JP5500417B2 - Surface treatment apparatus and transfer material treatment apparatus - Google Patents

Description

  The present invention relates to a surface treatment apparatus for treating the surface of a transfer material and a transfer material processing apparatus.

  Conventionally, an electrophotographic image forming apparatus represented by the Carlson process is known. In this image forming apparatus, generally, a photoconductor having photoconductive characteristics is uniformly charged, and is latent imaged as a charge distribution by image exposure according to an image pattern. The toner image is visualized with toner which is a resin-colored fine particle charged either positively or negatively. Thereafter, the toner image on the photosensitive member is transferred to the surface of the transfer material such as transfer paper by electrostatic force, and is fixed on the transfer material by using the elasticity of the toner by passing between the rollers under pressure. A final toner image can be obtained. The toner fixing means for fixing using the elasticity of the toner generally uses thermal energy.

  The toner fixing means using heat energy is an offset phenomenon in which a part of the toner image adheres to the surface of the fixing member because the surface of the fixing member composed of a heated roller or the like directly contacts the toner image on the transfer material. In addition, there is a possibility that a winding phenomenon occurs in which the transfer material is wound around the fixing member. In order to prevent the offset phenomenon and the wrapping phenomenon of the transfer material, a Teflon (registered trademark) or silicone release layer is provided on the surface of the fixing member, and oil (for example, silicone oil) as a release agent is used as the fixing member. A method of applying to the surface of this is known (for example, see Non-Patent Document 1). Further, there is a method of forming an image using toner added with wax as a release agent so that the amount of oil applied to the surface of the fixing member can be reduced or the oil application itself can be omitted. It is known (for example, see Patent Documents 1 to 4).

In recent years, image forming apparatuses using the electrophotographic system have been increased in speed and image quality, and peripheral devices for paper processing have been enhanced. In addition, it is not necessary to produce a plate in an image forming apparatus using an electrophotographic system. For these reasons, an image forming apparatus using an electrophotographic system has begun to be used in an area where a printing machine such as an offset is conventionally used as a print-on-demand (hereinafter referred to as “POD”) machine. When used as such a POD machine, in order to give added value by post-processing to a transfer material as a printed matter, it is represented by a coating process or a PP (polypropylene) laminate for applying a varnish to the surface of a fixed transfer material. The film may be coated. By such varnish or film coating treatment, it is possible to obtain added value such as a high-grade feeling due to high glossiness, scratches, and rubbing prevention.
However, when the coating process of the varnish or film is performed on the fixed transfer material output from the image forming apparatus (POD device) using the electrophotographic method, the oil for obtaining the above-mentioned release property is obtained. And wax may affect varnish application unevenness on the transfer material and adhesion between the transfer material and the film. That is, since the oil or wax as the release agent is present on the surface of the fixed transfer material, the adhesive of the varnish or film is repelled, and the phenomenon that the varnish cannot be applied uniformly and the transfer material There is a possibility that a phenomenon in which predetermined adhesiveness cannot be obtained with the film may occur.
In order to avoid these phenomena, leave the transfer material until the oil present on the surface of the transfer material decreases due to permeation, etc., or use a special varnish or adhesive added with a surfactant or alcohol. It is possible. However, if there is an inefficient work of leaving the transfer material, the work efficiency is lowered, and the use of a dedicated varnish or adhesive increases the cost.

  Further, when oil or wax as the release agent is present on the surface of the fixed transfer material output from the image forming apparatus using the electrophotographic method, the writing tool is applied to the surface of the fixed transfer material. There is also a problem that it is difficult to make additional writing or stamping, and good writing properties cannot be obtained.

  The present invention has been made in view of the above problems, and its purpose is to avoid a reduction in work efficiency and a high cost, while varnishing the surface of a fixed transfer material on which a toner image is fixed, a film, etc. It is to provide a surface treatment apparatus capable of performing the above coating process satisfactorily and improving the writing property on the surface of the fixed transfer material, and a transfer material processing apparatus including the surface treatment apparatus.

