JP2011102859A - Cleaning device, image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleaning device having stable electrical characteristics, and superior wear resistance, and providing a high-quality full-color image without abnormal images, such as clearing in mid section, density unevenness, and color unevenness. <P>SOLUTION: The cleaning device includes: an electrostatic cleaning member which is brought into contact with a photoreceptor surface and electrostatically removes toner on the photoreceptor surface by an applied voltage; a cleaning voltage application means for applying a voltage to the electrostatic cleaning member; and a toner polarity control blade which performs a control so that the electrostatic cleaning member comes into contact with the photoreceptor surface at a surface moving direction upstream side of a photoreceptor relative to a position, in contact with the photoreceptor and the charging polarity of the toner on the photoreceptor surface is opposite to the voltage applied to the electrostatic cleaning member by the cleaning voltage application means. The toner polarity control blade includes a two-layer structure; a face on a side abutting against the surface of the photoreceptor is a conductive layer with an electron conductive polymer added; and a face on a side which does not abut against the photoreceptor is an insulating layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a cleaning device, and an image forming method and an image forming apparatus including the same.

  Conventionally, in an electrophotographic image forming apparatus such as a copying machine, a printer, or a fax machine, an electrostatic latent image is formed on an image carrier and the electrostatic latent image is visualized as a toner image. After transfer to the recording medium, toner, paper powder, etc. that did not contribute to the transfer remained on the surface of the image carrier. For this reason, it is configured such that residual toner or the like adhering to the surface of the image carrier is removed by a cleaning device to prepare for the next image forming process.

  As such a cleaning device, a blade cleaning method, a conductive or insulating brush roller method is used. Among these, a blade cleaning method using a blade formed of urethane rubber is generally used. This blade cleaning system is a system in which the edge of the blade is brought into pressure contact with the surface of the image carrier to forcibly remove the toner remaining on the surface of the image carrier. The blade cleaning method is widely adopted because it has a simple structure and a high cleaning effect.

  On the other hand, in recent years, there has been a demand for a toner having a smaller particle size for higher image quality. As a toner manufacturing method for reducing the toner particle size, the polymerization method is effective from the viewpoint of manufacturing cost, not the conventional pulverization method. The small particle size toner produced by the polymerization method has a shape close to a sphere and a sharp particle size distribution, so that a good image with excellent fine line reproducibility and digital image dot reproducibility can be obtained. have. When such a small particle size polymerized toner is used, cleaning is performed because the toner shape is close to a true sphere and the particle size is smaller than that of a toner manufactured by a conventional pulverization method. However, there is a drawback that cleaning failure such as slip-through occurs. In particular, when the edge of the cleaning blade is worn or chipped due to repeated use, cleaning failure is likely to occur. Further, there has been a problem that due to the use, the photosensitive member is worn and fine irregularities are formed, and cleaning defects are likely to occur even when the surface roughness is increased.

  In order to solve such a problem, for example, using a conductive roll in which carbon black is dispersed in epichlorohydrin rubber as a conductive member, on the upstream side in the moving direction of the photosensitive member surface with respect to the position in contact with the member photosensitive member, A configuration is disclosed that includes a conductive member that is in contact with the photoreceptor and to which a voltage having a polarity opposite to that of the cleaning roller is applied (see Patent Document 1). However, the conductive roll has a narrow discharge area between the materials to be transferred, the discharge is concentrated locally, a hole is formed on the surface of the roller, the remaining toner enters the hole, and the toner melts and adheres. There was a problem that happened. Further, since the force acts in the direction in which the remaining toner is crushed because of the roll shape, the remaining toner is melted and fixed, and the portion where the fixing has occurred decreases the conductivity of the surface of the conductive roll, and serves as a conductive member. There was a problem that the function was lost.

  Moreover, the structure using the electroconductive fur brush which put the electroconductive substance in polyester, polyamide, and an acrylic resin fiber as said electroconductive member is disclosed (refer patent document 2). However, the fur brush fibers always have a problem of uneven density. For this reason, there is a problem in that it is difficult to uniformly contact the transfer material, the polarity of the remaining toner cannot be uniformly controlled, and a cleaning failure often occurs.

  A configuration using a toner polarity control blade in which carbon black or an ionic conductive material is dispersed in an elastic body such as urethane rubber is disclosed as the conductive member (see Patent Document 3). Compared to the conductive roll and conductive fur brush, the blade shape itself indicates a cleaning ability, and the discharge area with the transferred body is large. There were advantages such as stable charge injection from the polarity control blade to the remaining toner. As a result, the toner toward the position where the cleaning roller comes into contact with the photosensitive member is charged in the same polarity as the toner polarity control blade, and the toner polarity control blade is placed at the position where the cleaning roller comes into contact with the photosensitive member and the intermediate transfer belt. The transfer residual toner is attracted to the cleaning roller to which the reverse polarity voltage is applied and can be removed well. However, even with the electrostatic cleaning method using the toner polarity control blade, image formation When a large amount of toner is applied, the toner is fixed as in the case of the conductive roll. In addition, when carbon black is used as the conductive agent, sufficient conductivity can be ensured by adding a small amount of carbon black. However, since the resistance of the carbon black particles is low, discharge is concentrated in places where the dispersion of carbon black is insufficient. Cheap. In fact, in the urethane rubber that is the main component of the toner polarity control blade, the discharge concentrates at the location where the carbon black added as the conductive agent is agglomerated, and there are fine holes in the toner polarity control blade. It was caused by the phenomenon that the metal entered, melted and fixed. When the molten toner adheres to the toner polarity control blade, the discharge concentrates further on the location, the adhesion of the molten toner grows greatly, and the adhesion damages the material to be transferred, such as voids, uneven density, and uneven color. An abnormal image occurs. In addition, the uniformity of the hardness of the toner polarity control blade itself is remarkably lowered, and there is also a problem that a phenomenon of partial collapse occurs at the end.

  It was also considered to add an ionic conductive agent as a conductive agent. However, if a large amount of ionic conductive agent is added to ensure conductivity, the resilience of the urethane rubber tends to be lowered, and the toner polarity control blade and the transferred object are transferred. There was a problem that the coefficient of friction between the materials increased, scratched the material to be transferred, and abnormal images such as voids, density unevenness, and color unevenness occurred as in the case of the carbon black. Further, when the ionic conductive agent is continuously discharged, each ion is polarized, the conductivity is lowered, the polarity cannot be controlled, and there is a problem that the cleaning is poor.

  The toner polarity control blade is fixed to the support member. As the fixing method, an adhesive, a pressure-sensitive adhesive, mechanical caulking, or the like is used. However, since the bonding work is easy, bonding with an adhesive or a pressure-sensitive adhesive is particularly preferable. However, in the toner polarity control blade to which the ionic conductive agent is added, the ionic conductive agent in the toner polarity control blade bleeds due to voltage application and contact friction with the transfer material, and the adhesion to the support member deteriorates. As a result, the toner polarity control blade is detached from the support member.

  As described above, in the cleaning device, even when a large amount of image is formed, the toner polarity control blade is not perforated without causing a local discharge with the transfer material, and the molten toner is not fixed. The rebound resilience of the toner polarity control blade does not decrease, and further improvement is required in order to ensure adhesion between the toner polarity control blade and the support member.

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention provides a long-life cleaning device that provides a high-quality full-color image having stable electrical characteristics, excellent wear resistance, no abnormal images such as voids, density unevenness, and color unevenness, and the like. It is an object of the present invention to provide an image forming method and an image forming apparatus used.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have a toner polarity control blade having two or more layers in a cleaning device having a toner polarity control blade, and the surface of a photoreceptor as a transfer material. Electroconductive polymer is added to the layer on the side that contacts the surface, and the surface on the side that does not contact the surface of the material to be transferred is an insulating layer. The present inventors have found that there is no abnormal image such as unevenness and color unevenness and can provide a high-quality full-color image, and the present invention has been completed.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> An electrostatic cleaning member that comes into contact with the surface of a transferable transfer body and electrostatically removes toner on the surface of the transfer transfer body by an applied voltage, and the electrostatic cleaning member A cleaning voltage applying means for applying a voltage, and the electrostatic cleaning member is in contact with the surface of the transferred body upstream of the surface moving direction of the transferred body with respect to a position in contact with the transferred body, A toner polarity control blade for controlling the charging polarity of the toner on the surface of the transfer member so that the cleaning voltage applying means has a polarity opposite to the voltage applied to the electrostatic cleaning member. The toner polarity control blade has at least a two-layer structure, and the surface in contact with the surface of the transferred body is a conductive layer to which an electronic conductive polymer is added. The cleaning device is characterized in that the surface on the side not in contact with the surface is an insulating layer.
<2> The cleaning device according to <1>, wherein the average particle size of the electron conductive polymer particles is 0.1 μm to 4 μm.
<3> The cleaning device according to any one of <1> to <2>, wherein the electron conductive polymer is polyaniline.
<4> The cleaning device according to any one of <1> to <3>, wherein a metal soap containing zinc is applied to a surface of the transfer target.
<5> The cleaning device according to <4>, wherein the metal soap is a mixture of zinc stearate and zinc palmitate.
<6> An electrostatic latent image forming step for forming an electrostatic latent image on the surface of the image carrier, and the electrostatic latent image formed on the surface of the electrostatic latent image carrier is developed with a developer and visible A developing step for forming an image; a transferring step for transferring the visible image to a recording medium; and a cleaning step for removing transfer residual toner adhering to the surface using the image carrier after transfer as a cleaning target. An image forming method, wherein the cleaning step is performed using the cleaning device according to any one of <1> to <5>.
<7> An image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the surface of the image carrier, and a developer that develops the electrostatic latent image formed on the surface of the electrostatic latent image carrier Developing means for forming a visible image by developing, a transfer means for transferring the visible image to a recording medium, and a transfer residual toner adhering to the surface by using the image carrier after transfer as a body to be cleaned. An image forming apparatus comprising: a cleaning unit, wherein the cleaning unit according to any one of <1> to <5> is used as the cleaning unit.

