: 0.1 μm); trade name: FS-1 (made by Mizushima Alloy Iron Co., Ltd.) , Number average primary particle size: 0.2 μm), product name: S1-F (number average primary particle size: 0.5 μm), product name: S03 (number average primary particle size: 0.8 μm), (above, ESK Examples of the talc include trade name: D-800 (manufactured by Nippon Talc Co., Ltd., number average primary particle size: 0.8 μm). These may be used individually by 1 type and may use 2 or more types together.
The second inorganic lubricant is not particularly limited as long as the number average primary particle size is 2.0 μm or more, and a commercially available product can be used. Examples of the commercially available product include, as boron nitride, trade name: HP-P1 (manufactured by ESK Ceramics, number average primary particle size: 2.0 μm); trade name: HGP (manufactured by Denka Corporation, number average primary particle size) : Product name: HP-4W (Number average primary particle size: 8.0 μm), Product name: HP-2W (Number average primary particle size: 12.0 μm), (Mizushima Alloy Iron Co., Ltd.) Product name: S-15 (manufactured by ESK Ceramics, number average primary particle size: 15.0 μm), and the like. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said inorganic lubricant, Although it can select suitably according to the objective, 2 mass% or more and 30 mass% or less are preferable with respect to the said image carrier protective agent whole quantity, 5 More preferably, it is at least 25% by mass. When the content is 2% by mass or more, the amount of film formation becomes appropriate, contamination of the charging means can be prevented, and cleaning properties can be improved. Further, when the content is 30% by mass or less, the protective property of the image carrier is good.

[Mass ratio (first inorganic lubricant / second inorganic lubricant)]
The mass ratio (first inorganic lubricant / second inorganic lubricant) is preferably 30/70 or more and 50/50 or less. When the mass ratio (first inorganic lubricant / second inorganic lubricant) is 30/70 or more and 50/50 or less, the charging means is prevented from being contaminated, the image carrier is protected, and the blade squeal is prevented. It can be improved.

[Mass ratio (fatty acid metal salt / inorganic lubricant)]
The mass ratio (fatty acid metal salt / inorganic lubricant) between the content (mass%) of the fatty acid metal salt and the content (mass%) of the inorganic lubricant is preferably 70/30 or more and 98/2 or less. 75/25 or more and 95/5 or less is more preferable. When the mass ratio (fatty acid metal salt / inorganic lubricant) is 70/30 or more, the amount of the inorganic lubricant film increases, preventing contamination of the charging means and improving cleaning properties, and 98/2 or less. As a result, the protection of the image carrier and the moldability of the image carrier protective agent can be improved. Further, when the mass ratio (fatty acid metal salt / inorganic lubricant) is within a preferable numerical range, the film forming property by the inorganic lubricant is improved, the charging means can be prevented from being contaminated, the cleaning property, and the image carrier protection. And the moldability of the image carrier protecting agent can be improved.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. For example, inorganic particles such as silica, alumina, ceria, zirconia, clay, calcium carbonate, or surface hydrophobized particles thereof. Organic particles such as polymethyl methacrylate particles (PMMA), polystyrene particles, silicone resin particles, polytetrafluoroethylene resin (PTFE), organic molybdenum, α-olefin-norbornene copolymer resin particles, melamine formaldehyde, surfactants, etc. Is mentioned.

  The method for molding the image carrier protecting agent of the present invention into a fixed shape, for example, a prismatic or cylindrical shape, is not particularly limited, and a known method can be used as a method for molding a solid substance, For example, a compression molding method, a melt molding method, a powder molding method, a cold isostatic pressing method (CIP), a hot isostatic pressing method (HIP) and the like can be mentioned. Among these, the compression molding method and the melt molding method are preferable, and the compression molding method is more preferable from the viewpoint of ease of scraping of the molded body.

  As the compression molding method, for example, a mixture of the fatty acid metal salt and the inorganic lubricant is placed in a mold of a predetermined size, and then compression molded at a predetermined pressure and time. Examples include a method of removing a product from a mold and obtaining a molded body. Thereafter, the shape of the image carrier protecting agent can be adjusted by cutting or the like.

As the melt molding method, for example, a predetermined amount of a heated and melted fatty acid metal salt and an inorganic lubricant is poured into a mold having a predetermined shape, which is heated to a temperature higher than the melting temperature of the image carrier protecting agent. Accordingly, there may be mentioned a method of obtaining a molded article by maintaining at a temperature equal to or higher than the melting point for a certain time and then cooling by standing or cooling. In addition, in order to remove internal distortion of the molded body, after cooling proceeds to a temperature lower than the phase transition temperature of the fatty acid metal salt and the inorganic lubricant during the cooling, it is gradually restarted again to a temperature equal to or higher than the phase transition temperature. You may heat.
After cooling to a temperature close to room temperature, the molded body is removed from the mold to obtain a molded body of the image carrier protecting agent. After that, the shape of the image carrier protecting agent may be adjusted by cutting or the like.

The mold is preferably a metal mold such as steel, stainless steel or aluminum from the viewpoint of good thermal conductivity and good dimensional accuracy. The inner wall surface of the mold is preferably coated with a release agent such as a fluororesin or a silicone resin in order to improve the releasability.
The produced block-shaped image carrier protecting agent can be used by being bonded to a base material such as metal, alloy, plastic, etc. with an adhesive or the like.

There is no restriction | limiting in particular as an image carrier protection agent of this invention, According to the objective, a density etc. can be selected suitably.
The density of the image-bearing member protecting agent of the present invention is not particularly limited, as appropriate may be selected, 1.11 g / cm ³ or more 1.27 g / cm ³ or less are preferred according to the purpose, 1.11 g / cm ³ or more 1.190 g / cm ³ and more preferably less, 1.116 g / cm ³ or more 1.180 g / cm ³ or less is particularly preferred.
The density of the compression-molded image carrier protective agent is not particularly limited and may be appropriately selected depending on the intended purpose. However, when compression molding is performed at a pressure of 130 kN and a compression time of 10 seconds, 1.11 g / cm ³ or 1.190 g / cm ³ or less is preferable, 1.116 g / cm ³ or more 1.180 g / cm ³ or less is more preferable. Applying said density is, if it is 1.11 g / cm ³ or more 1.190 g / cm ³ or less, the image-bearing member protecting agent supplying member, in particular by using a urethane roller, easily image-bearing member protecting agent to the image bearing member can do.
The density can be calculated by dividing the mass (W) of the image carrier protective agent by the volume (V) of the image carrier protective agent. The mass (W) can be calculated using an analytical balance (device name: AB204-S, manufactured by METTLER TOLEDO CO., LTD.), And the volume (V) can be calculated using a micrometer or a caliper.