In order to achieve the above object, the invention according to claim 1 is a surface treatment apparatus for treating the surface of a transfer material, wherein the transfer material to be treated has a toner image formed on the surface and is a release mold made of oil. agent is a using fixing member coated transfer material the toner image is fixed, and conveying means for conveying the transfer material the toner image fixing has been that the fixing is performed is formed, the transfer material Discharge means for generating a dielectric barrier discharge on or near the surface of the sheet , and the discharge means forms a gap on the surface of the transfer material conveyed by the conveyance means on which the toner image is formed. A first electrode member having a roller-shaped outer peripheral surface that is opposed to each other and extends in a direction crossing the moving direction of the transfer material, and a dielectric on the entire outer peripheral surface of the roller-shaped conductive member. A layer is formed between the transfer materials A second electrode member provided to face the first electrode member, a voltage applying means for applying a voltage between the first electrode member and the conductive member of the second electrode member, Drive means for rotationally driving the second electrode member, and the conveying means does not wind the transfer material around the outer peripheral surfaces of the first electrode member and the second electrode member, The transfer material is transported so that the transfer material linearly moves in a region where the dielectric barrier discharge is generated opposite to the second electrode member, and is applied to the surface of the fixed transfer material. The release agent composed of the oil applied to the surface of the transfer material while the formed toner image remains is reduced by the dielectric barrier discharge .
Further, the invention of claim 2 is a surface treatment apparatus for treating the surface of a transfer material, wherein the transfer material to be treated uses a toner to which a release agent made of wax is added, and a toner image is formed on the surface. A transfer material formed and on which the toner image is fixed; a transfer means for transferring the transfer material on which the fixed toner image on which the fixing has been performed is formed ; and a surface of the transfer material or the surface of the transfer material comprising a discharge means for generating a dielectric barrier discharge in the vicinity, wherein the discharge means is opposed to the transfer through the voids in the surface of the toner image of the transfer material being conveyed by said conveying means is formed A first electrode member having a roller-shaped conductive outer peripheral surface that extends in a direction crossing the moving direction of the material, and a dielectric layer formed on the entire outer peripheral surface of the roller-shaped conductive member. The first electrode part with a material in between A second electrode member provided so as to face the electrode, voltage applying means for applying a voltage between the first electrode member and the conductive member of the second electrode member, and rotating the second electrode member Driving means, and the conveying means includes the first electrode member and the second electrode member without winding the transfer material around the outer peripheral surfaces of the first electrode member and the second electrode member, respectively. The transfer material is transported so that the transfer material linearly moves in a region where the dielectric barrier discharge is generated opposite to each other, and a toner image formed on the surface of the fixed transfer material is transferred. The release agent composed of the wax existing on the surface of the toner image of the transfer material in the remaining state is reduced by the dielectric barrier discharge .
According to a third aspect of the present invention, in the surface treatment apparatus according to the first or second aspect, a contact angle of water with respect to a portion of the surface of the transfer material treated by the discharge that is present in the toner image is 90 °. It is characterized by the following.
According to a fourth aspect of the present invention, in the surface treatment apparatus according to the first or second aspect, a portion of the surface of the transfer material treated by the discharge is present in the toner image and present in the toner image. The contact angle of water with respect to each non-existing portion is 90 ° or less .
Also, the invention of claim 5, either a surface treatment apparatus smell of claims 1 to 4 Te, before Symbol voltage that the frequency is 20 [kHz] or more and 500 [kHz] in which AC voltage or less It is characterized by.
Further, the invention of claim 6 is the surface treatment apparatus according to claim 5 , wherein the peak-to-peak voltage value of the AC voltage is 5 [kV _p-p ] or more per unit length [mm] of the gap. [KV _p−p ] or less.
According to a seventh aspect of the present invention, in the surface treatment apparatus according to any one of the first to sixth aspects, the material of the first electrode member is stainless steel.
The invention of claim 8, in any of a surface treatment apparatus according to claim 1 to 7, the diameter of the second electrode member is for being greater than the diameter of said first electrode member.
Also, the invention of claim 9, in any of a surface treatment apparatus according to claim 1 to 8, the dielectric constant of the dielectric layer of the second electrode member is 2 or more and 10 or less, the dielectric layer The thickness of is not less than 0.1 [mm] and not more than 5 [mm] .
Also, the invention of claim 1 0, a transfer material processing apparatus for processing a transfer material, a transfer material supplying section which supplies the fixed transfer material the toner image toner image is formed on the surface is fixed A surface treatment device that processes the surface of the transfer material sent from the transfer material supply unit on which the toner image is fixed; and a transfer material output that outputs the transfer material surface-treated by the surface treatment device The surface treatment apparatus is a surface treatment apparatus according to any one of claims 1 to 9 .

  According to the present invention, a transfer material in which a toner image is fixed using a fixing member to which a release agent made of oil is applied, or a toner image formed using a toner to which a release agent made of wax is added. The fixed transfer material is treated so that electric discharge is generated on the surface of the fixed transfer material or in the vicinity of the surface. By this discharge, oil and wax existing on the surface of the transfer material can be reduced and wettability of the surface of the transfer material can be improved. Accordingly, it is possible to satisfactorily perform a coating process such as varnish or film on the surface of the fixed transfer material, and improve the writing property on the surface of the fixed transfer material. In addition, there is no need to perform an inefficient operation of leaving the fixed transfer material for a long time, and it is not necessary to use a special varnish or adhesive added with a surfactant or alcohol for the coating treatment. A decrease in work efficiency and an increase in cost can be avoided.