  According to the present invention, the conventional problems can be solved, and the uniformity of the conductivity of the toner polarity control blade is improved, so that local discharge between the toner polarity control blade and the transfer material is eliminated, and the molten toner is fixed. Can be provided, and an image forming method and an image forming apparatus using the same can be provided, and a reduction in rebound resilience of the toner polarity control blade can also be prevented. In addition, according to the present invention, it is possible to ensure adhesion between the toner polarity control blade and the support.

FIG. 1 is an explanatory diagram showing a schematic configuration of the entire printer according to the present embodiment. FIG. 2 is an explanatory diagram showing a schematic configuration of the cleaning device. 3A is a charge distribution before passing through the blade contact portion, and FIG. 3B is a charge distribution after passing through the blade contact portion. FIG. 4 is a conceptual diagram of electrostatic cleaning. FIG. 5 is an explanatory diagram showing a schematic configuration around the toner polarity control blade.

(Cleaning device)
As shown in FIGS. 1 and 2, the cleaning device 7 of the present invention has a toner polarity control blade 75, an electrostatic cleaning member, and a cleaning voltage applying means, and further, if necessary, the toner polarity control blade 75. And other means such as a housing for storing the transfer residual toner removed by the above.

  FIG. 2 is an explanatory diagram showing a schematic configuration of the cleaning device 7. The cleaning device 7 includes a brush roller 71 as an electrostatic cleaning member in which countless brush fibers 71a and 71b are planted on the surface of a roller-shaped core member 71c that is a rotating shaft body. The cleaning device 7 includes a recovery roller 72 as a brush roller cleaning member that cleans the toner attached to the brush fibers, and a scraper member 73 as a peeling member that peels off the toner attached to the recovery roller 72. Further, the cleaning device 7 includes a toner polarity control blade 75 constituting a polarity control unit and a blade power source 706 as a blade voltage application unit. The toner polarity control blade 75 will be described later.

<Electrostatic cleaning member and cleaning voltage applying means>
The brush roller 71 of the electrostatic cleaning member is not shown so that the tip of the brush fiber moves in the direction opposite to the surface of the photosensitive member 1 while the tip of the brush fiber is in contact with the photosensitive member 1. It is rotated in the clockwise direction in the figure by the driving means. Then, the transfer residual toner is captured by a plurality of brush fibers that rub against the surface of the photoreceptor 1. The collection roller 72 is disposed so as to sandwich the brush roller 71 between itself and the photoreceptor 1, and moves on the surface in a direction opposite to the moving direction of the brush tip of the brush roller 71 at a contact portion with the brush roller 71. In this way, it is driven to rotate clockwise in the figure by a driving means (not shown). The plate-shaped scraper member 73 has its tip edge abutted against the surface of the collection roller 72 with a predetermined pressure. Further, the conveying means (not shown) is disposed below the scraper member 73 in the direction of gravity.

  A brush power source 701 as a cleaning voltage application unit is connected to the core member 71c which is a rotating shaft body of the brush roller 71, and a positive bias is applied thereto. Therefore, the transfer residual toner that is made negative in polarity by the toner polarity control blade 75 is electrostatically attracted to the brush roller 71 to which the positive polarity is applied. Thereby, the transfer residual toner is removed from the surface of the photoreceptor 1.

  Further, a recovery power source 702 is connected to the shaft portion of the recovery roller 72, and a positive polarity bias is applied. The negative toner electrostatically attracted to the brush roller 71 is collected by the collection roller 72 due to a potential gradient between the brush roller 71 and the collection roller 72. The toner collected on the collection roller 72 is mechanically scraped off from the surface of the collection roller 72 by the scraper member 73. The toner scraped off is transported to a waste toner bottle (not shown) by a transport means (not shown). Note that the toner may be transported to the developing device 6 for reuse.

  FIG. 4 is a conceptual diagram of electrostatic cleaning. In the transfer step, when a positive transfer voltage is applied to the negatively charged toner after development, all the toner on the photoreceptor 1 is originally transferred onto the transfer paper P or intermediate transfer belt. However, since an electric field is formed between the narrow gaps in the transfer portion, peeling discharge occurs, and the transfer residual toner T0 contains both positive and negative polarity toners.

  The charged polarity of the toner is leveled by the toner polarity control blade 75 so that the toner having the charged polarity mixed therein has either a positive or negative polarity. Next, the toner is attached to the brush roller 71 by an electrostatic force larger than the electrostatic force with which the toner is attached to the photoreceptor 1. This process is called primary cleaning. Next, the process of moving the transfer residual toner T2 attached to the brush roller 71 to the collection roller 72 is referred to as secondary cleaning. Finally, the process of removing the transfer residual toner T3 adhering to the recovery roller 72 is called tertiary cleaning, and the transfer residual toner on the photoreceptor 1 is recovered as waste toner.

It is essential that the brush fiber of the brush roller 71 is a conductive brush in which a conductive material is mixed in acrylic, PET, polyester, or the like. The structure of the conductive material at this time is not simply dispersed on the brush surface, but must be a core-sheath structure that is inserted inside and not exposed to the surface. If the conductive material is exposed on the surface, the electric charge is injected into the toner and the potential Vb on the brush surface cannot be maintained. The brush resistance is preferably 104 to 109 [Ω]. If the resistance is small, it is easy to inject charges into the toner. If the resistance is large, the electric field strength is small, and the electric field for attracting the toner is not applied unless a high voltage is applied. Cannot be secured. In order to increase the probability of contact with the toner, the flocking density is also an important factor, preferably 7 [10,000 / inch ² ] or more, and more preferably 10 [10,000 / inch ² ] or more. In order to increase the contact probability, a preferable contact state is obtained by rotating the photosensitive member 1 in the counter direction and setting the linear velocity ratio to 0.7 or more. Another important factor is brush fall. In general, brush fibers are said to be straight hair. However, if the hair is in a straight-haired state with a core-sheath structure, the tip of the brush fiber where the conductive material is exposed is in contact with the toner. For this reason, it is preferable that the brush fibers are tilted by brushing or brushing so that the brush fibers are not digged in by rotation of the photosensitive member 1 so that the toner does not directly contact the conductive material.

<Toner polarity control blade>
The toner polarity control blade 75 is rotationally driven and is preferably arranged in a counter manner so as to come into contact with a transfer material (photosensitive member 1) such as a drum shape or an endless belt shape that carries a toner image. After the toner image carried on the material is transferred to a transfer material such as a recording medium such as paper or an intermediate transfer medium such as an endless belt, the transfer residual toner remaining on the surface of the image carrier is removed.

  The toner polarity control blade 75 receives a bias application from the blade power source 706 to inject charges into the transfer residual toner on the surface of the photoreceptor 1, and has the same polarity as the bias polarity received from the blade power source 706. Align. Here, the normal charging polarity of the toner in the present embodiment is negative, but as a result of the action of a positive bias in the transfer nip, some of the toner is positively charged. Therefore, as shown in FIG. 3A, the charge distribution of the transfer residual toner is in a state where the negative polarity toner and the positive polarity toner are mixed. In the present invention, the polarity of the bias supplied from the blade power source 706 is preferably negative. Therefore, the transfer residual toner in a state where the negative polarity toner and the positive polarity toner are mixed is subjected to negative polarity charge injection by the toner polarity control blade 75, so that the polarity as shown in FIG. Uniformly negative polarity. In this embodiment, the case where the polarity of the untransferred toner is made to have a negative polarity by the toner polarity control blade 75 is taken as an example.

FIG. 5 is an explanatory diagram showing a schematic configuration around the toner polarity control blade 75. The toner polarity control blade 75 has a layer structure consisting of at least two layers, and the layer on the side in contact with the surface 11 of the transfer material (photoreceptor) is a conductive layer 75b in which an electronic conductive polymer is dispersed (added). The surface that does not come into contact with the photoreceptor surface 11 is an insulating layer 75a. Since the toner polarity control blade has a two-layer structure, adhesion to the support member is ensured, and the toner polarity control blade can be prevented from coming off.
The contact pressure of the toner polarity control blade 75 with respect to the surface of the photoreceptor 1 is adjusted by changing the elastic force of the spring 42 that is an elastic member connected via the support plate 41. The support plate 41 is rotatable about a fulcrum 40, a spring 42 is fixed to one end, and a toner polarity control blade 75 is fixed to the other end. The side of the spring 42 opposite to the side fixed to the support plate 41 is fixed to the moving element end 43. Then, by changing the position of the moving element end 43, the length of the spring 42 is changed, and the elastic force of the spring 42 is changed. As a result, the support plate 41 rotates about the fulcrum 40 to change the blade linear pressure, which is the contact pressure of the toner polarity control blade 75 with respect to the photoreceptor 1.

  The fixing of the toner polarity control blade 75 and the support plate 41 can be appropriately changed according to the purpose of use. For example, the conductive layer 75b and the support plate 41 are preferably bonded. Since conductivity must be ensured between the conductive layer 75b and the support plate 41, it is necessary to use a conductive tape, a conductive adhesive, or the like for bonding. Since conduction may be performed from the surface of the conductive layer 75b, the adhesive between the conductive layer 75b and the support plate 41 is an insulator, and the surface of the conductive layer 75b and the support plate 41 are electrically conductive tape, conductive adhesive, You may adhere | attach by electroplating or vapor-depositing or sputtering | spattering electroconductive substances, such as gold | metal | money, platinum, and aluminum.