(Protective layer forming device)
The protective layer forming apparatus of the present invention has the image carrier protective agent of the present invention and an image carrier protective agent supply member, preferably a protective layer forming member, and further, if necessary, a pressing force is applied. It has other members, such as a member.

As the image carrier protecting agent, the image carrier protecting agent of the present invention is used.
The image carrier protecting agent supply member is a member that supplies the image carrier protecting agent to the surface of the image carrier.
The protective layer forming member is a member that forms a protective layer on the surface of the image carrier by pressing the image carrier protective agent supplied to the image carrier.
The pressing force applying member is a member that presses the image carrier protecting agent and presses it against the image carrier protecting agent supply member.

  In the case where the protective layer forming member is provided in the protective layer forming apparatus, the protective layer forming member may also serve as a cleaning unit. However, in order to more reliably form the protective layer, an image carrier is previously formed by the cleaning unit. It is preferable to remove the residue mainly composed of the toner above so that the residue does not enter the protective layer.

Here, FIG. 3 is a schematic view showing an example of the protective layer forming apparatus of the present invention.
The protective layer forming apparatus 2 disposed opposite to the photosensitive drum as the image carrier 1 includes the image carrier protective agent 21, the image carrier protective agent supply member 22, the pressing force applying member 23, and the protection of the present invention. The layer forming member 24 is configured.

The image carrier protecting agent 21 of the present invention contacts the image carrier protecting agent supply member 22 such as a foam roller by the pressing force from the pressing force applying member 23. The image carrier protecting agent supply member 22 rotates and rubs with the image carrier 1 with a linear velocity difference. At this time, the image carrier protecting agent 21 held on the surface of the image carrier protecting agent supply member 22 is imaged. Supply to the surface of the carrier 1.
Since the image carrier protecting agent 21 supplied to the surface of the image carrier 1 may not be a sufficient protective layer at the time of supply depending on the selection of the material type, in order to form a more uniform protective layer, for example, The protective layer forming member 24 is thinned to form a protective layer.

  The image bearing member on which the protective layer is formed is, for example, in a minute gap by bringing the charging roller 3 to which a DC voltage or a voltage obtained by superimposing an AC voltage is applied with a high voltage power source (not shown) into contact or in proximity. The image carrier 1 is charged by discharging. At that time, a part of the protective layer is decomposed or oxidized by electrical stress. In addition, the air discharge product adheres to the surface of the protective layer.

  The deteriorated image carrier protecting agent is removed by the cleaning unit together with other components such as toner remaining on the image carrier 1 by a normal cleaning unit. Such a cleaning means 4 may be used also as the protective layer forming member 24. However, the function of removing the residue on the surface of the image carrier and the function of forming the protective layer are different from each other. Since the states may be different, the functions are separated, and a cleaning unit 4 including a cleaning member 41 and a cleaning member pressing mechanism 42 is provided upstream of the image carrier protecting agent supply unit 22 as shown in FIG. It is preferable.

  There is no restriction | limiting in particular as a material of the braid | blade used for the said protective layer formation member 24, According to the objective, it can select suitably, For example, urethane rubber, hydrin rubber, silicone rubber, fluororubber etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. In these rubber blades, the contact portion with the image carrier may be coated or impregnated with a low friction coefficient material. Moreover, in order to adjust the density of an elastic body, you may disperse fillers, such as an organic filler and an inorganic filler.

The blade is fixed to the blade support by any method such as adhesion or fusion so that the tip can be pressed against the surface of the image carrier. The thickness of the blade is not particularly limited, and varies depending on the balance with the force applied by pressing and cannot be uniquely defined, but is preferably 0.5 mm or more and 5 mm or less, more preferably 1 mm or more and 3 mm or less.
Also, the length of the cleaning blade that protrudes from the blade support and can bend, that is, the so-called free length, is not unambiguously defined in consideration of the force applied by pressing in the same manner. Is preferably 2 mm or more and 10 mm or less.

  As another configuration of the blade, a coating layer is formed on a surface of an elastic metal blade such as a spring plate by a method such as coating or dipping via a coupling agent or a primer component as necessary, and if necessary, heat is applied. Curing or the like may be performed, and surface polishing or the like may be performed as necessary.

The coating layer contains at least a binder resin and a filler, and further contains other components as necessary.
The binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fluorine resins such as PFA, PTFE, FEP and PVDF; silicone elastomers such as fluorine rubber and methylphenyl silicone elastomer. Etc.

  There is no restriction | limiting in particular as thickness of the said elastic metal braid | blade, Although it can select suitably according to the objective, 0.05 mm or more and 3 mm or less are preferable, and 0.1 mm or more and 1 mm or less are more preferable. In the elastic metal blade, in order to suppress twisting of the metal blade, a process such as bending may be performed in a direction substantially parallel to the support shaft after attachment.

  The force that presses the image carrier 1 with the protective layer forming member 24 is sufficient as the force that the image carrier protective agent extends to become a protective layer or a protective film, and there is no particular limitation on the linear pressure. Although it can be appropriately selected according to the purpose, it is preferably 5 gf / cm or more and 80 gf / cm or less, more preferably 10 gf / cm or more and 60 gf / cm or less.

  Examples of the image carrier protecting agent supply member 22 include a brush-like member and a foam roller. Among these, a foam roller is preferable.

-Foam roller-
The foam roller has at least a core material and a foam layer formed on the outer periphery of the core material and having a plurality of bubbles, and further includes other members as necessary.

--- Core material--
There is no restriction | limiting in particular as a material of the said core material, a shape, a magnitude | size, and a structure, According to the objective, it can select suitably.
Examples of the material of the core material include resins such as epoxy resins and phenol resins; metals such as iron, aluminum, and stainless steel.
Examples of the shape of the core material include a columnar shape and a cylindrical shape.
Moreover, you may provide an contact bonding layer on the core metal surface.

-Foam layer-
The foam layer is a layer formed on the outer periphery of the core material, and has a plurality of bubbles (sometimes referred to as “cell”, “hole”, “void”, etc.).
There is no restriction | limiting in particular as a shape of the said foam layer, According to the objective, it can select suitably, For example, cylindrical shape etc. are mentioned.
There is no restriction | limiting in particular as a material of the said foam layer, According to the objective, it can select suitably, For example, foaming polyurethane etc. are mentioned.

  As the image carrier protecting agent supply member, a conventional brush-like member as described in JP 2010-39304 A can be used. However, the foam roller includes a brush-like member and In comparison, since the image carrier protecting agent can be uniformly supplied onto the image carrier, the protection of the image carrier can be improved. Further, it is possible to solve the problem that the shaving amount of the image carrier protecting agent changes due to the sag of the brush over time when a brush-like member is used.

  There is no restriction | limiting in particular as said foaming polyurethane, According to the objective, a well-known manufacturing method can be selected suitably. Examples of the raw material for the foamed polyurethane include polyols, polyisocyanates, catalysts, foaming agents, foam stabilizers, and the like.