1 is a schematic configuration diagram of an image forming apparatus according to an embodiment of the present invention. FIG. 3 is an enlarged configuration diagram illustrating a configuration example of a fixing device. FIG. 5 is a schematic diagram showing a state of a transfer material surface before and after a fixing process for fixing a toner image using a fixing member coated with oil on the surface. FIG. 4 is a schematic diagram illustrating a state of a transfer material surface before and after fixing processing for fixing a toner image formed on transfer paper using toner containing wax. FIG. 3 is an explanatory diagram illustrating a state of an additive such as wax added to the toner. Explanatory drawing of a contact angle. The schematic block diagram which shows the example of 1 structure of a surface treatment apparatus. Explanatory drawing of the dimension and positional relationship of a 1st electrode roller and a 2nd electrode roller. FIG. 5 is a schematic diagram showing the surface state before and after discharge processing of a fixed transfer paper on which a toner image has been fixed using a fixing member coated with oil. FIG. 5 is a schematic diagram showing the surface state of a fixed transfer paper, on which a toner image formed on the transfer paper is fixed using toner containing wax, before and after the discharge treatment. (A) And (b) is the SEM photograph of the surface of the transfer paper used in the Example, respectively. Explanatory drawing of the principle of FTIR-ATR method. The graph which shows the wave number dependence of ATR analysis depth (digging depth) dp. (A) and (b) are SEM photographs of the surface of the fixed transfer paper before and after the discharge treatment, respectively. The graph which shows the time transition of the contact angle on the toner image after the discharge process measured about the transfer paper after the fixing process fixed by each of two types of fixing processes. The graph which shows the time transition of the pH value of the surface measured about the transfer paper after the fixing process fixed by each of two types of fixing processes. The graph which shows the time transition of the contact angle of the transfer paper surface measured about each of the transfer paper after discharge processing, and the unprocessed transfer paper. The schematic block diagram of the experimental apparatus used for confirmation of the effect of discharge processing. The schematic block diagram of the surface treatment apparatus which concerns on other embodiment of this invention. FIG. 10 is a schematic configuration diagram of an image forming system according to still another embodiment of the present invention. The schematic block diagram of the transfer material processing apparatus which concerns on other embodiment of this invention. The schematic block diagram of the transfer material processing apparatus which concerns on other embodiment of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic configuration diagram of an image forming apparatus according to an embodiment of the present invention. The image forming apparatus 1 according to the present embodiment is a full color image forming apparatus capable of forming a full color image using an electrophotographic method, and can be used as a full color POD machine.

  The image forming apparatus 1 of this embodiment includes two optical writing units 21 and four toners for forming yellow (Y), magenta (M), cyan (C), and black (K) toner images, respectively. Process units 18Y, 18M, 18C, and 18K as image forming units are provided. The image forming apparatus 1 also forms a registration roller so as to form a transfer paper conveyance path 48 through which transfer paper P as a transfer material supplied from a paper supply unit 43 having two paper supply cassettes 44 is conveyed and output. A pair 49, a manual feed roller 50, a manual tray 51, a manual paper feed path 53, a transport switching device 28, a post-fixing discharge roller pair 56, a transport roller pair 57, 58 for transporting a fixed transfer paper P to be surface-treated. A paper discharge tray 59 as a transfer material output unit is further provided. The image forming apparatus 1 also includes an intermediate transfer unit that transfers the toner image formed by the process units 18Y, 18M, 18C, and 18K to the transfer paper P via the intermediate transfer belt 10 as an intermediate transfer member, and the transfer paper P. A fixing device 25 as a fixing unit for fixing the toner image on the upper side, and a conveying belt for conveying the transfer paper P, onto which the toner image is transferred by the intermediate transfer unit, to the fixing device 25 by a conveying belt 24 stretched around a support roller 23. A unit and a transfer paper re-sending device 28 for forming a toner image on both sides of the transfer paper P are further provided. The image forming apparatus 1 further includes a surface processing device 70 that processes the surface of the fixed transfer paper P output from the fixing device 25, as will be described in detail later.

  Each sheet feeding cassette 44 accommodates a bundle of transfer sheets P, and the uppermost transfer sheet P in the sheet bundle of the sheet feeding cassette 44 is sent out by the rotation driving of the sheet feeding roller 42. The transfer paper delivered from the paper feed cassette 44 is conveyed toward the transfer paper conveyance path 48 by the paper supply rollers 45 and 47 and the paper supply path 46. The manual feed tray 51 on the side surface of the housing is disposed so as to be openable and closable with respect to the housing, and a bundle of paper is manually fed to the upper surface of the tray in an open state with respect to the housing. The uppermost transfer paper in the manually fed paper bundle is sent out toward the transfer paper transport path 48 by the manual feed roller 50.

  Each of the two optical writing units 21 has a laser diode, a polygon mirror, various lenses, and the like, and is sent from an external device such as image information read by an external image reading device (scanner) or a computer device. By driving a light source such as a semiconductor laser (LD) based on the incoming image information, the photoconductors 40Y, M, C, and K of the process units 18Y, 18M, 18C, and 18K are optically scanned. Specifically, the photoconductors 40Y, M, C, and K of the process units 18Y, 18M, 18C, and 18K are rotationally driven in the counterclockwise direction in the drawing by driving means (not shown). The optical writing unit 21 on the left side in the drawing performs optical scanning processing by irradiating the photoconductors 40Y and 40M that are rotationally driven while deflecting laser light in the direction of the rotation axis. Thereby, electrostatic latent images based on the Y and M image information are formed on the photoreceptors 40Y and 40M, respectively. Further, the optical writing unit 21 on the right side in the drawing performs optical scanning processing by irradiating the photoconductors 40C and 40K being rotationally driven while deflecting the laser light in the direction of the rotation axis. Thereby, electrostatic latent images based on the C and K image information are formed on the photoreceptors 40C and 40K.

  Each of the four process units 18Y, 18M, 18C, and 18K has a drum-like photoconductor 40Y, M, C, or K as a latent image carrier. The process units 18Y, 18M, 18C, and 18K support various devices arranged around the photoreceptors 40Y, 40M, 40C, and 40K as a single unit on a common support. Is detachable from the main body of the image forming apparatus. The process units 18Y, 18M, 18C, and 18K have the same configuration except that the colors of the toners used are different from each other. In the image forming apparatus 1 of the present embodiment, these four process units 18Y, 18M, 18C, and 18K are arranged along the endless movement direction so as to face the stretched portion between the support rollers of the intermediate transfer belt 10. It has a so-called tandem configuration.