  In the electrophotographic field, a urethane rubber blade is generally used as a cleaning blade. The urethane rubber has excellent wear resistance compared to rubber elastic bodies such as natural rubber, styrene rubber, butadiene rubber, nitrile rubber, ethylene propylene rubber, butyl rubber, silicon rubber (silicone), chloroprene rubber, hydrin rubber, and the like. Physical properties can be controlled only by a combination of materials. Therefore, urethane rubber is the most excellent material as the main body of the toner polarity control blade of the present invention. For this reason, the material constituting the toner polarity control blade is preferably urethane rubber. The insulating layer is preferably urethane rubber, and the conductive layer is preferably configured such that an electronically conductive polymer is dispersed in urethane rubber. Further, a small amount of an ionic conductive agent may be added to the conductive layer 75b as an auxiliary of the conductive agent together with the electronic conductive polymer.

  The urethane rubber used for the insulating layer and the conductive layer can be produced by a conventionally known composition and construction method. Urethane rubber usually uses a polyethylene adipate ester or polycaprolactone ester as a polyol component, and a prepolymer is prepared using 4,4′-diphenylmethane diisocyanate as a polyisocyanate component. It is manufactured by adding a curing catalyst, crosslinking in a predetermined mold, post-crosslinking in a furnace, and then aging at room temperature.

  As the high molecular weight polyol, for example, a polyester polyol which is a condensate of an alkylene glycol and an aliphatic dibasic acid, for example, ethylene adipate ester polyol, butylene adipate ester polyol, hexylene adipate ester polyol, ethylene propylene adipate ester polyol, ethylene Polyester polyols such as butylene adipate ester polyol, polyester glycols of alkylene glycol and adipic acid such as ethylene neopentylene adipate ester polyol, polycaprolactone polyols such as polycaprolactone ester polyol obtained by ring-opening polymerization of caprolactone, Poly (oxy (tetramethylene) glycol, poly (oxypropylene) glycol, etc. Ether-based polyols, or the like is used.

  Other examples of the low molecular weight polyol include 1,4-butanediol, ethylene glycol, neopentyl glycol, hydroquinone-bis (2-hydroxyethyl) ether, 3,3′-dichloro-4,4′-diaminodiphenyl. Dihydric alcohols such as methane, 4,4'-diaminodiphenylmethane, 1,1,1-trimethylolpropane, glycerin, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylol Mention may be made of trihydric and higher polyhydric alcohols such as ethane, 1,1,1-tris (hydroxyethoxymethyl) propane, diglycerin, pentaerythritol.

  Specific examples of the curing catalyst include 2-methylimidazole and 1,2-dimethylimidazole, and 1,2-dimethylimidazole is particularly preferably used. Usually, such a catalyst is preferably used in an amount of 0.01 to 0.5 parts by mass, more preferably 0.05 to 0.3 parts by mass with respect to 100 parts by mass of the main agent.

[Electroconductive polymer]

The electronic conductive polymer is not particularly limited, and examples thereof include polymers such as heterocyclic compounds, condensed polycyclic compounds, and amine compounds. More specifically, polyacetylene, polypyrrole, poly-3,4-alkylpyrrole, polythiophene, poly-3-methylthiophene, poly-N alkylaniline, poly-2,5-alkoxyaniline, polycarbazole, polyphenylene vinylene, polyphenylene, polyazulene. , Polyaniline, polydiphenylbenzidine, isothionaphthene and derivatives thereof. These may be used alone or in combination of two or more. Here, the electron conductive polymer refers to a polymer having a volume resistance of 10 ³ Ω · cm or less.

  Among the electron conductive polymers, it is particularly preferable to use polyaniline represented by the following structural formula. Polyaniline has a clearly identified molecular structure, does not lose conjugation due to steric hindrance, is easily synthesized and purified, and its conductivity does not depend on heat or humidity.

  The polyaniline is a polymer containing a monomer composed of aniline and / or the monomer derivative. That is, the polyaniline may be any one of a homopolymer of the monomer, a homopolymer of the monomer derivative, and a copolymer of the monomer and the monomer derivative.

  Examples of the monomer derivative include one or two or more substitutions at the 2-3 and 5-6 positions. For example, 2,5-dialkylaniline, 2,6-dialkoxyaniline, 3,6- Examples include dichloroaniline, 3,5-dicarboxyaniline, 4-aminoaniline, 6-methylphenylaminoaniline and the like.

  The structure of the (co) polymer forming the electron conductive polymer is generally that the monomer is bonded at the 2nd and 5th positions of the monomer ring, and in some cases, a bond is formed at the 3rd or 4th position. However, a polymer in which the monomer rings are connected at positions 2 and 5 is more preferable in order to maintain good electrical conductivity.

  Substances that can be doped into polyaniline as a dopant are classified into an electron donating dopant and an electron accepting dopant.

  Examples of the electron-donating dopant include alkali metals such as lithium, sodium, potassium, and cesium, alkylammoniums such as tetraethylammonium and tetrabutylammonium, and amines having primary and secondary amino groups.

  Examples of the electron-accepting dopant include halogens such as bromine, iodine, chlorine, bromine iodide, boron trifluoride, phosphorus pentafluoride, sulfite ion, arsenic pentafluoride, antimony pentafluoride, and silicon tetrafluoride. Lewis acids such as phosphorus pentachloride, aluminum chloride, aluminum bromide, aluminum fluoride, nitric acid, sulfuric acid, hydrochloric acid, hydrogen fluoride, perchloric acid, p-toluenesulfonic acid, fluorosulfuric acid, trifluoromethanesulfuric acid, chlorosulfuric acid, etc. Protonic acid, ferric chloride, molybdenum pentachloride, tungsten pentachloride, tin tetrachloride, molybdenum pentafluoride, ruthenium pentafluoride, tantalum pentabromide, tin tetraiodide transition metal halides, tetracyanoethylene, Tetracyanoquinone dimethane, chloranil, 2,3-dichloro-5,6 dicyanoparabenzoquinone, 2,3-dibromomu 5,6 Organic substances such as cyanoparabenzoquinone, surfactants such as alkyl sulfonates and alkyl benzene sulfonates, ecological substances such as glutamic acid, uridine acid, guaninoic acid, aspartic acid, inosinic acid, lysine, arginine, penicillin, protein, and porphyrin And phthalocyanines.

  There is no restriction | limiting in particular as the synthesis | combining method of the said polyaniline, Although it can change suitably according to the intended purpose, For example, the following method is mentioned. First, aniline is melted in an acidic aqueous solution such as hydrochloric acid which is an electron-accepting dopant, neutralized with an alkaline aqueous solution, filtered, washed with water and methanol, and dried to obtain a polyaniline powder. This polyaniline powder is sieved, added to a urethane rubber prepolymer, and stirred and dispersed with a ball mill to synthesize polyaniline.

  Although there is no restriction | limiting in particular as a preparation method of the said conductive layer, For example, it can manufacture by adding to an electroconductive polymer in the prepolymer prepared from the said polyol component and polyisocyanate component, and making it disperse | distribute. .

  The average particle size of the electroconductive polymer is preferably 0.1 μm to 4 μm, more preferably 0.5 to 3 μm, and particularly preferably 1.5 to 2.5 μm. When the average particle size is less than 0.1 μm, the electronically conductive polymer particles easily aggregate in the urethane rubber prepolymer, and uniform dispersibility cannot be obtained. When the average particle size exceeds 4 μm, the particle size is large. As a result, local discharge occurs between the toner polarity control blade and the transfer material.

  In addition to mixing and dispersing the electron conductive polymer in urethane rubber, it may be one in which the electron conductive polymer monomer is infiltrated, but it is considered from the aspect of shape and conductivity reproducibility and productivity. However, it is preferable to mix and disperse the electronically conductive polymer particles in the urethane rubber. If necessary, a conductive oxide such as titanium oxide or tin oxide may be added to the conductive layer 75b. Also, cationic or anionic surfactants, polymers having ion dissociation ability such as polyethylene oxide, polypropylene oxide, polyphosphazene, alkali metal salts, ionic salt bodies, and the like may be mixed.

  There is no restriction | limiting in particular as addition amount of the said electronic conductive polymer, According to the objective, it can select suitably, It is preferable that it is 3 mass%-20 mass%, and it is 5 mass%-15 mass%. It is more preferable, and it is especially preferable that they are 8 mass%-12 mass%. If the amount added is less than 3% by mass, sufficient conductivity cannot be ensured, and toner polarity cannot be controlled, resulting in poor cleaning. On the other hand, if the content exceeds 20% by mass, the conductivity is too high, and if the dispersibility of the electroconductive polymer is poor, the discharge tends to concentrate, the rebound resilience of the conductive layer 75b decreases, and the wear resistance decreases. As a result, the conductive layer becomes brittle and breaks, resulting in poor cleaning.

  The electroconductive polymer can be confirmed for dispersibility in urethane rubber by an electron microscope. When the surface of the conductive layer 75b is observed with an electron microscope, the particles of the electron conductive polymer dispersed in the urethane rubber can be confirmed, and if the portion where the particles are aggregated is not observed, good dispersibility is obtained. Can be confirmed.

  The thickness of the conductive layer is preferably 0.3 mm or more, more preferably 0.7 mm to 4 mm, and particularly preferably 1 mm to 3 mm. If the thickness is less than 0.3 mm, sufficient conductivity cannot be ensured, and toner polarity cannot be controlled sufficiently. On the other hand, if the thickness is less than 0.3 mm, it is difficult to produce a uniform film, and uneven conductivity tends to occur. Further, the thickness of the conductive layer is more advantageous as it is reduced in cost.