--- Polyol ---
There is no restriction | limiting in particular as said polyol, According to the objective, it can select suitably from conventionally well-known various polyols, For example, polyether polyol, polyester polyol, etc. are mentioned. Among these, polyether polyol is preferable from the viewpoint of easy adjustment of processability and foam layer hardness.

As the polyether polyol, for example, at least one of a low molecular polyol and a low molecular polyamine having 2 to 8 active hydrogen groups is used as an initiator, and at least one of ethylene oxide and propylene oxide is opened. Examples include polyether polyols obtained by cycloaddition polymerization.
Examples of the polyether polyol include polyether polyether polyols, polyester polyether polyols, and polymer polyether polyols that are generally used in the production of flexible polyurethane foams.
The polyether polyol is preferably a polyether polyether polyol in which ethylene oxide is bonded to the terminal at 5 mol% or more from the viewpoint of moldability.

Examples of the polyester polyol include dibasic acids such as adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and maleic anhydride, and anhydrides thereof, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Examples thereof include polyester polyols obtained by polymerizing glycols and triols such as propylene glycol, 1,4-butanediol, glycerin and trimethylolpropane.
Further, as the polyester polyol, those obtained by depolymerizing a waste material of polyethylene terephthalate resin with the above-mentioned glycol can also be used.
The said polyol may be used individually by 1 type, and may use 2 or more types together.

--- Polyisocyanate ---
There is no restriction | limiting in particular as said polyisocyanate, According to the objective, it can select suitably from conventionally well-known various polyisocyanate, For example, 2, 4- tolylene diisocyanate (2, 4-TDI), 2 , 6-tolylene diisocyanate (2,6-TDI), tolidine diisocyanate (TODI), naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI), 4,4'-diphenylmethane diisocyanate (MDI), carbodiimide-modified MDI, poly Examples include methylene polyphenyl polyisocyanate and polymeric polyisocyanate. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as content of the said polyisocyanate, Although it can select suitably according to the objective, As an equivalent ratio (NCO / OH) of the isocyanate group of the said polyisocyanate with respect to the hydroxyl group of the said polyol, it is 1.0. Above 3.0 is preferable.

---- Catalyst ---
There is no restriction | limiting in particular as said catalyst, According to the objective, it can select suitably from the catalysts used for a conventionally well-known urethanation reaction, For example, an amine catalyst, an organometallic catalyst, etc. are mentioned. .
Examples of the amine catalyst include triethylenediamine, dimethylethanolamine, and bis (dimethylamino) ethyl ether.
Examples of the organometallic catalyst include dioctyltin and distearyltin dibutyrate.
The catalyst may be a reactive catalyst such as dimethylaminoethanol having active hydrogen.
These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as content of the said catalyst, Although it can select suitably according to the objective, 0.01 mass part or more and 20 mass parts or less are preferable with respect to 100 mass parts of said polyols.
By appropriately selecting the type of the catalyst and controlling the amount of the catalyst used, it is possible to adjust the cell wall width, open cell diameter, hardness, air flow rate, and the like of the foam layer.

---- Foaming agent ---
There is no restriction | limiting in particular as said foaming agent, According to the objective, it can select suitably, For example, water, a fluorocarbon compound, a low boiling point hydrocarbon type compound etc. are mentioned. These may be used alone or in combination of two or more. Among these, water is preferable from the viewpoint of the environment.
Examples of the fluorocarbon compounds include HCFC-141b, HFC-134a, HFC-245fa, HFC-365mfc, and the like.
Examples of the low-boiling hydrocarbon compound include cyclopentane, n-pentane, iso-pentane, and n-butane.

There is no restriction | limiting in particular as content of the said foaming agent, Although it can select suitably according to the objective, 5 to 50 mass parts is preferable with respect to 100 mass parts of said polyols.
By appropriately selecting the type of the foaming agent and controlling the amount of the foaming agent used, the cell wall width, the open cell diameter, the hardness, the air flow rate, and the like of the foam layer can be adjusted.

---- Foam stabilizer ---
There is no restriction | limiting in particular as said foam stabilizer, According to the objective, it can select suitably, For example, silicone type surfactant etc. are mentioned.
As the silicone-based surfactant, a commercially available product can be used. Examples of the commercially-available product include a dimethylsiloxane foam stabilizer (for example, “SRX-253” manufactured by Toray Dow Corning Silicone, Shin-Etsu Chemical Co., Ltd.). "F-122" manufactured by Kogyo Co., Ltd.), polyether-modified dimethylsiloxane foam stabilizers (for example, "L-5309", "SZ-1311" manufactured by Nippon Unicar Co., Ltd.) and the like. These may be used alone or in combination of two or more.
There is no restriction | limiting in particular as content of the said foam stabilizer, Although it can select suitably according to the objective, 0.2 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of said polyols.

--- Other ingredients ---
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a crosslinking agent, a foam breaker, an electrically conductive agent, an antistatic agent, a flame retardant, a viscosity reducing agent, a pigment, a stabilizer , Coloring agents, anti-aging agents, ultraviolet absorbers, antioxidants and the like. These may be used alone or in combination of two or more.

The crosslinker and the foam breaker are contained for the purpose of controlling the closed cell property and open cell property of the foam layer.
There is no restriction | limiting in particular as said crosslinking agent, Although it can select suitably according to the objective, Triethanolamine, diethanolamine, etc. are mentioned.
There is no restriction | limiting in particular as said foam breaker, According to the objective, it can select suitably, For example, the thing with high foam breakability is mentioned in the said foam stabilizer.
There is no restriction | limiting in particular as content of the said crosslinking agent and the said foam breaker, According to the objective, it can select suitably.

  Usually, components other than the polyisocyanate are mixed in advance and mixed with the polyisocyanate component immediately before molding.

  A commercially available product can be used as the polyurethane foam. Examples of the commercially available products include HR20, HR30, QM60, QZK50, and QZK70 (all manufactured by Bridgestone Chemicals Co., Ltd.).

  There is no restriction | limiting in particular as a structure of the said foam layer, According to the objective, it can select suitably, For example, a closed cell type, an open cell type, these mixed types etc. are mentioned.

  FIG. 1A is a schematic cross-section showing an example of the open-cell foam layer. The open cell foam layer is a foam layer in which adjacent bubbles are connected to each other. Therefore, the foam layer has a structure that allows air and water to pass through. FIG. 1B is a schematic cross section showing an example of the closed cell foam layer. The closed cell foam layer is a foam layer having a structure in which bubbles are independent and air and water are not allowed to pass through.