  Taking the process unit 18Y for forming a yellow (Y) toner image as an example, the process unit 18Y develops an electrostatic latent image formed on the surface thereof into a Y toner image in addition to the photoreceptor 40Y. have. In addition, a charging device that uniformly charges the surface of the photoconductor 40Y that is driven to rotate, or residual toner that adheres to the surface of the photoconductor 40Y after passing through the primary transfer nip for Y is cleaned. And a drum cleaning device. These charging device, developing device, and drum cleaning device are arranged in that order in the rotational direction of the photoreceptor 40Y.

  As the photoreceptor 40Y, a drum-shaped member is used in which a photosensitive layer is formed by coating a photosensitive organic photosensitive material on a base tube made of aluminum or the like. However, an endless belt may be used.

  The developing device for Y develops a latent image using a two-component developer (hereinafter simply referred to as “developer”) containing a magnetic carrier (not shown) and non-magnetic Y toner. As the developing device, a developing device that performs development with a one-component developer not containing a magnetic carrier may be used instead of the two-component developer. The Y toner in the Y toner bottle 180Y is appropriately supplied to the developing device by a Y toner supply device (not shown). The toner that can be used in the developing devices of the process units 18Y, 18M, 18C, and 18K will be exemplified later.

  As the drum cleaning device for Y, a system in which a polyurethane rubber cleaning blade as a cleaning member is pressed against the photoreceptor 40Y is used, but another system may be used. Further, for the purpose of improving the cleaning property, this image forming apparatus employs a system in which a rotatable fur brush is brought into contact with the photoreceptor 40Y. This fur brush also serves to apply the lubricant to the surface of the photoreceptor 40Y while scraping the lubricant from a solid lubricant (not shown) into a fine powder.

  An unillustrated neutralizing lamp is disposed above the photoreceptor 40Y, and this neutralizing lamp is also a part of the process unit 40Y. The neutralizing lamp neutralizes the surface of the photoreceptor 40Y after passing through the drum cleaning device by light irradiation. The surface of the photoreceptor 40Y that has been neutralized is uniformly charged by a charging device, and then subjected to optical scanning by the YM optical writing unit 21 described above. The charging device is rotationally driven while receiving a charging bias from a power source (not shown). Instead of this method, a scorotron charger method in which the photosensitive member 40Y is charged in a non-contact manner may be employed.

  The Y process unit 18Y has been described above, but the M, C, and K process units 40M, C, and K have the same configuration as that for the Y.

  The intermediate transfer unit is disposed below the four process units 40Y, 40M, 40C, and 40K. The intermediate transfer unit is configured to contact the photoreceptors 40Y, M, C, and K with the intermediate transfer belt 10 that is stretched over a plurality of rollers 14, 15, 15 ′, 16, and 63 while being stretched. It is moved endlessly in the clockwise direction in the figure by the rotational drive of any one of the rollers. As a result, primary transfer nips for Y, M, C, and K where the photoreceptors 40Y, M, C, and K abut against the intermediate transfer belt 10 are formed.

  In the vicinity of each of the primary transfer nips for Y, M, C, and K, the intermediate transfer belt 10 is exposed by primary transfer rollers 62Y, 62M, 62C, and 62K as primary transfer members disposed inside the belt loop. It is pressing toward the bodies 40Y, M, C, K. A primary transfer bias is applied to the primary transfer rollers 62Y, 62M, 62C, 62K by a power source (not shown). As a result, a primary transfer electric field for electrostatically moving the toner images on the photoreceptors 40Y, 40M, 40C, 40K toward the intermediate transfer belt 10 is formed in the primary transfer nips for Y, M, C, and K. Has been.

  In the drawing, the toner image is transferred to the front surface of the intermediate transfer belt 10 that sequentially passes through the primary transfer nips for Y, M, C, and K along with the endless movement in the clockwise direction. Are sequentially superimposed and primarily transferred. By this primary transfer of superposition, a four-color superposed toner image (hereinafter referred to as “four-color toner image”) is formed on the front surface of the intermediate transfer belt 10.

  A secondary transfer roller 16 ′ as a secondary transfer member is disposed in the secondary transfer portion 22 below the intermediate transfer belt 10 in the drawing. The secondary transfer roller 16 ′ is in contact with the secondary transfer backup roller 16 on the intermediate transfer belt 10 from the belt front surface to form a secondary transfer nip. As a result, a secondary transfer nip is formed in which the front surface of the intermediate transfer belt 10 and the secondary transfer roller 16 'come into contact with each other.

  A secondary transfer bias is applied to the secondary transfer roller 16 'by a power source (not shown). On the other hand, the secondary transfer backup roller 16 in the belt loop is grounded. Thereby, a secondary transfer electric field is formed in the secondary transfer nip.

  The above-described registration roller pair 49 is disposed on the right side of the secondary transfer unit 22 in the drawing, and the timing at which the transfer paper P sandwiched between the rollers can be synchronized with the four-color toner image on the intermediate transfer belt 10. To feed to the secondary transfer nip. In the secondary transfer nip, the four-color toner images on the intermediate transfer belt 10 are secondarily transferred onto the transfer paper P under the influence of the secondary transfer electric field and the nip pressure, and are combined with the white color of the transfer paper P to form a full-color image.