(toner)
Next, the toner suitably used in the present invention will be described. First, the toner used in the present invention preferably has an average circularity of 0.93 to 1.00. In the present invention, the value obtained from the following formula (1) is defined as circularity. This circularity is an index of the degree of unevenness of the toner particles, and indicates 1.00 when the toner is a perfect sphere, and the circularity becomes smaller as the surface shape becomes more complicated.

Circularity SR = perimeter of a circle having the same area as the particle projection area / perimeter of the particle projection image (1)

  When the average circularity is in the range of 0.93 to 1.00, the surface of the toner particles is smooth, and the contact area between the toner particles and between the toner particles and the photosensitive member is small, so that the transferability is excellent. Since the toner particles have no corners, the developer agitation torque in the developing device is small, and the agitation drive is stabilized, so that no abnormal image is generated. Since there are no angular toner particles in the toner that forms the dots, when the pressure is brought into contact with the transfer medium during the transfer, the pressure is uniformly applied to the entire toner that forms the dots, and the transfer is not easily lost. Since the toner particles are not angular, the abrasive power of the toner particles themselves is small, and the surface of the image carrier is not damaged or worn.

  Next, a method for measuring the circularity will be described. The circularity can be measured using a flow type particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics. As a specific measurement method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance. About 0.1 to 0.5 g. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape and particle size of the toner are measured by the above apparatus with the dispersion concentration being 3000 to 10000 / μl.

  In the present invention, it is preferable to use a toner having a weight average diameter D4 of 3 to 10 μm. In this range, since the toner particles have a sufficiently small particle size with respect to the minute latent image dots, the dot reproducibility is excellent. When the weight average diameter D4 is less than 3 μm, phenomena such as a decrease in transfer efficiency and a decrease in blade cleaning properties tend to occur. When the weight average diameter D4 exceeds 10 μm, it is difficult to suppress scattering of characters and lines. The toner used in the present invention preferably has a ratio (D4 / D1) of the weight average diameter D4 and the number average diameter D1 of 1.00 to 1.40. The closer the value of (D4 / D1) is to 1, the sharper the particle size distribution of the toner. Therefore, when (D4 / D1) is in the range of 1.00 to 1.40, the selective development due to the toner particle size does not occur, and the stability of the image quality is excellent. Since the toner particle size distribution is sharp, the triboelectric charge amount distribution is also sharp, and fogging is suppressed. When the toner particle diameter is uniform, the latent image dots are developed so as to be arranged in a precise and orderly manner, so that the dot reproducibility is excellent.

  Next, a method for measuring the particle size distribution of toner particles will be described. Examples of the measuring device for the particle size distribution of toner particles by the Coulter counter method include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.

  First, 0.1 to 5 ml of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average diameter D4 and the number average diameter D1 of the toner can be obtained.

  The channels include 2.00 μm to 2.52 μm, 2.52 μm to 3.17 μm, 3.17 μm to 4.00 μm, 4.00 μm to 5.04 μm, 5.04 μm to 6.35 μm, 6.35 μm to 8.35 μm. 00 μm, 8.00 μm to 10.08 μm, 10.08 μm to 12.70 μm, 12.70 μm to 16.00 μm, 16.00 μm to 20.20 μm, 20.20 μm to 25.40 μm, 25.40 μm to 32.00 μm, 13 channels of 32.00 μm to 40.30 μm are used, and particles having a particle size of 2.00 μm to less than 40.30 μm are targeted.

  In addition, as such a substantially spherical toner, a toner composition containing a polyester prepolymer having a functional group containing a nitrogen atom, a polyester, a colorant, and a release agent in an aqueous medium in the presence of fine resin particles. A toner that undergoes crosslinking and / or elongation reaction is preferred. The toner manufactured by this reaction can reduce the hot offset by curing the surface of the toner, and it can be suppressed that the fixing device becomes dirty and appears on the image.

  Examples of the prepolymer comprising a modified polyester resin that can be used for toner production include a polyester prepolymer (A) having an isocyanate group, and examples of the compound that extends or crosslinks with the prepolymer include amines (B). Can be mentioned. Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (A1) and a polycarboxylic acid (A2) and a polyester having an active hydrogen group, which is further reacted with a polyisocyanate (A3). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (A1) include a diol (A1-1) and a tri- or higher valent polyol (A1-2). (A1-1) alone or (A1-1) and a small amount of (A1-2) Mixtures are preferred. Examples of the diol (A1-1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.), alkylene ether glycol (diethylene glycol). , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.), alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols, Alkylene oxide phenols (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

  Examples of the trivalent or higher polyol (A1-2) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.), and trivalent or higher phenols. (Trisphenol PA, phenol novolak, cresol novolak, etc.), alkylene oxide adducts of the above trivalent or higher polyphenols, and the like.

  Examples of the polycarboxylic acid (A2) include dicarboxylic acid (A2-1) and trivalent or higher polycarboxylic acid (A2-2). (A2-1) alone and (A2-1) with a small amount of ( A mixture of A2-2) is preferred. Dicarboxylic acids (A2-1) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

  Examples of the trivalent or higher polycarboxylic acid (A2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (A2), you may make it react with a polyol (A1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing. The ratio of the polyol (A1) to the polycarboxylic acid (A2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (A3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.), alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.), araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.), isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactams, etc. And a combination of two or more of these.

  The ratio of the polyisocyanate (A3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (A3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, more preferably 2 to 20% by mass. It is. If it is less than 0.5% by mass, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by mass, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 2/1 to 1/2, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates. In this toner, the polyester (i) modified with a urea bond may contain a urethane bond as well as a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

  By these reactions, the modified polyester used in the present toner, especially urea-modified polyester (i) can be prepared. These urea-modified polyesters (i) are produced by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

  In the present toner, not only the polyester (i) modified with a urea bond but also the polyester (ii) not modified can be contained as a binder resin component together with the (i). By using (ii) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to the single use. Examples of (ii) include the same polycondensates of polyol (A1) and polycarboxylic acid (A2) as in the polyester component (i), and preferred ones are also the same as (i). Further, (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, for example, may be modified with a urethane bond. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions. In the case of containing (ii), the mass ratio of (i) and (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. If the mass ratio of (i) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (ii) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is usually 1-30, preferably 5-20. By having an acid value, it tends to be negatively charged.

In the present toner, the glass transition point (Tg) of the binder resin is usually preferably 50 ° C to 70 ° C, and more preferably 55 ° C to 65 ° C. When the glass transition point is less than 50 ° C., the blocking of the toner during high temperature storage deteriorates, and when it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the urea-modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners. As the storage elastic modulus of the binder resin, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10000 dyne / cm ² is preferably usually 100 ° C. or higher, and more preferably 110 ° C. to 200 ° C. When the temperature is less than 100 ° C., the hot offset resistance deteriorates. As the viscosity of the binder resin, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is preferably usually 180 ° C. or less, more preferably 90 ° C. to 160 ° C. When the temperature exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 or more, more preferably 10 or more, and particularly preferably 20 or more. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100, more preferably 10 to 90, and particularly preferably 20 to 80.

  The binder resin can be produced by the following method. The polyol (A1) and the polycarboxylic acid (A2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (A3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group. Further, (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond. When reacting (A3) and reacting (A) and (B), a solvent may be used as necessary. Solvents that can be used include aromatic solvents (toluene, xylene, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, etc.), amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to the isocyanate (A3), such as tetrahydrofuran (such as tetrahydrofuran). When polyester (ii) not modified with urea bond is used in combination, (ii) is produced in the same manner as polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of (i) and mixed. To do.

  In addition, the toner used in the present invention can be produced generally by the following method, but is not limited thereto. The toner may be formed by reacting a dispersion composed of a prepolymer (A) having an isocyanate group in an aqueous medium with (B), or a urea-modified polyester (i) produced in advance may be used. . As a method for stably forming a dispersion comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium, a toner raw material comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium is used. And a method of dispersing by shearing force.

  The prepolymer (A) and other toner compositions (hereinafter sometimes referred to as toner raw materials), colorants, colorant master batches, release agents, charge control agents, unmodified polyester resins, Mixing may be performed when the dispersion is formed in the medium, but it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium. It may be added later. For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method.

  The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The amount of the aqueous medium used relative to 100 parts of the toner composition containing the urea-modified polyester (i) and the prepolymer (A) is usually 50 to 2000 parts by mass, preferably 100 to 1000 parts by mass. If the amount is less than 50 parts by mass, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle size cannot be obtained. If it exceeds 20000 parts by mass, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotation speed is not particularly limited, but is usually 1,000 rpm to 30,000 rpm, preferably 5,000 rpm to 20,000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion made of urea-modified polyester (i) or prepolymer (A) has a low viscosity and is easy to disperse.

  In the step of synthesizing the urea-modified polyester (i) from the prepolymer (A), the amine (B) may be added and reacted before the toner composition is dispersed in the aqueous medium, or may be dispersed in the aqueous medium. An amine (B) may be added later to cause a reaction from the particle interface. In this case, urea-modified polyester is preferentially produced on the surface of the manufactured toner, and a concentration gradient can be provided inside the particles.

  In the reaction, it is preferable to use a dispersant as necessary. There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and by using a surfactant having a fluoroalkyl group, the anionic surfactant can be used in a very small amount. Can be effective. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms (hereinafter referred to as C2 to C10) and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ Omega-fluoroalkyl (C6-C11) oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, Fluoroalkyl (C11 to C20) carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and metal salt thereof, perfluoroalkyl (C4 to C12) sulfonic acid and metal salt thereof, perfluorooctane sulfonic acid diethanolamide , N-P Pyr-N- (2hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate etc. are mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-l10, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, benza Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

  Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives. Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

  Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

  Polymeric protective colloids include, for example, acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers with vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, amide compounds Alternatively, homopolymers or copolymers of these methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, celluloses, and the like can be mentioned.