  The foam layer is preferably an open-cell type because it has a small compressive residual strain and is easy to return to its original shape even when compressed, so that it hardly deforms even during long-term use. In addition, the open cell type is less costly than the closed cell type, and it is advantageous in terms of cost, and the amount of protective agent supplied (protective agent block shaving amount) is uniform. Since the image carrier can be sufficiently protected, filming of the image carrier can be prevented, a smaller protective agent block can be obtained, and the apparatus can be downsized.

The average cell diameter of the foam roller is not particularly limited as long as it is equal to or smaller than the number-based median diameter (D ₅₀ ) of the image carrier protective agent, and the grinding performance for the image carrier protective agent and the image carrier protective agent are as follows. 400 μm or more and 850 μm or less are preferable, and 500 μm or more and 700 μm or less are more preferable from the viewpoint of supplying uniformly to the image carrier surface. When the average cell diameter is 400 μm or more, it becomes easy to grind the image carrier protective agent, and when the molded body on the block is used as the image carrier protective agent, the supply amount of the image carrier protective agent is stable. Prone. On the other hand, when the average cell diameter is 850 μm or less, the contact area between the image carrier protecting agent and the image carrier is partially increased, so that it is easy to uniformly supply the image carrier protecting agent. .

The average cell diameter of the foam roller can be obtained, for example, from a value obtained by dividing 1 inch (= 25.4 mm) by the number of cells measured by the following method.
In the surface of the foam layer 80 of the foam roller 72, three measurement points are arbitrarily selected between the axial end portions and the central portion (here, in FIG. 2A, 70 is the end measurement portion and 71 is the center). Part of measurement.). Next, two more points are selected in the circumferential direction at each measurement point, and a total of nine measurement points are determined. Next, the photograph screen of each measurement location is observed using a microscope. Then, as shown in FIG. 2B, a line X having a length corresponding to the actual size d (1 inch) is drawn at the center of the photo screen, and the number of cells in the line is counted. Find the average value. A cell that touches even a d (1 inch) line is counted as one. For example, in the case shown in FIG. 2B, since the number of cells is 12, the average cell diameter is 25.4 (mm) ÷ 12 (cells) = 2.117 (mm) = 2,117 (μm). .

There is no restriction | limiting in particular as average thickness of the said foam layer, Although it can select suitably according to the objective, 1 mm or more and 4 mm or less are preferable. If the average thickness is 1 mm or more, it is difficult to pick up the influence of the shaft (core material), and if it is 4 mm or less, it is possible to prevent the image carrier protecting agent from being scraped off.
When the foam layer is cylindrical, the thickness is defined as the distance between the cylindrical inner peripheral surface and the outer peripheral surface. Here, the average thickness is an average value when the thickness of the foam layer is arbitrarily measured at three points.

There is no restriction | limiting in particular as hardness of the said foam layer, Although it can select suitably according to the objective, 40N or more and 430N or less are preferable, and 40N or more and 300N or less are more preferable. When the hardness is 40N or more, the image carrier can be prevented from being contaminated. When the hardness is 430N or less, the image carrier can be prevented from being contaminated. When the hardness is in the more preferable range, it is advantageous in that the suppression of contamination of the image carrier is more excellent.
The hardness is an average value of values measured based on JIS K 6400 at arbitrary three points on the surface of the foam layer.

  In the foam layer, the form of the bubbles (open-cell type or closed-cell type), the number of the bubbles, the hardness of the foam layer, and the like are the types of the polyurethane foam raw material when producing the foam layer, It can be controlled by appropriately adjusting the amount of the foaming agent, reaction conditions, and the like.

[Method for Manufacturing Image Carrier Protecting Agent Supply Member]
There is no restriction | limiting in particular as a manufacturing method of the said image carrier protection agent supply member, According to the objective, it can select suitably.
As an example of the manufacturing method of the image carrier protecting agent supply member, a manufacturing example in the case where the foamed polyurethane is used as the material of the foam layer will be described.
First, a foamed polyurethane raw material is foam-cured by a known method to form a block-shaped foamed polyurethane. Then, after cutting into a required shape, polishing the surface, processing into a cylindrical shape having bubbles opened on the surface, the core material is inserted into the cylindrical shape. Thereafter, a polishing blade or the like is applied while rotating the polyurethane foam using a polishing machine and a cutting machine, and the blade is moved parallel to the axial direction of the image carrier protecting agent supply member to cut to a predetermined thickness (traverse grinding). ). Thereby, a cylindrical image carrier protecting agent supply member having bubbles opened on the surface is obtained. Further, irregular irregularities can be formed on the surface of the foam layer by changing the rotation speed or the moving speed of the image carrier protecting agent supply member.
An adhesive may be applied to the core material in order to improve the adhesiveness with the foam layer. Through these steps, the image carrier protecting agent supply member is manufactured.

Another example of the method for manufacturing the image carrier protecting agent supply member will also be described.
A foamed polyurethane raw material is injected into a molding die for molding the image carrier protecting agent supply member containing the core material, and foamed and cured. Thereby, the image carrier protecting agent supply member is manufactured.

Among these production methods, the method using a mold is preferable because the formation of the foam layer and the surface thereof can be simultaneously opened, and the processing accuracy is good.
The manufacturing method using the mold does not require complicated processing, and the foam layer having a suitable opening property can be formed. Therefore, the inner surface of the mold is separated by a fluororesin coating agent, a release agent, or the like. It is preferable to provide a mold layer.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a protective layer forming step, and other steps appropriately selected as necessary, for example, a fixing step, Includes cleaning process, static elimination process, recycling process, control process, etc.
The image forming apparatus according to the present invention includes at least an image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a protective layer forming unit, and other components appropriately selected as necessary. For example, a cleaning means, a fixing means, a charge eliminating means, a recycling means, a control means and the like.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the protective layer forming step can be performed by the protective layer forming unit, and the other steps can be performed by the other unit. it can.

<Image carrier>
There is no restriction | limiting in particular as said image carrier, According to the objective, it can select suitably, For example, the image carrier etc. which were described in Paragraph [0049]-[0084] of Unexamined-Japanese-Patent No. 2014-142538 etc. Can be mentioned.

<Electrostatic latent image forming step and electrostatic latent image forming means>
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the image carrier, and can be performed by an electrostatic latent image forming unit.

  Next, the formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the image carrier and then exposing the image like the image, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming unit includes, for example, at least a charger that uniformly charges the surface of the image carrier and an exposure unit that exposes the surface of the image carrier imagewise.

The charging can be performed, for example, by applying a voltage to the surface of the image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons, corotrons and scorotrons.
The charger preferably has voltage applying means for applying a voltage having an AC component.

The exposure can be performed, for example, by exposing the surface of the image carrier imagewise using the exposure device.
The exposure device is not particularly limited as long as it can be exposed like an image to be formed on the surface of the image carrier charged by the charger, and can be appropriately selected according to the purpose. Examples thereof include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.