  Transfer residual toner that has not been transferred to the transfer paper P at the secondary transfer nip is attached to the front surface of the intermediate transfer belt 10 that has passed through the secondary transfer nip. This transfer residual toner is cleaned by a belt cleaning device 17 that contacts the intermediate transfer belt 10.

  The transfer paper P that has passed through the secondary transfer nip is separated from the intermediate transfer belt 10 and transferred to the above-described transport belt unit. In this conveyor belt unit, an endless conveyor belt 24 is stretched endlessly in the counterclockwise direction in the figure by rotating the drive roller while being stretched by two rollers (drive roller, driven roller) 23. The transfer sheet P delivered from the secondary transfer nip is conveyed along with the endless movement of the conveyance belt 24 while being held on the stretched surface on the upper part of the conveyance belt, and is transferred to the fixing device 25.

  FIG. 2 is an enlarged configuration diagram illustrating a configuration example of the fixing device 25. The fixing device 25 includes a fixing belt 26, a fixing roller 27, an elastic drive roller 261, a heating roller 262, a toner removing unit 263, an oil application roller 264, an oil supply roller 265, an oil permeation felt 266, an oil tray 267, and the like. Yes.

  The endless fixing belt 26 is wound around an elastic driving roller 261 and a heating roller 262 including a heat source such as a halogen lamp, and the elastic driving roller 261 is rotated in the clockwise direction in the drawing. Endlessly moves clockwise in the figure. Then, it is heated by the heating roller 262 at a position where it is wound around the heating roller 262. On / off of power supply to the heat source of the heating roller 262 is controlled by a fixing temperature control unit (not shown). The fixing temperature control unit controls the above-described power supply on and off so that a detection result by a temperature sensor (not shown) that detects the surface temperature of the fixing belt 26 becomes a predetermined value.

  A fixing roller 27 containing a heat source such as a halogen lamp is brought into contact with the elastic belt 261 around the fixing belt 26 to form a fixing nip. The fixing roller 27 is driven to rotate counterclockwise in the figure while forming the fixing nip. On / off of the power supply to the heat source of the fixing roller 27 is also controlled by the fixing temperature control unit. The fixing temperature control unit controls the above-described power supply on and off so that a detection result by a temperature sensor (not shown) that detects the surface temperature of the fixing roller 27 becomes a predetermined value.

  The transfer paper P that has passed through the secondary transfer nip is sent into the fixing device 25 and is sandwiched between the fixing nips. The toner image on the transfer paper P is fixed by an action such as pressurization or heating.

  The cleaning web of the toner removing unit 263 is in contact with the fixing belt 26 after passing through the fixing nip. The toner that has adhered to the surface of the fixing belt 26 is wiped off by the cleaning web. The toner removing unit 263 winds a belt-shaped web around a winding roll. And the web extended | stretched from this winding roll can be wound up by rotation of a winding roll. A portion of the web between the winding roll and the winding roll is brought into contact with the fixing belt 26, and an appropriate amount of the web is wound according to the progress of the degree of dirt (wiping operation time) at the portion. By taking up with a take-up roll, a portion of the web that is not soiled is brought into contact with the fixing belt 26.

  An oil application roller 264 is in contact with a portion where the fixing belt 26 is wound around the heating roller 262. The oil application roller 264 rotates while being in contact with the surface of the fixing belt 26 to apply oil (for example, silicone oil) as a release agent to the surface.

  In the vicinity of the oil application roller 264, an oil tray 267, an oil permeating felt 266, and an oil supply roller 265 are disposed. Oil is stored in the oil tray 267. The oil tray 267 is provided with an overflow pipe (not shown) that overflows the oil in the oil tray 267 at a predetermined height position. Oil is regularly supplied to the oil tray 267 by an oil supply device (not shown). At this time, excess oil is returned to the oil supply device via the overflow pipe.

  An oil permeating felt 266 is partially immersed in the oil in the oil tray 267. The oil-penetrating felt 266 soaks the oil into the non-penetrating portion with respect to the oil by capillary action.

  The oil supply roller 265 applies oil wiped from the oil permeation felt 266 to the oil application roller 264 by rotating in contact with the oil permeation felt 266 and the oil application roller 264. As a result, new oil is supplied to the surface of the oil application roller 264 that has lost oil due to oil application to the fixing belt 26.

  The fixing device 25 suppresses toner offset with respect to the fixing belt 26 by applying oil to the fixing belt 26 as described above. Further, by transferring the oil applied to the fixing belt 26 to the fixing roller 27 at the fixing nip where the transfer paper P is not sandwiched, toner offset with respect to the fixing roller 27 is also suppressed.

  In FIG. 1 described above, the transfer paper on which the toner image is transferred to the surface at the secondary transfer nip and the toner image is fixed by the fixing device 25 is sent out toward the surface processing device 70. The transfer paper output from the fixing device 25 is conveyed to the surface processing device 70 via the post-fixing discharge roller pair 56 and the conveyance roller pair 57. The transfer paper surface-treated by the surface treatment device 70 is discharged onto the paper discharge tray 59 via the conveyance roller pair 58.