  Examples of acids include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or hydroxyl groups (meth) Acrylic monomers, such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as pinyl acetate, pinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinyl pyridine, vinyl pyrrolidone, vinyl imidazole , Homopolymers or copolymers such as those having a nitrogen atom such as ethyleneimine or its heterocyclic ring, polyoxyethylene, polyoxy Propylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene Polyoxyethylenes such as nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  In the preparation of the dispersion, a dispersion stabilizer can be used as necessary. Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts. When a dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme. In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  Furthermore, in order to lower the viscosity of the toner composition, a solvent in which the urea-modified polyester (i) or the prepolymer (A) is soluble can be used. Since the particle size distribution becomes sharp when a solvent is used, it is preferable to use a solvent. The solvent is preferable because it is volatile and can be easily removed. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred, and aromatic solvents such as toluene and xylene are more preferred. The usage-amount of the solvent with respect to 100 mass parts of prepolymers (A) is 0-300 mass parts normally, Preferably it is 0-100 mass parts, More preferably, it is 25-70 mass parts. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after elongation and / or crosslinking reaction.

  The elongation and / or crosslinking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. In general, the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer, rotary kiln.

  When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution. In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet. The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above. By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.

  Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

  As the colorant used in the present toner, pigments and dyes conventionally used as toner colorants can be used. Specifically, carbon black, lamp black, iron black, ultramarine, nigrosine dye, Aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow G, rhodamine 6C lake, calco oil blue, chrome yellow, quinacridone red, benzidine yellow, rose bengal and the like can be used alone or in combination.

  Further, if necessary, in order to give the toner particles magnetic properties, magnetic components such as iron oxides such as ferrite, magnetite and maghemite, metals such as iron, cobalt and nickel, or alloys of these with other metals. May be contained alone or in combination in the toner particles. Moreover, these components can also be used and used together as a coloring agent component.

  In addition, the number average diameter of the colorant in the toner used in the present invention is preferably 0.5 μm or less, more preferably 0.4 μm or less, and particularly preferably 0.3 μm or less. When the number average diameter of the colorant in the toner exceeds 0.5 μm, the dispersibility of the pigment does not reach a sufficient level, and preferable transparency may not be obtained.

  A colorant having a fine particle diameter smaller than 0.1 μm is sufficiently smaller than a half wavelength of visible light, and thus is considered not to adversely affect light reflection and absorption characteristics. Therefore, the colorant particles having a particle size of less than 0.1 μm contribute to good color reproducibility and transparency of the OHP sheet having a fixed image. On the other hand, if there are many colorants having a particle size larger than 0.5 μm, the transmission of incident light is hindered or scattered, and the brightness and vividness of the projected image of the OHP sheet tend to decrease. There is. Further, if there are many colorants having a particle size larger than 0.5 μm, the colorant is detached from the surface of the toner particles, and various problems such as fogging, drum contamination, and poor cleaning are liable to occur. In particular, the colorant having a particle size larger than 0.7 μm is preferably 10% by number or less, more preferably 5% by number or less of the total colorant.

  In addition, by adding a wetting liquid in advance with a part or all of the binder resin and kneading the colorant, the binder resin and the colorant are initially sufficiently adhered, In the toner production process, the colorant is dispersed more effectively in the toner particles, the dispersed particle diameter of the colorant is reduced, and better transparency can be obtained.

  As the binder resin used for kneading in advance, the resins exemplified as the binder resin for toner can be used as they are, but are not limited thereto. As a specific method for kneading the mixture of the binder resin and the colorant together with the wetting liquid in advance, for example, the binder resin, the colorant and the wetting liquid can be obtained after mixing with a blender such as a Henschel mixer. The obtained mixture is kneaded at a temperature lower than the melting temperature of the binder resin by a kneader such as a two-roll or three-roll to obtain a sample.

  As the wetting liquid, a general one can be used in consideration of the solubility of the binder resin and the wettability with the colorant. In particular, organic solvents such as acetone, toluene, butanone and water are used as the colorant. It is preferable from the viewpoint of dispersibility. Among these, the use of water is more preferable from the viewpoint of environmental considerations and maintaining the dispersion stability of the colorant in the subsequent toner production process. According to this manufacturing method, not only the particle diameter of the colorant particles contained in the obtained toner is reduced, but also the uniformity of the dispersion state of the particles is increased, so that the color reproducibility of the projected image by OHP is further improved. Get better.

  In addition, as long as the configuration of the present invention is adopted, a release agent represented by wax can be contained in the toner together with the binder resin and the colorant. As the release agent, known ones can be used, and examples thereof include polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sazol wax, etc.), carbonyl group-containing wax, and the like. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate), polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.), polyalkanoic acid amides (ethylenediamine dibehenylamide, etc.), polyalkylamides (trimellitic acid tristearylamide, etc.) , And dialkyl ketones (such as distearyl ketone).

  Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of these release agents is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by mass, preferably 3 to 30% by mass.

  In order to accelerate the toner charge amount and its rise, a charge control agent may be contained in the toner as necessary. Here, since a color change occurs when a colored material is used as the charge control agent, a material that is colorless and close to white is preferable.

  Any known charge control agent can be used. Examples include triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkyls. Amide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, salicylic acid derivative metal salt, and the like. Specifically, Bontron P-51 of a quaternary ammonium salt, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex, E-89 of a phenol condensate (above, Orient Chemical Co., Ltd.) Manufactured), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, Quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, boron complex LR-147 (manufactured by Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups , A polymer having a functional group such as a carboxyl group or a quaternary ammonium salt. Compounds.

  The amount of charge control agent used in this toner is uniquely determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method. However, it is preferably used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Preferably, the range of 0.2-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or may be added when directly dissolving and dispersing in an organic solvent, or may be fixed on the toner surface after preparation of toner particles. Also good.

  When the toner composition is dispersed in the aqueous medium during the toner production process, resin fine particles for mainly stabilizing the dispersion may be added. The resin fine particles used may be any resin that can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resins, polyurethane resins, epoxy resins, polyester resins, Examples thereof include polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.

  The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include, but are not limited to, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

  Further, inorganic fine particles can be preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner particles. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 to 2.0% by mass.

  Examples of the polymer fine particles include polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as methacrylic acid ester and acrylic acid ester copolymer, silicone, benzoguanamine, and nylon, heat Examples thereof include polymer particles made of a curable resin.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, such as polymethyl methacrylate fine particles, polystyrene. Examples thereof include fine polymer particles produced by soap-free emulsion polymerization of fine particles and the like. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  By using these toners, a high-quality toner image having excellent development stability can be formed as described above. The toner is not particularly limited and can be appropriately selected from those used as electrophotographic toners according to the purpose. The toner includes at least a binder resin and a colorant, and includes a release agent, a charging agent. It is preferable to use a control agent and, if necessary, other components.

  The cleaning device of the present invention can be applied not only to the use of the toner having a configuration suitable for obtaining a high quality image as described above, but also to an irregular shaped toner by a pulverization method, and has a good cleaning property. It goes without saying that it is obtained. As a material constituting such a pulverized toner, those usually used as an electrophotographic toner can be applied without particular limitation.

  Examples of general binder resins used for the toner include styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and the like, and homopolymers thereof; styrene / p-chlorostyrene copolymer Styrene / propylene copolymer, styrene / vinyl toluene copolymer, styrene / vinyl naphthalene copolymer, styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer Styrene / octyl acrylate copolymer, styrene / methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer, styrene / α-chloromethyl methacrylate copolymer, styrene / Acrylonitrile copolymer, styrene / vinyl methyl ketone copolymer Styrene copolymers such as styrene / butadiene copolymer, styrene / isoprene copolymer, styrene / maleic acid copolymer; polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate, etc. Acrylic ester monopolymers and copolymers thereof; polyvinyl derivatives such as polyvinyl chloride and polyvinyl acetate; polyester polymers, polyurethane polymers, polyamide polymers, polyimide polymers, polyol polymers An epoxy polymer, a terpene polymer, an aliphatic or alicyclic hydrocarbon resin, an aromatic petroleum resin, and the like can be used, and these can be used alone or in combination, but are not particularly limited thereto. Among these, at least one selected from styrene-acrylic copolymer resins, polyester resins, and polyol resins is more preferable from the viewpoint of electrical characteristics, cost, and the like. Furthermore, it is more preferable to use a polyester-based resin and / or a polyol-based resin as having good fixing characteristics.

  In the pulverized toner, together with these resin components, the colorant component, wax component, charge control component, and the like as described above are premixed as necessary, and then kneaded at a temperature close to the melting temperature of the resin component, and then cooled. Thereafter, a toner may be prepared through a pulverization and classification step, and the above-mentioned external additive components may be appropriately added and mixed as necessary.

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

  In the developing device, 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 (photosensitive member), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is caused by the electric attractive force. It moves to the surface of the image carrier (photoreceptor). As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the image carrier (photoconductor).

  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.

(Image forming method and image forming apparatus)
According to the image forming apparatus according to the present invention, as described above, the electrical characteristics are stable, the wear resistance is excellent, there is no abnormal image such as void, density unevenness, and color unevenness, and a high-quality full-color image is obtained. An image forming apparatus can be provided. The image forming method of the present invention can be performed by the image forming apparatus of the present invention.