<Development process and development means>
The developing step is a step of developing the electrostatic latent image using a toner or a developer to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer, and can be appropriately selected from known ones. For example, the toner or developer is accommodated, A preferable example is one having at least a developing unit capable of applying the toner or the developer to the electrostatic latent image in a contact or non-contact manner.

<< Toner >>
There is no restriction | limiting in particular as said toner, According to the objective, it can select suitably, For example, the toner etc. of Paragraph [0089]-[0179] of Unexamined-Japanese-Patent No. 2014-142538 are mentioned.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multicolor developing unit. For example, a toner having a stirrer that charges the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

In the developing unit, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted to the image carrier. Move to the surface. As a result, the electrostatic latent image is developed with the toner to form a visible image with the toner on the surface of the image carrier.
The developer accommodated in the developing device is a developer containing the toner, but the developer may be a one-component developer or a two-component developer.

<Transfer process and transfer means>
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the image carrier with the visible image using a transfer charger, and can be performed by the transfer unit. The transfer unit includes a primary transfer unit that transfers a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer unit that transfers the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

  The image carrier is used to perform image transfer by a so-called intermediate transfer method in which a toner image formed on the image carrier is primarily transferred to perform color superposition and then transferred to a recording medium. It may be a body.

<< Intermediate transfer body >>
There is no restriction | limiting in particular as said intermediate transfer body, According to the objective, it can select suitably, For example, the intermediate transfer body as described in Paragraph [0184]-[0185] of Unexamined-Japanese-Patent No. 2014-142538 etc. are mentioned. It is done.

The transfer unit (the primary transfer unit and the secondary transfer unit) preferably includes at least a transfer unit that peels and charges the visible image formed on the image carrier to the recording medium side. . There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

<Protective layer forming step and protective layer forming means>
The protective layer forming step is a step of forming a protective layer by applying the image carrier protecting agent of the present invention to the surface of the image carrier after transferring a visible image.
The protective layer forming means is a means for forming the protective layer by applying the image carrier protective agent of the present invention to the surface of the image carrier after transferring the visible image.

<Other processes and other means>
Examples of the other processes include a fixing process, a cleaning process, a static elimination process, a recycling process, and a control process.
Examples of the other means include a fixing means, a cleaning means, a static elimination means, a recycling means, and a control means.

<< Fixing process and fixing means >>
The fixing step is a step of fixing the visible image transferred to the recording medium using the fixing unit, and may be performed each time the toner of each color is transferred to the recording medium, or the toner of each color. On the other hand, it may be carried out at the same time in a state where these are laminated.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose, but a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller, and an endless belt.
There is no restriction | limiting in particular in the heating in the said heating-pressing means, Although it can select suitably according to the objective, 80 to 200 degreeC is preferable.
In the present invention, for example, a known optical fixing device may be used together with or instead of the fixing step and the fixing unit depending on the purpose.

<< Cleaning process and cleaning means >>
The cleaning step is a step of removing the toner remaining on the image carrier and can be suitably performed by a cleaning unit.
The cleaning unit is preferably provided downstream of the transfer unit and upstream of the protective layer forming unit.
The cleaning means is not particularly limited as long as the toner remaining on the image carrier can be removed, and can be selected as appropriate. For example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade Examples include cleaners, brush cleaners, and web cleaners.

<< Static elimination process and static elimination means >>
The neutralization step is a step of performing neutralization by applying a neutralization bias to the image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the image carrier. It is done.

<< Recycling process and recycling means >>
The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, According to the objective, it can select suitably, For example, a well-known conveyance means etc. are mentioned.

<< Control process and control means >>
The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

Here, FIG. 4 is a cross-sectional view showing an example of the image forming apparatus 100 having the protective layer forming apparatus of the present invention.
Around the drum-shaped image carriers 1Y, 1M, 1C, and 1K, a protective layer forming device 2, a charging unit 3, an exposure unit 8, a developing unit 5, a transfer unit 6, and a cleaning unit 4 are arranged, respectively. Image formation is performed by operation. Y represents yellow, M represents magenta, C represents cyan, and K represents black.

Next, a series of processes for image formation will be described using a negative-positive process.
An image carrier represented by an organic photoconductor (OPC) having an organic photoconductive layer is neutralized by a neutralizing lamp (not shown) or the like, and is uniformly negatively charged by the charging means 3.
When the image carrier is charged by the charging unit 3, the image carrier 1Y, 1M, 1C, 1K is suitable for charging the image carrier 1Y, 1M, 1C, 1K to a desired potential from a voltage application mechanism (not shown). A voltage having an appropriate magnitude or a charging voltage obtained by superimposing an AC voltage thereon is applied.
In the charged image carriers 1Y, 1M, 1C, and 1K, a latent image is formed by laser light irradiated by the exposure means 8 such as a laser optical system (the absolute value of the exposed portion potential is the absolute value of the non-exposed portion potential). Lower potential).
Laser light is emitted from a semiconductor laser, and the surfaces of the image carriers 1Y, 1M, 1C, and 1K are scanned in the direction of the rotation axis of the image carrier by a polygonal polygonal mirror (polygon) that rotates at high speed.
The latent image formed in this way is developed with the toner supplied on the developing sleeve, which is a developer carrying member in the developing means 5, or with the developer composed of toner and carrier, and a toner image is formed. The
At the time of developing the electrostatic latent image, a voltage of an appropriate magnitude is present between the exposed portion and the non-exposed portion of the image carrier 1Y, 1M, 1C, 1K from the voltage application mechanism (not shown) to the developing sleeve. Alternatively, a developing bias in which an AC voltage is superimposed on this is applied.

The toner images formed on the image carriers 1Y, 1M, 1C, and 1K corresponding to the respective colors are transferred onto the intermediate transfer body 60 by the transfer unit 6 and fed from the paper supply unit 200, such as paper. A toner image is transferred onto the recording medium.
At this time, it is preferable that a potential having a polarity opposite to the polarity of toner charging is applied to the transfer unit 6 as a transfer bias. Thereafter, the intermediate transfer member 60 is separated from the image carrier to obtain a transfer image.
In addition, the toner remaining on the image carrier is collected by the cleaning unit 4 in the toner collecting chamber in the cleaning unit 4.

  As the image forming apparatus, a plurality of the developing units are used, and a plurality of toner images of different colors sequentially produced by the plurality of developing units are sequentially transferred onto a recording medium, and then sent to a fixing unit, where Even after a plurality of toner images prepared in the same manner are sequentially transferred onto an intermediate transfer member, and then transferred to a recording medium such as paper, Similarly, a fixing means may be used.