Next, transfer paper surface treatment using the surface treatment device 70 of the image forming apparatus 1 will be described.
FIG. 3 is a schematic diagram showing the state of the surface of the transfer material before and after fixing processing for fixing a toner image using a fixing member (fixing belt 26, fixing roller 27) coated with oil as a release agent. is there. As shown in FIG. 3, the toner T on the transfer paper P before fixing is fixed on the transfer paper P by electrostatic force in a powder state, but the toner T on the transfer paper P is melted by the fixing process. And fixed on the transfer paper P. The oil 268 for obtaining releasability from the toner surface moves to the surface of the toner image T ′ on the transfer paper P or the surface of the transfer paper P where no toner exists. Therefore, after the fixing process, the oil 268 transferred from the fixing member exists on the entire surface of the transfer paper P including the portion where the toner image T ′ is formed. If an attempt is made to apply a varnish to the surface of the transfer paper P on which the oil 268 exists for the purpose of adding value such as a high-class feeling or a coating treatment of a film such as PP, the adhesion of the varnish or film The agent may be repelled, resulting in a phenomenon that the varnish cannot be applied uniformly and a phenomenon that the predetermined adhesiveness cannot be obtained between the transfer paper P and the film. Further, the surface of the transfer paper P after the fixing on which the oil 268 is present cannot be additionally written with a writing tool or stamped, and there is a possibility that good writing properties may not be obtained.

  FIG. 4 is a schematic diagram showing the state of the transfer material surface before and after the fixing process for fixing the toner image formed on the transfer paper P using toner containing wax as a release agent. FIG. 3 is an explanatory diagram showing a state of an additive such as wax added to the toner. As will be described later, the toner T may include a pigment Tp and a charge control agent Tc, which are mainly composed of a resin Tr, and a wax W as a release agent. Even when the toner image formed on the transfer paper P is fixed using the toner T containing the wax W, the toner T on the transfer paper P before fixing is electrostatically charged in the powder state as in the case of FIG. The toner T is fixed on the transfer paper P by force, and the toner T on the transfer paper P is melted and fixed on the transfer paper P by a fixing process. The wax W contained in the toner exudes to the surface of the toner image T ′ at the time of fixing and exhibits the effect of obtaining releasability from the fixing member (fixing roller), but the toner image T ′ on the transfer paper P after fixing. Remains on the surface. The wax W on the surface of the toner image T ′ may spread and exist on the transfer paper surface around the toner image T ′. Therefore, the phenomenon that the varnish or film cannot be satisfactorily coated and the phenomenon that good writing properties cannot be obtained are not only the case where oil is used for the fixing member of the fixing device 25 but also the toner containing wax. This may also occur when a toner image is formed on the transfer paper. Note that oil may be applied to the fixing member of the fixing device 25 even when toner containing wax is used for the purpose of improving the release margin in fixing.

  Since the oil and wax are for obtaining an effect of improving releasability, they are materials with very low wettability, and it is considered that varnish, adhesive and the like are easy to play. There is a “contact angle” θ as an index representing the wettability, and the wettability can be expressed by the magnitude of the contact angle θ. The contact angle θ is an angle formed between the object 900 and the tangent L of the droplet 901 as shown in FIG.

Generally, the wettability of the surface of the object can be classified into the following three types (1) to (3) according to the magnitude of the contact angle θ.
(1) Spreading wetting: In the case of θ = 0 °, the droplet spreads as far as a thin film.
(2) Immersion wetting: Wetting when a solid is immersed in a liquid when 0 ° <θ ≦ 90 °.
(3) Adhesional wetting: When 90 ° <θ ≦ 180 °, morning dew is on the taro leaf. Although it is said to adhere, it may be said that it does not get wet.

  For the transfer paper on which the toner image is fixed by the oil-coated fixing member or the transfer paper on which the toner image is formed using the wax-containing toner, the present inventors dropped a pure water droplet Dw to drop the contact angle. When θ was measured, it was found that the contact angle θ was a value of 95 ° or more, which was the “adhesion wetting” region of (3) above. Since it is in this “adhesion wet” region, it is considered that the varnish or adhesive does not get wet on the transfer paper after fixing and is easy to play.

  Accordingly, the image forming apparatus 1 according to the present embodiment processes the surface of the transfer paper P output from the fixing device 25 so that the wettability of the surface of the transfer paper P after the fixing can be improved. A device 70 is provided. The surface treatment apparatus 70 includes a discharge unit that generates a discharge on the surface of the transfer paper P on which the fixed toner image is formed or in the vicinity of the surface.

  FIG. 7 is a schematic configuration diagram illustrating a configuration example of the surface treatment apparatus 70 of the present embodiment. The surface treatment device 70 includes a discharge processing unit 700 serving as the discharge unit, and a pair of conveyance rollers serving as conveyance units that convey the transfer paper so that the transfer paper P sent from the fixing device 25 passes through the discharge generation region. 701, 702. The discharge processing unit 700 includes a first electrode roller 703 as a conductive first electrode member, a second electrode roller 704 as a second electrode member provided so as to face the first electrode roller 703, a first Voltage application means for applying a predetermined voltage is provided between the electrode roller 703 and the second electrode roller 704. The first electrode roller 703 faces the surface of the transfer paper P conveyed by the conveyance roller pair 701 and 702 on the surface on which the toner image is formed via a gap G and extends in a direction crossing the moving direction of the transfer paper P. Exist. The second electrode roller 704 is provided so that a dielectric layer 704b is formed on the surface of a roller-shaped cored bar portion 704a made of a conductive member and faces the first electrode roller 703 with the transfer paper P interposed therebetween. Yes. The voltage application means uses a high-frequency transmitter 705 that generates an AC voltage having a predetermined frequency f, and a high-voltage transformer 706 that boosts the magnitude of the AC voltage output from the high-frequency transmitter 705 to a predetermined voltage. Configured. As the high-frequency transmitter 705, for example, a high-frequency power source (CT-0212) manufactured by Kasuga Electric Co., Ltd. can be used, and as the high-voltage transformer 706, for example, a transformer (CT-T02W) manufactured by Kasuga Electric Co., Ltd. is used. be able to. In the example of FIG. 7, the cored bar 704 a of the second electrode roller 704 and the ground terminal of the high-frequency transmitter 705 are both grounded, and an AC voltage having a predetermined frequency and voltage value of the high-voltage transformer 706 is output. The output terminal 706a is connected to the first electrode roller 703. When a predetermined AC voltage is applied to the first electrode roller 703, a dielectric is generated in the gap G between the first electrode roller 703 and the surface of the transfer paper P being conveyed in contact with the second electrode roller 704. Body barrier discharge occurs.