  FIG. 1 is an explanatory diagram showing a schematic configuration of the entire printer 500 according to the present embodiment. A charging device 2, an exposure device (not shown), a developing device 6, a transfer device 5, a cleaning device 7, and a charge eliminating lamp 8 are sequentially arranged around a drum-shaped photoconductor 1 as an image carrier. Above the photosensitive member 1, a charging device 2 as a charging unit that uniformly charges the surface of the photosensitive member 1 with a charging roller 2a, and an electrostatic latent image is formed on the surface of the charged photosensitive member 1 with a laser beam L. An exposure apparatus as a latent image forming means (not shown) is arranged. Further, on the right side of the photoreceptor 1 in FIG. 1, development that forms a toner image by attaching toner charged to a predetermined polarity (negative polarity in this embodiment) to the electrostatic latent image on the surface of the photoreceptor 1. A developing device 6 is arranged as a means. A transfer device 5 is provided below the photoconductor 1 as transfer means for transferring the toner image on the photoconductor 1 to the transfer paper P conveyed from the paper feed cassette 3 by the transfer roller 12a. Further, on the left side of the photoreceptor 1 in FIG. 1, a cleaning device 7 as a latent image carrier cleaning means for removing transfer residual toner remaining on the photoreceptor 1 after transfer, and a residual potential on the photoreceptor 1 are shown. A static elimination lamp 8 to be removed is provided.

  After the surface of the photoreceptor 1 is uniformly charged by the charging device 2, an electrostatic latent image based on the image information is formed by the laser light L irradiated based on the image information by an exposure device (not shown). On the surface of the photoreceptor 1 on which the electrostatic latent image is formed, toner is supplied to the electrostatic latent image by the developing device 6 to form a toner image.

  The surface friction resistance of the photoreceptor is preferably 0.25 or less. Deformation of the edge of the toner polarity control blade occurs when the photoconductor drags the toner polarity control blade. However, when the frictional resistance of the photoconductor is sufficiently low, stress applied to the toner polarity control blade 71 is reduced and deformation is prevented. To prevent deformation of the toner polarity control blade edge, the contact with the toner can be stably performed, and the stress applied to the toner polarity control blade edge is reduced to reduce wear and damage of the toner polarity control blade edge. , Leading to prevention.

  Further, the photoconductor may be provided with a protective layer as necessary, and a structure that lowers the friction coefficient may be incorporated in the protective layer. For example, there are a method in which a resin having a low friction coefficient is used as a protective layer, a method in which fine particles having a low friction coefficient such as a fluorine-containing resin are dispersed in a photoreceptor, and a method in which a lubricant is applied. The surface of the photoreceptor is deteriorated by various external factors such as toner, carrier, conveying member, and charging. By applying a lubricant to the surface of the photoconductor, the photoconductor is not directly exposed to the external factors as described above, and the degree of deterioration can be reduced.

  Further, the present invention can also be applied to an intermediate transfer type image forming apparatus that transfers a toner image on the photoreceptor 1 to an intermediate transfer belt and transfers the toner image on the intermediate transfer belt onto a transfer sheet. At this time, the cleaning device of the present invention can be applied not only as a cleaning device that cleans the transfer residual toner attached on the photosensitive member but also as an intermediate transfer belt cleaning device that cleans the transfer residual toner attached on the intermediate transfer belt. .

  The intermediate transfer belt applicable in the present invention is not particularly limited, and can be appropriately selected from known intermediate transfer belts according to the purpose.

  The static friction coefficient of the intermediate transfer belt is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer belt is preferably several Ωcm to 103 Ωcm. By setting the volume resistance to several Ωcm to 103 Ωcm, the intermediate transfer belt itself is prevented from being charged, and the charge imparted by the charge imparting means is less likely to remain on the intermediate transfer belt. Unevenness can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

  The material of the intermediate transfer belt is not particularly limited and can be appropriately selected from known materials according to the purpose. For example, (1) a material having a high Young's modulus (tensile elastic modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT (polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, blend material of PC / PAT, thermosetting polyimide dispersed in carbon black, and the like. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and registration is not likely to occur particularly during color image formation. (2) A belt having a two- to three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery of the belt. Therefore, the line image has a performance capable of preventing the line image from being lost. (3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the belt width is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .

  In the present invention, as a means for reducing the frictional resistance on the surface of the intermediate transfer belt, a method of applying a lubricant may be used. The surface of the intermediate transfer belt is deteriorated by various external factors such as toner, carrier, conveying member, charging, and paper. By applying a lubricant to the surface of the intermediate transfer belt, the intermediate transfer belt is not directly exposed to the external factors as described above, and the degree of deterioration can be reduced.

  Below the transfer device 5, a paper feed cassette 3 that stores a plurality of transfer papers P as recording materials is disposed. The paper feed cassette 3 rotates the paper feed roller 3a pressed against the uppermost transfer paper P at a predetermined timing, and feeds the transfer paper P to the paper feed conveyance path. In the paper feed conveyance path, the transferred transfer paper P passes through the plurality of conveyance roller pairs 13 and then is sandwiched between the rollers of the registration roller pair 14 and stopped. The registration roller pair 14 faces the transfer nip between the transfer roller 12a and the photoconductor 1 at a timing at which the sandwiched transfer paper P can be superimposed on the toner image formed on the photoconductor 1 as described above. Send it out. As a result, the toner image on the photosensitive member 1 and the transfer paper P sent out by the registration roller pair 14 are brought into close contact with each other at the transfer nip. The toner image on the photoreceptor 1 is electrostatically transferred onto the transfer paper P under the action of a transfer bias.

  A paper transport belt 12 is wound around the transfer roller 12a. The paper conveying belt 12 is stretched between a transfer roller 12a and a driving roller 12b, and moves endlessly counterclockwise in the drawing. A fixing device 9 as a fixing unit and a paper discharge roller pair 10 are provided on the left side of the paper conveying belt 12 in the drawing. The transfer paper P on which the toner image is electrostatically transferred is sent to the fixing device 9 by the paper transport belt 12. The transfer paper P that has entered the fixing device 9 is subjected to heat treatment and pressure treatment. As a result, the toner melts while receiving pressure, and the toner image is fixed on the transfer paper P. Then, the transfer paper P is discharged out of the apparatus from the fixing device 9 through the paper discharge roller pair 10.

  Untransferred toner remaining on the photoreceptor without being transferred is collected by the cleaning device 7. The surface of the photoreceptor 1 from which the transfer residual toner has been removed is initialized by the charge eliminating lamp 8 and used for the next image forming process. Unnecessary toner that has been transferred onto the paper transport belt 12 is removed from the paper transport belt 12 by the belt cleaning device 15.

  In the present embodiment, the photosensitive member 1, the developing device 6, the charging device 2, and the cleaning device 7 are accommodated in a process cartridge 100 as a unit device that includes a structure that integrally supports them. The process cartridge 100 is detachable from the printer body. Therefore, when the life of a component housed in the process cartridge 100 is reached or maintenance is required, the process cartridge 100 may be replaced, which improves convenience.

  As the image forming apparatus, a lubricant may be applied to the surface of the photoreceptor 1 as a transfer target. As the lubricant used in the present invention, metal soaps containing zinc are preferable. As the metal soap, zinc stearate, zinc oleate, zinc palmitate, or the like can be used. These tend to be organic solid metal soaps and have good compatibility with toner. In particular, the metal soap used in the present invention is particularly preferably a mixture of zinc stearate and zinc palmitate. By mixing a certain amount of zinc palmitate and zinc stearate, metal soap is stretched onto the transfer material even when the linear speed of the photoconductor or intermediate transfer belt as the transfer material is high, and the transfer target The surface frictional resistance on the material can be efficiently reduced.

  Further, as the lubricant, a mixture of zinc stearate and zinc palmitate may be used. Zinc stearate and zinc palmitate are both fatty acid metal salts, but stearic acid in the fatty acid portion has 18 carbon atoms, and palmitic acid has 16 carbon atoms. Therefore, zinc stearate and zinc palmitate are similar in structure, are well compatible and behave as substantially the same material, and both can protect the material to be transferred in the same way. In addition, since zinc palmitate has a lower melting point than zinc stearate, if soap palmitate is contained in a certain amount or more, metal soap tends to be stretched, so the linear velocity on the transfer material is high. However, the metal soap can sufficiently cover the intermediate transfer belt.

  In addition, as the linear velocity of the photosensitive member 1 increases, the charging energy poured onto the intermediate transfer belt, particularly the AC charging energy, becomes stronger. Therefore, in order to enhance the protection effect of the intermediate transfer belt by metal soap, It is necessary to increase the thickness of the metal soap.

  Zinc stearate is not attached randomly on the intermediate transfer belt, but is stable when attached with two molecules. That is, even if zinc stearate is applied on the intermediate transfer belt, it is saturated at the thickness of two molecules of zinc stearate. Here, when zinc palmitate having a slightly smaller molecular length than zinc stearate is contained in a certain amount or more, the height of the molecular layer is not constant, and the low part and the high part coexist. Then, the next molecule enters the lower part and forms a molecular layer. Therefore, as a result, a metal soap layer thicker than two molecules can be formed, and it is considered that the protective effect of the intermediate transfer belt is improved. Naturally, when the amount of zinc palmitate becomes too large, a zinc palmitate bimolecular layer is likely to be formed, and the thickness of the metal soap does not increase. In addition, since zinc palmitate has a smaller molecule than zinc stearate, the protective effect of the intermediate transfer belt is reduced compared to zinc stearate alone.

  Therefore, the mass ratio of zinc stearate and zinc palmitate in the metal soap used in the image forming apparatus of the present invention is preferably 73:27 to 45:55. In this mass ratio range, the metal soap protects the entire intermediate transfer belt even when the linear transfer belt is fast, and the thickness of the metal soap layer is not reduced, and the protective effect of the metal soap is enhanced.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples without departing from the gist thereof.