The charging means 3 is preferably a charging means disposed in contact with or close to the surface of the image carrier. As the charging means, a discharge wire is used. As a result, the amount of ozone generated during charging can be greatly suppressed as compared with corona dischargers such as so-called corotrons and scorotrons.
In the charging means for charging in contact with or close to the surface of the image carrier, as described above, the discharge is performed in the region near the surface of the image carrier, so that the electrical stress on the image carrier tends to increase. It is. However, by using the protective layer forming apparatus using the image carrier protecting agent of the present invention, the image carrier can be maintained for a long time without deteriorating, so that stable image quality can be ensured.

<Process cartridge>
The process cartridge of the present invention comprises at least an image carrier and the protective layer forming means of the present invention, and further, charging means, exposure means, developing means, transfer means, cleaning means, charge eliminating means as necessary. And other means.
The process cartridge can be detachably mounted on various electrophotographic image forming apparatuses, and is preferably detachably mounted on the image forming apparatus of the present invention.

Here, FIG. 5 is a schematic view showing an example of the process cartridge of the present invention.
The process cartridge includes a protective layer forming device 2, an image carrier protective agent 21, an image carrier protective agent supply member 22, a pressing force applying member 23, which are disposed to face a photosensitive drum as the image carrier 1. The protective layer forming member 24 is configured.
Further, the image carrier 1 has a surface on which the image carrier protective agent or toner partially deteriorated after the transfer process remains, but the surface residue is cleaned and cleaned by the cleaning unit 4.
In FIG. 5, the cleaning unit 4 is provided upstream of the image carrier protecting agent supply unit, and includes a cleaning member 41 and a cleaning pressing mechanism 42, and is brought into contact with an angle similar to a so-called counter type (leading type). ing.
The image carrier protective agent 21 is supplied from the image carrier protective agent supply member 22 to the surface of the image carrier 1 from which the residual toner and the deteriorated image carrier protective agent on the surface have been removed by the cleaning unit 4. A film-like protective layer is formed by the layer forming member 24. At this time, the image carrier protecting agent 21 of the present invention has a better adsorptivity to the portion of the surface of the image carrier that is highly hydrophilic due to electrical stress. Even if a stress is applied and the surface of the image carrier starts to deteriorate partially, the image carrier itself can be prevented from progressing by adsorption of the protective agent.
The image carrier 1 on which the film-like protective layer is formed in this way is charged by the charging means 3, and then an electrostatic latent image is formed by exposure L such as a laser, and developed by the developing means 5 to be a visible image. And transferred to the recording medium 7 by the transfer means 6 outside the process cartridge.

  According to the image forming apparatus and the process cartridge of the present invention, it is possible to prevent wear and filming of the image carrier, contamination of the charging unit, and toner slippage in the cleaning process, so that an extremely high quality image can be obtained over a long period of time. It can be formed stably.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

The number average primary particle size of the inorganic lubricant used in the following examples and comparative examples was measured as follows.
[Number average primary particle size of inorganic lubricant]
The number average primary particle size of the inorganic lubricant was determined by using an observation image with a scanning electron microscope (SEM) (thermal F-SEM, manufactured by Zeiss, ULTRA55), image analysis / measurement software (Image-pro plus 4.0j). , Manufactured by Media Cybernetics), and the average of the 10 was obtained.

Example 1
-Production of image carrier protective agent-
80 parts by mass of zinc stearate as a fatty acid metal salt (manufactured by Wako Pure Chemical Industries, Ltd.), boron nitride B as an inorganic lubricant (trade name: FS-1, manufactured by Mizushima Alloy Iron Co., Ltd., number average primary particle size: 0.2 μm) 10 parts by mass and boron nitride G (trade name: HP-P1, Mizushima Alloy Iron Co., Ltd., number average primary particle size: 2.0 μm) Compressed and molded at a pressure of 130 kN and a compression time of 10 seconds. After cooling, the solid is removed from the mold, cut into a size of 10 mm × 21 mm × 300 mm, and attached to a metal support with double-sided tape. Then, an image carrier protecting agent was prepared.

<Image formation>
An image carrier protecting agent was applied to an image carrier as an image carrier using an apparatus obtained by modifying the image forming apparatus (image MPC4500, manufactured by Ricoh Co., Ltd.) shown in FIG. 4 as follows. That is, in the image forming unit of the image forming apparatus (image MP C4500, manufactured by Ricoh Co., Ltd.), an image carrier used in the image forming apparatus as an image carrier (product equipped with imgio MP C4500), a cleaning blade ( Bando Chemical Co., Ltd.) and an image carrier protecting agent coating blade (Bando Chemical Co., Ltd.) were used. The image carrier protecting agent used in the image forming apparatus was replaced with the produced image carrier protecting agent of Example 1. A urethane roller was used as an image carrier protecting agent supply member used in the image forming apparatus. The urethane roller has a metal core having an outer diameter of 6 mm and a length of 365 mm, on which an open-cell foam layer made of polyurethane is formed so that the outer diameter is 12 mm (Co., Ltd.) (Manufactured by Bridgestone), the number of cells is 60, and the cell diameter of the open cell is 420 μm. In addition, a toner used in the image forming apparatus (a product equipped with imagio MP C4500) was used as the toner.

(Examples 2-18 and Comparative Examples 1-4)
Example 2 is the same as Example 1 except that the type, content, and protective agent molding method of the fatty acid metal salt and the inorganic lubricant are changed as shown in Tables 1 to 5 below. To 18 and Comparative Examples 1 to 4 were prepared.
Using the produced image carrier protecting agents of Examples 2 to 17 and Comparative Examples 1 to 4, the image forming apparatuses in Examples 2 to 17 and Comparative Examples 1 to 4 are the same as in the image forming apparatus in Example 1. did.
Example 18 is the same as the image forming apparatus in Example 1 except that the urethane roller of the image forming apparatus in Example 1 is changed to a brush roller (trade name: SA-7 (acrylic), manufactured by Toray Industries, Inc.). Similarly, an image forming apparatus in Example 18 was obtained.
The compositions are shown in Tables 1 to 5 below.

(Examples 19 and 20)
-Production of image carrier protective agent-
80 parts by mass of zinc stearate as a fatty acid metal salt (manufactured by Wako Pure Chemical Industries, Ltd.), boron nitride B as an inorganic lubricant (trade name: FS-1, manufactured by Mizushima Alloy Iron Co., Ltd., number average primary particle size: A mixture of 10 parts by mass of 0.2 μm) and 10 parts by mass of boron nitride H (trade name: HGP, manufactured by Denka Co., Ltd., number average primary particle size: 5.0 μm) is heated and melted and injected into a mold. After cooling and solidifying, the solid material was removed from the mold, cut into a size of 10 mm × 21 mm × 300 mm, and attached to a metal support with double-sided tape to produce an image carrier protective agent. .
The image forming apparatus in Example 19 was made in the same manner as the image forming apparatus in Example 1 using the produced image carrier protecting agent of Example 19.
As for Example 20, the image formation in Example 19 was performed except that the urethane roller of the image forming apparatus in Example 19 was changed to a brush roller (trade name: SA-7 (acrylic), manufactured by Toray Industries, Inc.). The image forming apparatus in Example 20 was made in the same manner as the apparatus.
The composition is shown in Table 4.