  In the surface treatment apparatus 70 having the above configuration, the frequency f of the AC voltage output from the high-frequency transmitter 705 is preferably in the range of 20 [kHz] or less and 500 [kHz] or less. A region lower than 20 [kHz] and up to 20 [Hz] overlaps with the human audible region, and the sound generated during discharge is unpleasant and unpleasant, which is not preferable. Further, in a frequency range up to a direct current lower than 20 [Hz], uniform discharge does not occur in the axial direction of the first electrode roller 703 and the second electrode roller 704 (discharge is concentrated locally), which is preferable. Absent. On the other hand, in a frequency region higher than 500 [kHz], a low-resistance discharge channel is easily formed by residual ions generated by the stay of ions generated by discharge in the gap G, and the discharge is locally concentrated and uniform. In addition to being unable to process, a large current flows and high heat is generated, which is not preferable for safety. In this case, the waveform of the AC voltage output from the high-frequency transmitter 705 is not particularly limited as long as the frequency is in the range of 20 [kHz] to 500 [kHz], and even a sine wave is a square wave. (Including a pulse waveform).

  The output voltage value (peak-to-peak voltage) of the high-voltage transformer 706 applied to the first electrode roller 703 includes the dielectric characteristics and thickness of the transfer paper P and the dielectric layer 704b of the second electrode roller 704, and the first electrode roller 703 What is necessary is just to determine suitably according to the magnitude | size of the gap | interval with the 2nd electrode roller 704, but this gap is the range of 5 [kVp-p] or more and 30 [kVp-p] or less with respect to 1 [mm]. Is preferred. When the output voltage value of the high-voltage transformer 706 is lower than 5 [kVp-p], it is not preferable because the breakdown voltage of the air existing in the gap may not be reached and the discharge may not be performed. On the other hand, when the output voltage value of the high-voltage transformer 706 is higher than 30 [kVp-p], there is a high possibility that arc discharge will occur between the first electrode roller 703 and the surrounding members. Since the gap between the first electrode roller 703 and the second electrode roller 704 and the preferred range of the output voltage value of the high-voltage transformer 706 are substantially proportional to each other, when the gap is other than 1 [mm] What is necessary is just to determine the output voltage value of the high voltage | pressure transformer 706 with respect to the said gap | interval based on 5-30 [kVp-p] which is a suitable range in the case of said 1 [mm].

  Further, the size of the gap g (see FIG. 8) between the first electrode roller 703 and the second electrode roller 704 may be not less than the thickness of the transfer paper P to be processed, and is generally not more than 3 [mm]. Is preferred. If it is larger than 3 [mm], a high voltage is required for discharging, which is not preferable.

  The material of the first electrode roller 703 may be appropriately selected from metals such as iron, copper, aluminum, and stainless steel, but stainless steel that is not easily corroded by ozone generated during discharge is preferable. The core material of the second electrode roller 704 is the same as the material of the first electrode roller 703.

  The diameter R2 of the second electrode roller 704 is preferably larger than the diameter R1 of the first electrode roller 703 (see FIG. 8). That is, it is more preferable that the second electrode roller 704 is regarded as a flat surface when viewed from the first electrode roller 703 side. Thus, since the second electrode roller 704 appears to be regarded as a flat surface from the first electrode roller 703 side, a wider and uniform discharge region at a position where the first electrode roller 703 and the second electrode roller 704 face each other ( It is possible to apply a so-called creeping discharge region generated in the transfer paper moving direction) to the surface of the transfer paper P, and a uniform and efficient processing effect can be obtained. On the other hand, when the diameter of the second electrode roller 704 is smaller than the diameter of the first electrode roller 703, the discharge region concentrates on the shortest distance region between the first electrode roller 703 and the second electrode roller 704, and creeping discharge occurs. Since the distance is shortened, processing is performed in a very narrow region (line shape). Accordingly, even if the transfer speed of the transfer paper P is very slight, processing unevenness occurs in the surface of the transfer paper P, and deterioration of the dielectric layer and the like is promoted due to the concentrated discharge power. End up.

  The material of the dielectric layer 704b of the second electrode roller 704 is a plastic such as acrylic, polyester, polyethylene, polytetrafluoroethylene, polyimide, rubber such as silicon rubber, ceramics such as glass, quartz, alumina, zirconia, and titania. However, glass, quartz, alumina, or the like that is not easily eroded by discharge and has a relative dielectric constant of 2 or more and 10 or less is preferable. A relative dielectric constant smaller than 2 is not preferable because a high voltage is required for discharging. Further, when the relative dielectric constant is larger than 10, the discharge tends to concentrate locally, which is not preferable.