Example 1
<Synthesis of polyaniline powder A>
20.4 g of aniline was dissolved in 300 mL of a sulfuric acid aqueous solution having a concentration of 2.8 mol / L and cooled to 1.5 ° C. or lower. A solution prepared by dissolving 5 g of ammonium persulfate in 50 mL of an aqueous sulfuric acid solution having a concentration of 2.8 mol / L was added dropwise thereto.

  After completion of dropping, the mixture was stirred at 5 ° C. or lower for 2 hours, sufficiently washed in the order of filtration, water and methanol, and dried to obtain polyaniline. The obtained product was pulverized in an agate mortar and passed through a predetermined sieve to obtain polyaniline powder A having an average particle size of 0.005 μm.

<Preparation of Toner Polarity Control Blade A>
10 parts by mass of polyaniline powder A is added to 90 parts by mass of the prepolymer with respect to the ethylene adipate-based prepolymer (NCO content 16.5%) degassed for 3 hours at 60 ° C. under the condition of 3 mmHg. After mixing with a sand mill in a molten state at 90 ° C., it is mixed with a liquid material in which polyethylene adipate / 1,4 butanediol / ethylene glycol (mass ratio 88.6 / 6.8 / 4.6) is mixed as a curing agent. Then, blade coating was performed to a thickness of about 1 mm on one side of a mold coated with a fluorine-based release agent, and the conductive layer was held at 150 ° C. for 20 minutes. Thereafter, the mixture of the prepolymer and the curing agent was injected, the whole was made to have a thickness of 2 mm, held at 150 ° C. for 1 hour to form an insulating layer, and then the polyurethane rubber cured in a sheet shape was demolded. The polyurethane rubber was allowed to stand on a flat plate at 23 ° C. for 7 days, and then cut into a strip shape to obtain a toner polarity control blade A.

  The dispersibility of the polyaniline powder A in the conductive layer was confirmed by observing 10 points with a field emission scanning electron microscope (FE-SEM: JSM-7400F manufactured by JEOL Ltd.) at a magnification of 5000 times and an acceleration voltage of 5 kV. The dispersibility of the polyaniline powder A was good to some extent, but about one small aggregated portion was observed at each observed location.

<Preparation of metal soap A>
Zinc stearate and zinc palmitate (primary particle size: 0.18 μm) are weighed to the following ratios, heated to 145 ° C. to melt, poured molten metal soap into the mold and cooled. Thus, a metal soap block having a size of 40 mm × 8 mm × length 350 mm was produced (because it is produced by melt molding, the degree of compression is 100%). This lubricating block was attached to a base material for metal soap with an adhesive to obtain metal soap A.
-Zinc stearate 45 mass ratio-Zinc palmitate 55 mass ratio Metal soap A was used as a lubricant on the surface of the photoreceptor which is a transfer target.

<Evaluation>
The toner polarity control blade A, metal soap A, and toner are installed in the printer shown in FIG. 1, and a test chart with an image density of 7% in an ordinary state in which toner and paper are supplied is an environment of 23 ° C. and 45%. 50,000 images were formed. The adhesion of the toner polarity control blade A was performed by using a conductive tape between the conductive layer 75b of the toner polarity control blade shown in FIG. As the conductive tape, X-7001 made by Sumitomo 3M Limited was used. At this time, the toner was prepared by a polymerization method having a mass average particle diameter (D4) = 5.2 μm, a number average particle diameter (D1) = 4.5 μm, D4 / D1 = 1.16, and an average circularity = 0.98. The toner used was used. The paper used was TYPE 6200 (Ricoh). The linear speed of image formation was 250 mm / second. At the same time, each image output under the above conditions was evaluated. The results are shown in Table 1.

[Evaluation criteria at a linear speed of 250 mm / sec]
A: An abnormal image was not seen at all, and a high-quality image was obtained.
○: Although it was within the allowable range, an image with slight streaks was obtained when viewed with a magnifier.
Δ: When viewed with a magnifying glass, an image having a plurality of streaks was obtained.
X: A streak that could be recognized with the naked eye beyond the allowable range was observed.

  Next, in the case of “◎” and “◯” in the above evaluation, the linear velocity of image formation was increased to 450 mm / second, and a test chart with an image density of 7% was measured at an environment of 23 ° C. and 45%. A total of 500,000 images were formed at a time, and each output image was evaluated. The results are shown in Table 1.

[Evaluation criteria at a linear speed of 450 mm / sec]
A: An abnormal image was not seen at all, and a high-quality image was obtained.
○: Although it was within the allowable range, an image with slight streaks was obtained when viewed with a magnifier.
Δ: When viewed with a magnifying glass, an image having a plurality of streaks was obtained.
X: A streak that could be recognized with the naked eye beyond the allowable range was observed.

(Example 2)
<Synthesis of polyaniline powder B>
A polyaniline powder A described in Example 1 was prepared in the same manner as that except for the average particle size. The predetermined sieve was changed to obtain polyaniline powder B having an average particle size of 0.1 μm.

<Preparation of Toner Polarity Control Blade B>
A toner polarity control blade B was obtained by the same method except that the polyaniline powder B was added instead of the polyaniline powder A of the toner polarity control blade A described in Example 1. In addition, metal soap A was used as a lubricant on the surface of the photoreceptor, which is a transfer target. The dispersibility of the polyaniline powder B in the conductive layer was confirmed by the same method as described in Example 1. The dispersibility of the polyaniline powder B was good with no aggregation sites.

  The evaluation method of Example 2 was performed in the same manner as in Example 1. The results are shown in Table 1. In Example 2, the same toner as in Example 1 was used.

(Example 3)
<Synthesis of polyaniline powder C>
A polyaniline powder A described in Example 1 was prepared in the same manner as that except for the average particle size. The predetermined sieve was changed to obtain polyaniline powder C having an average particle size of 4 μm.

<Preparation of Toner Polarity Control Blade C>
Toner polarity control blade C was obtained in the same manner except that polyaniline powder C was added in place of polyaniline powder A of toner polarity control blade A described in Example 1. In addition, metal soap A was used as a lubricant on the surface of the photoreceptor, which is a transfer target. The dispersibility of the polyaniline powder C in the conductive layer was confirmed by the same method as described in Example 1. The dispersibility of the polyaniline powder C was good with no aggregation sites.

  The evaluation method of Example 3 was performed in the same manner as in Example 1. The results are shown in Table 1. In Example 3, the same toner as in Example 1 was used.

Example 4
<Synthesis of polyaniline powder D>
A polyaniline powder A described in Example 1 was prepared in the same manner as that except for the average particle size. The predetermined sieve was changed to obtain a polyaniline powder D having an average particle size of 5 μm.

<Preparation of Toner Polarity Control Blade D>
A toner polarity control blade D was obtained in the same manner except that the polyaniline powder D was added instead of the polyaniline powder A of the toner polarity control blade A described in Example 1. In addition, metal soap A was used as a lubricant on the surface of the photoreceptor, which is a transfer target. The dispersibility of the polyaniline powder D in the conductive layer was confirmed by the same method as described in Example 1. The dispersibility of the polyaniline powder D was good with no agglomerated sites.

  The evaluation method of Example 4 was performed in the same manner as in Example 1. The results are shown in Table 1. In Example 4, the same toner as in Example 1 was used.

(Example 5)
The toner polarity control blade C described in Example 3 was used. The same procedure as in Example 1 was performed, except that no lubricant was used for the photoreceptor to be transferred.

  The evaluation method of Example 5 was performed in the same manner as in Example 1. The results are shown in Table 1. In Example 5, the same toner as in Example 1 was used.

(Example 6)
<Preparation of metal soap B>
Zinc stearate (primary particle size: 0.18μm) is heated to 145 ° C and melted, and molten metal soap is poured into the mold and cooled to produce a 40mm x 8mm x 350mm long metal soap block. (Because it is made by melt molding, the degree of compression is 100%). This lubricating block was attached to a base material for metal soap with an adhesive to obtain metal soap B.

  The toner polarity control blade C described in Example 3 was used. In addition, metal soap B was used as a lubricant on the surface of the photoreceptor, which is a transfer target.

  The evaluation method of Example 6 was performed in the same manner as in Example 1. The results are shown in Table 1. In Example 6, the same toner as in Example 1 was used.

(Example 7)
<Synthesis of polypyrrole powder A>
20.1 g of pyrrole was dissolved in 300 mL of a hydrochloric acid aqueous solution having a concentration of 1.3 mol / L and cooled to 1.5 ° C. or lower. A solution prepared by dissolving 30.6 g of ammonium persulfate in 53.4 mL of pure water was added dropwise thereto. After completion of dropping, the mixture was stirred at 5 ° C. or lower for 2 hours, sufficiently washed in order of filtration, acetone, water and acetone, and dried to obtain polypyrrole. The product was pulverized in an agate mortar and passed through a predetermined sieve to obtain polypyrrole powder A having an average particle size of 0.005 μm.

<Preparation of toner polarity control blade E>
A toner polarity control blade E was obtained in the same manner except that the polypyrrole powder A was added in place of the polyaniline powder A of the toner polarity control blade A described in Example 1. In addition, metal soap A was used as a lubricant on the surface of the photoreceptor, which is a transfer target. The dispersibility of the polypyrrole powder A in the conductive layer was confirmed by the same method as described in Example 1. The dispersibility of the polypyrrole powder A was good to some extent, but about one small aggregated portion was observed at each observation location.