  Next, using the image forming apparatus, the prevention of contamination of the charging unit, the protection of the image carrier, the cleaning property, and the anti-blade noise were evaluated as follows. The results are shown in Tables 1 to 5 below.

<Preventing contamination of charging means>
Using a test chart (A4 size) with an image area ratio of 5%, output 100,000 sheets of images in either a normal temperature environment (23 ° C, 50% RH) or a low temperature environment (10 ° C, 15% RH). The charging means (charging roller) was visually observed, and the prevention of contamination of the charging means was evaluated based on the following evaluation criteria.
〔Evaluation criteria〕
A: The charging unit is hardly soiled, and an abnormal image (an image that appears as a black streak on the image) does not occur over time (about 20,000 sheets). O: The charging unit is slightly soiled, but the room temperature environment (23 ° C., 50% RH), the image is not affected, and an abnormal image (an image that appears as a black streak on the image) does not occur over time (about 20,000 sheets). , 15% RH), abnormal images (images appearing as black streaks on the image) are generated over time (about 20,000 sheets). X: The charging means is very dirty and low temperature environment (10 ° C., 15% RH) ), Abnormal images (images that appear as black streaks on the image) are generated from an early stage (approximately 5,000 images).

<Protection of image carrier>
Using a test chart (A4 size) with an image area ratio of 5%, output 100,000 sheets of images in a normal temperature environment (23 ° C., 50% RH), visually observe the image carrier, and based on the following evaluation criteria The protective properties of the image carrier were evaluated.
〔Evaluation criteria〕
A: There is almost no wear and filming on the image carrier, and abnormal images (images appearing as white stripes on the image) do not occur over time (about 20,000 sheets). O: Slight filming on the image carrier However, abnormal images (images appearing as white streaks on the image) do not occur over time (about 20,000 sheets). Δ: Filming on the image carrier and over time (about 20,000 sheets) An abnormal image (image that appears as white streaks on the image) is generated ×: The image carrier has filming, and an abnormal image (image that appears as white streaks on the image) at an early stage (approximately 5,000 sheets) ) Occurs

<Cleanability>
After running 500 sheets (passing paper), it is replaced with a new image carrier, and a linear sponge tape (Scotch tape 4016, with an average thickness of 2 mm) is formed downstream of the cleaning blade and at the upper end of the opening of the developing means. “Through-through toner catcher” (average thickness: 1 mm, felt of 8 mm × 310 mm, manufactured by Ashiya Co., Ltd.) was used. After 100 runs (passing) using a chart with an image area ratio of 5%, the toner slipped downstream of the cleaning blade during the run (passing) of 20 sheets with an image area ratio of 5% is passed through the “slip-through”. Collected with "toner catcher". The collected toner was converted into digital data by an image scanner, and the black streaks on the image were visually observed to confirm the presence or absence of toner slip, and the cleaning property was evaluated based on the following evaluation criteria.
〔Evaluation criteria〕
A: There is almost no toner passing through, and no abnormal image (image that appears as black streaks on the image) occurs. ○: Although there is toner passing through, an abnormal image (image that appears as black streaks on the image) does not occur. Δ: Toner slippage may occur and an abnormal image (image that appears as black streaks on the image) may occur. ×: Toner slippage occurs frequently and an abnormal image (image that appears as black streaks on the image) ) Occurs frequently

<Blade resistance>
Using a test chart (A4 size) with an image area ratio of 5%, under a high temperature environment (32 ° C., 54% RH), the photosensitive member linear velocity is 10,000 sheets at full speed (normal printing speed), and The output of 10,000 sheets was performed at a photosensitive linear speed of half speed (thick paper mode), and “blade squeal resistance” was evaluated based on the following evaluation criteria.
〔Evaluation criteria〕
A: No abnormal noise is generated. ○: At half speed, a slight abnormal noise is generated at a level that cannot be heard unless the ear is brought close to the 1,000 sheets once per half. Noise occurs at both full speed and half speed

  The details of the fatty acid metal salt and the inorganic lubricant in Tables 1 to 5 are as follows.

-Fatty acid metal salt-
-Zinc stearate: Wako Pure Chemical Industries, Ltd.-Calcium stearate: Wako Pure Chemical Industries, Ltd.-Zinc laurate: Wako Pure Chemical Industries, Ltd.

-Inorganic lubricant-
--First inorganic lubricant--
Boron nitride A: manufactured by Momentive Performance Materials Japan LLC, product name: HCV, number average primary particle size: 0.1 μm
Boron nitride B: manufactured by Mizushima Alloy Iron Co., Ltd., trade name: FS-1, number average primary particle size: 0.2 μm
Boron nitride C: manufactured by ESK Ceramics, trade name: S1-F, number average primary particle size: 0.5 μm
Boron nitride D: manufactured by ESK Ceramics, trade name: S03, number average primary particle size: 0.8 μm
・ Talc: manufactured by Nippon Talc Co., Ltd., trade name: D-800, number average primary particle size: 0.8 μm
-Mica: Topy Industries, Ltd., developed product, number average primary particle size: 0.8 μm
Boron nitride E: Made by Mizushima Alloy Iron Co., Ltd., developed product, number average primary particle size: 1.0 μm
-Other inorganic lubricants-
Boron nitride F: manufactured by ESK Ceramics, trade name: S06, number average primary particle size: 1.5 μm
--Second inorganic lubricant--
Boron nitride G: manufactured by Mizushima Alloy Iron Co., Ltd., trade name: HP-P1, number average primary particle size: 2.0 μm
Boron nitride H: manufactured by Denka Co., Ltd., trade name: HGP, number average primary particle size: 5.0 μm
・ Mica: Topy Industries, Ltd., developed product, number average primary particle size: 5.0 μm
Boron nitride I: manufactured by Mizushima Alloy Iron Co., Ltd., trade name: HP-4W, number average primary particle size: 8.0 μm
Boron nitride J: Mizushima Alloy Iron Co., Ltd., trade name: HP-2W, number average primary particle size: 12.0 μm
Boron nitride K: manufactured by ESK Ceramics, trade name: S-15, number average primary particle size: 15.0 μm