  The evaluation method of Example 7 was performed in the same manner as Example 1. The results are shown in Table 1. In Example 7, the same toner as in Example 1 was used.

(Example 8)
<Synthesis of polypyrrole powder B>
It was produced by the same method except for the polypyrrole powder A described in Example 7 and the average particle size. The predetermined sieve was changed to obtain polypyrrole powder B having an average particle size of 0.1 μm.

<Preparation of toner polarity control blade F>
A toner polarity control blade F was obtained in the same manner except that the polypyrrole powder B was added in place of the polyaniline powder A of the toner polarity control blade A described in Example 1. In addition, metal soap A was used as a lubricant on the surface of the photoreceptor, which is a transfer target. The dispersibility of the polypyrrole powder B in the conductive layer was confirmed by the same method as described in Example 1. The dispersibility of the polypyrrole powder B was good with no agglomerated sites.

  The evaluation method of Example 8 was performed in the same manner as in Example 1. The results are shown in Table 1. In Example 8, the same toner as in Example 1 was used.

Example 9
<Synthesis of polypyrrole powder C>
It was produced by the same method except for the polypyrrole powder A described in Example 7 and the average particle size. The predetermined sieve was changed to obtain polypyrrole powder C having an average particle size of 4 μm.

<Production of Toner Polarity Control Blade G>
A toner polarity control blade G was obtained in the same manner except that the polypyrrole powder C was added instead of the polyaniline powder A of the toner polarity control blade A described in Example 1. In addition, metal soap A was used as a lubricant on the surface of the photoreceptor, which is a transfer target. The dispersibility of the polypyrrole powder C in the conductive layer was confirmed by the same method as described in Example 1. The dispersibility of the polypyrrole powder C was good with no aggregation sites.

  The evaluation method of Example 9 was performed in the same manner as in Example 1. The results are shown in Table 1. In Example 9, the same toner as in Example 1 was used.

(Example 10)
<Synthesis of polypyrrole powder D>
It was produced by the same method except for the polypyrrole powder A described in Example 7 and the average particle size. The predetermined sieve was changed to obtain a polypyrrole powder D having an average particle size of 5 μm.

<Preparation of Toner Polarity Control Blade H>
A toner polarity control blade H was obtained in the same manner except that the polypyrrole powder D was added in place of the polyaniline powder A of the toner polarity control blade A described in Example 1. In addition, metal soap A was used as a lubricant on the surface of the photoreceptor, which is a transfer target. The dispersibility of the polypyrrole powder D in the conductive layer was confirmed by the same method as described in Example 1. The dispersibility of the polypyrrole powder D was good with no aggregation sites.

  The evaluation method of Example 10 was performed in the same manner as in Example 1. The results are shown in Table 1. In Example 10, the same toner as in Example 1 was used.

(Example 11)
<Preparation of Toner Polarity Control Blade I>
A toner polarity control blade I was obtained in the same manner except that the thickness of the conductive layer of the toner polarity control blade C described in Example 3 was 0.2 mm. In addition, metal soap A was used as a lubricant on the surface of the photoreceptor, which is a transfer target. The dispersibility of the polyaniline powder C in the conductive layer was confirmed by the same method as described in Example 1. The dispersibility of the polyaniline powder C was good with no aggregation sites.

  The evaluation method of Example 11 was performed in the same manner as in Example 1. The results are shown in Table 1. In Example 11, the same toner as in Example 1 was used.

(Comparative Example 1)
<Preparation of toner polarity control blade J>
Toner polarity control is performed in the same manner except that 4 parts by mass of carbon black Specialblack 4A (manufactured by Degussa) is added to 96 parts by mass of the prepolymer instead of the polyaniline powder A of the toner polarity control blade A described in Example 1. Blade J was obtained. In addition, metal soap A was used as a lubricant on the surface of the photoreceptor, which is a transfer target. The dispersibility of carbon black in the conductive layer was confirmed by the same method as described in Example 1. The dispersibility of the carbon black was good to some extent, but several small aggregated portions were observed at each observed location.

  The evaluation method of Comparative Example 1 was performed in the same manner as in Example 1. The results are shown in Table 1. In Comparative Example 1, the same toner as in Example 1 was used.

(Comparative Example 2)
<Preparation of Toner Polarity Control Blade K>
For ethylene adipate-based prepolymer (NCO content 16.5%) degassed for 3 hours under conditions of 3 mmHg at 60 ° C., the ionic liquid 1,2-Dimethyl-3-propyryl-imidazoliumbis (trifluoromethylsulfonyl) imide (Sigma) 4 parts by weight of Aldrich Japan Co., Ltd.) was added to 96 parts by weight of the prepolymer, mixed in a sand mill in a molten state at 90 ° C., and then a polyethylene adipate / 1,4 butanediol / ethylene glycol (mass by weight). The mixture is mixed with a liquid material in which a ratio of 88.6 / 6.8 / 4.6) is mixed, and blade coating is performed to a thickness of about 1 mm on one side of a mold coated with a fluorine-based release agent. The conductive layer was kept at 20 ° C. for 20 minutes. Thereafter, the mixture of the prepolymer and the curing agent was injected, the whole was made to have a thickness of 2 mm, held at 150 ° C. for 1 hour to form an insulating layer, and then the polyurethane rubber cured in a sheet shape was demolded. The polyurethane rubber was allowed to stand on a flat plate at 23 ° C. for 7 days and then cut into a strip shape to obtain a toner polarity control blade K. In addition, metal soap A was used as a lubricant on the surface of the photoreceptor, which is a transfer target.

  The evaluation method of Comparative Example 2 was performed in the same manner as in Example 1. The results are shown in Table 1. In Comparative Example 2, the same toner as in Example 1 was used.

  From the above results, the toner polarity control blade used as a conductive member to which a voltage having a polarity opposite to that of the cleaning roller is applied in the electrostatic cleaning method has a two-layer structure, and the surface on the side in contact with the surface of the transfer material is an electron. When a conductive layer is added with a conductive polymer and the surface that does not come into contact with the surface of the photoreceptor is an insulating layer, a large amount of images can be formed using a small particle size and spherical toner manufactured by a polymerization method. It can be seen that a high-quality full-color image can be obtained without performing an abnormal image.

  In addition, by making the electroconductive polymer polyaniline, preferably polyaniline having an average particle size of 0.1 to 4 μm, the degree of dispersion of the electroconductive polymer becomes preferable, and the metal soap containing zinc in the photoreceptor, It can be seen that the effects of the present invention are maximized by using a mixture of zinc stearate and zinc palmitate.

  As described above, according to the present invention, a long-life full-color cleaning apparatus that provides a high-quality full-color image with stable electrical characteristics, excellent wear resistance, no abnormal images such as voids, uneven density, and uneven color. It has become possible to provide an image forming method and an image forming apparatus using the same.

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Charging device 2a Charging roller 3 Paper feeding cassette 3a Paper feeding roller 5 Transfer device 6 Development device 7 Cleaning device 8 Static elimination lamp 9 Fixing device 10 Paper discharge belt pair 12 Paper conveyance belt 12a Transfer roller 12b Drive roller 13 Conveyance roller Pair 14 Registration roller pair 15 Belt cleaning device 40 Support point 41 Support plate 42 Spring 43 Moving element end 71 Brush roller 71a Brush fiber 71c Core member 72 Collection roller 73 Scraper member 75 Toner polarity control blade 75a Insulating layer 75b Conductive layer 100 Process cartridge 200 Contact Pressure Control Unit 500 Printer 701 Brush Power Supply 702 Recovery Power Supply 706 Blade Power Supply

JP 2006-267737 A JP 2004-239999 A JP 2002-202702 A

Claims (7)

An electrostatic cleaning member that comes into contact with the surface of the transferable transfer body and electrostatically removes toner on the surface of the transfer transfer body by an applied voltage;
Cleaning voltage applying means for applying a voltage to the electrostatic cleaning member;
The electrostatic cleaning member contacts the surface of the transfer body upstream of the surface movement direction of the transfer body with respect to a position where the electrostatic cleaning member contacts the transfer body, and the toner on the surface of the transfer body is charged. A toner polarity control blade that controls the polarity so that the polarity is opposite to the voltage applied to the electrostatic cleaning member by the cleaning voltage applying means,
The toner polarity control blade has at least a two-layer structure, and the surface that contacts the surface of the transfer object is a conductive layer to which an electron conductive polymer is added, and the surface that does not contact the transfer object Is an insulating layer.   The cleaning device according to claim 1, wherein the average particle size of the particles of the electron conductive polymer is 0.1 μm to 4 μm.   The cleaning apparatus according to claim 1, wherein the electron conductive polymer is polyaniline.   The cleaning apparatus according to claim 1, wherein a metal soap containing zinc is applied to the surface of the transfer object.   The cleaning apparatus according to claim 4, wherein the metal soap is a mixture of zinc stearate and zinc palmitate. An electrostatic latent image forming step of forming an electrostatic latent image on the surface of the image carrier;
A developing step of developing the electrostatic latent image formed on the surface of the electrostatic latent image carrier with a developer to form a visible image;
A transfer step of transferring the visible image to a recording medium;
A cleaning step of removing the transfer residual toner attached to the surface using the image carrier after transfer as a member to be cleaned, and an image forming method comprising:
An image forming method, wherein the cleaning step is performed using the cleaning device according to claim 1. An image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the image carrier;
Developing means for developing a latent image formed on the surface of the latent electrostatic image bearing member with a developer to form a visible image;
Transfer means for transferring the visible image to a recording medium;
An image forming apparatus comprising: a cleaning unit that removes transfer residual toner attached to the surface using the image carrier after transfer as a cleaning target;
An image forming apparatus using the cleaning device according to claim 1 as the cleaning unit.