As an aspect of this invention, it is as follows, for example.
<1> Contains a fatty acid metal salt and an inorganic lubricant,
The inorganic lubricant includes a first inorganic lubricant having a number average primary particle size of 1.0 μm or less and a second inorganic lubricant having a number average primary particle size of 2.0 μm or more. It is a characteristic image carrier protecting agent.
<2> The <1>, wherein the inorganic lubricant is at least one selected from mica, boron nitride, molybdenum disulfide, tungsten disulfide, talc, kaolin, montmorillonite, calcium fluoride, and graphite. It is an image carrier protecting agent.
<3> The image carrier protecting agent according to any one of <1> to <2>, wherein the second inorganic lubricant is boron nitride.
<4> The image carrier protecting agent according to any one of <1> to <3>, wherein the fatty acid metal salt is at least one selected from zinc stearate, calcium stearate, and zinc laurate. .
<5> The image carrier protective agent according to any one of <1> to <4>, which is a compression molded product of a mixture including the fatty acid metal salt and the inorganic lubricant.
<6> The image carrier protecting agent according to any one of <1> to <5>, wherein the fatty acid metal salt is zinc stearate.
<7> The image carrier protecting agent according to <1> to <6>, wherein the inorganic lubricant is boron nitride.
<8> The image carrier protecting agent according to <1> to <7>, wherein the content of the fatty acid metal salt is 70% by mass or more and 98% by mass or less.
<9> The image carrier protective agent according to <1> to <8>, wherein the number average primary particle size of the first inorganic lubricant is 0.8 μm or less.
<10> The image carrier protective agent according to <1> to <9>, wherein the number average primary particle size of the first inorganic lubricant is 0.1 μm or more and 0.8 μm or less.
<11> The image carrier protective agent according to <1> to <10>, wherein the number average primary particle diameter of the first inorganic lubricant is 0.1 μm or more and 0.5 μm or less.
<12> The image carrier protective agent according to <1> to <11>, wherein the number average primary particle size of the second inorganic lubricant is 2.0 μm or more and 15.0 μm or less.
<13> The image carrier protective agent according to <1> to <12>, wherein the number average primary particle size of the second inorganic lubricant is 2.0 μm or more and 12.0 μm or less.
<14> The image carrier protective agent according to <1> to <13>, wherein the number average primary particle size of the second inorganic lubricant is 2.0 μm or more and 8.0 μm or less.
<15> The image carrier protecting agent according to any one of <1> to <14>,
And an image carrier protecting agent supply member that supplies the image carrier protecting agent to the surface of the image carrier.
<16> The protective layer forming apparatus according to <15>, wherein the image carrier protective agent supply member has a foam layer.
<17> The protective layer forming apparatus according to <16>, wherein the foam layer is an open-cell type.
<18> Any one of <15> to <17>, further comprising a protective layer forming member that presses the image carrier protective agent supplied to the image carrier and forms a protective layer on the surface of the image carrier. A protective layer forming apparatus according to claim 1.
<19> an electrostatic latent image forming step of forming an electrostatic latent image on the image carrier;
A developing step of developing the electrostatic latent image with toner to form a visible image;
A transfer step of transferring the visible image to a recording medium;
A protective layer forming step of forming a protective layer by applying the image carrier protective agent according to any one of <1> to <14> to the surface of the image carrier after transferring the visible image. This is an image forming method.
<20> an image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the image carrier;
Developing means for developing the electrostatic latent image with toner to form a visible image;
Transfer means for transferring the visible image onto a recording medium;
Protective layer forming means for forming a protective layer by applying the image carrier protective agent according to any one of <1> to <14> to the surface of the image carrier after transferring the visible image; An image forming apparatus including the image forming apparatus.
<21> The image forming apparatus according to <20>, further including a cleaning unit that removes toner remaining on the surface of the image carrier on the downstream side of the transfer unit and the upstream side of the protective layer forming unit. .
<22> an image carrier;
And a protective layer forming means for forming a protective layer by applying the image carrier protective agent according to any one of <1> to <14> on a surface of the image carrier. It is.

  The image carrier protective agent according to any one of <1> to <14>, the protective layer forming apparatus according to <15> to <18>, the image forming method according to <19>, and <20 > To <21> and the process cartridge according to <22> can solve the conventional problems and achieve the object of the invention.

JP 2009-300861 A JP 2010-39304 A JP 2012-58539 A

DESCRIPTION OF SYMBOLS 1 Image carrier 2 Protection layer formation apparatus 4 Cleaning means 5 Development means 6 Transfer means 7 Recording medium 21 Image carrier protection agent 22 Image carrier protection agent supply member 24 Protection layer formation member

Claims (13)

Containing a fatty acid metal salt and an inorganic lubricant,
The inorganic lubricant includes a first inorganic lubricant having a number average primary particle size of 1.0 μm or less and a second inorganic lubricant having a number average primary particle size of 2.0 μm or more. An image carrier protective agent characterized.   2. The image carrier protection according to claim 1, wherein the inorganic lubricant is at least one selected from mica, boron nitride, molybdenum disulfide, tungsten disulfide, talc, kaolin, montmorillonite, calcium fluoride, and graphite. Agent.   The image carrier protecting agent according to claim 1, wherein the second inorganic lubricant is boron nitride.   The image carrier protecting agent according to any one of claims 1 to 3, wherein the fatty acid metal salt is at least one selected from zinc stearate, calcium stearate, and zinc laurate.   The image carrier protecting agent according to any one of claims 1 to 4, which is a compression molded product of a mixture comprising the fatty acid metal salt and the inorganic lubricant. An image carrier protecting agent according to any one of claims 1 to 5,
An image carrier protecting agent supply member for supplying the image carrier protecting agent to the surface of the image carrier;   The protective layer forming apparatus according to claim 6, wherein the image carrier protective agent supply member has a foam layer.   The protective layer forming apparatus according to claim 7, wherein the foam layer is of an open cell type.   The protective layer according to claim 6, further comprising a protective layer forming member that presses the image carrier protective agent supplied to the image carrier and forms a protective layer on the surface of the image carrier. Forming equipment. An electrostatic latent image forming step of forming an electrostatic latent image on the image carrier;
A developing step of developing the electrostatic latent image with toner to form a visible image;
A transfer step of transferring the visible image to a recording medium;
A protective layer forming step of forming a protective layer by applying the image carrier protective agent according to any one of claims 1 to 5 to the surface of the image carrier after transferring the visible image. An image forming method. An image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the image carrier;
Developing means for developing the electrostatic latent image with toner to form a visible image;
Transfer means for transferring the visible image onto a recording medium;
Protective layer forming means for forming a protective layer by applying the image carrier protective agent according to any one of claims 1 to 5 to the surface of the image carrier after transferring the visible image. An image forming apparatus.   The image forming apparatus according to claim 11, further comprising a cleaning unit that removes toner remaining on the surface of the image carrier on the downstream side of the transfer unit and the upstream side of the protective layer forming unit. An image carrier;
6. A process cartridge comprising: a protective layer forming unit that forms a protective layer by applying the image carrier protective agent according to claim 1 to a surface of the image carrier.