  The thickness t2 (see FIG. 8) of the dielectric layer 704b is preferably 0.1 [mm] or more and 5 [mm] or less. When it is thinner than 0.1 [mm], arc discharge is caused by dielectric breakdown, which is not preferable for safety. In the case of glass, quartz, alumina or the like, it is more preferable if it is 1 [mm] or more in consideration of mechanical strength. If it is thicker than 5 [mm], a high voltage is required for discharge, which is not preferable.

  Further, in order to reduce erosion of the dielectric layer 704b due to electric discharge, it is preferable that the second electrode roller 704 is covered with a dielectric over the entire circumference and rotated. The second electrode roller 704 can be rotationally driven by driving means such as a motor (not shown).

  FIG. 9 is a schematic diagram showing the surface state before and after the discharge treatment of the fixed transfer paper on which the toner image is fixed using the fixing member having the oil applied to the surface. As shown in the figure, when a surface treatment that generates discharge DS is performed on the surface of the fixed transfer paper P having oil 268 on the surface, a toner image portion and a toner image are formed on the surface of the transfer paper P. The oil 268 that was present on the surface of any unexposed portion is reduced. Thus, although the mechanism by which the oil 268 is reduced is not clearly understood, the phenomenon that the oil 268 existing on the surface of the transfer paper P permeates into the toner image and the transfer paper P due to the discharge DS. It is considered that the promoting action and the discharging action such as “oxidation”, “crosslinking”, “decomposition” are related. Further, the discharge DS is considered to have an action of generating a hydrophilic functional group on the surface of the fixed transfer paper P. The wettability on the surface of the fixed transfer paper P is improved by the generation of the hydrophilic functional group and the reduction of the oil. When the contact angle θ of pure water is actually measured on the surface of the transfer paper P after the discharge treatment, the contact angle θ of 95 ° or more before the surface treatment is reduced to 90 ° or less. By improving the wettability on the surface of the fixed transfer paper P in this way, the surface of the fixed transfer paper P can be satisfactorily coated with varnish, film, and the like. The writing property on the surface of the paper P can be improved.

  FIG. 10 is a schematic diagram showing the surface state of the fixed transfer paper on which the toner image formed on the transfer paper is fixed using the toner containing wax before and after the discharge treatment. As shown in the figure, when a surface treatment for generating a discharge DS is performed on the surface of the fixed transfer paper P on which the toner image T ′ is formed using the toner containing wax on the surface, the toner on the transfer paper P The wax W existing on the surface of the image T ′ is reduced. Although the mechanism for reducing the wax W is not clearly elucidated in this way, the action of promoting the phenomenon of the wax W existing on the surface of the transfer paper P penetrating into the toner image due to the discharge DS, It is considered that the discharge action such as “oxidation”, “crosslinking”, “decomposition” is related. Also in this case, the discharge DS is considered to have a function of generating a hydrophilic functional group on the surface of the fixed transfer paper P. Due to the generation of the hydrophilic functional group and the reduction of the wax, the wettability on the surface of the fixed transfer paper is improved. Then, when the contact angle θ of pure water is actually measured on the surface of the transfer paper P after the discharge treatment, what is 95 ° or more before the surface treatment is reduced to 90 ° or less. By improving the wettability on the surface of the fixed transfer paper P in this way, the surface of the fixed transfer paper P can be satisfactorily coated with varnish, film, and the like. The writing property on the surface of the paper P can be improved.

  Next, an example in which a more quantitative result is obtained regarding the improvement of the wettability of the fixed transfer paper P by the discharge process will be described. In this embodiment, two types of transfer paper X (manufactured by Oji Paper Co., Ltd., POD gloss coated paper) and transfer paper Y (manufactured by Oji Paper Co., Ltd., POD mat coated paper) are used, and two types of toner to which wax is added. After forming a toner image using A and toner B, a fixing process was performed using a fixing member on which the oil was applied.

  FIGS. 11A and 11B are photographs (magnification: 250 times) obtained by scanning the surface of transfer paper X and transfer paper Y before forming a toner image with a scanning electron microscope (SEM), respectively. From these SEM image photographs, it can be seen that the smoothness of the surface of the transfer paper X is higher than that of the transfer paper Y.

The toner A and the toner B are manufactured as follows.
(Manufacture of toner A)
After pre-mixing two types of binder resin, two types of release agents, and coloring agents shown below using a Henschel mixer (Mitsui Miike Chemical Industries, Ltd., FM10B), a twin-screw kneader (stock) It was melted and kneaded at a temperature of 100 to 130 ° C. by a company Ikekai, PCM-30). The obtained kneaded product was cooled to room temperature and then coarsely pulverized to 200 to 300 μm with a hammer mill. Next, after finely pulverizing using a supersonic jet pulverizer, Labo Jet (manufactured by Nippon Pneumatic Industry Co., Ltd.), adjusting the pulverization air pressure appropriately so that the weight average particle diameter becomes 6.0 ± 0.3 μm. The louver opening is adjusted so that the weight average particle size is 6.8 ± 0.3 μm, and the amount of fine powder of 4 μm or less is 10% by number or less with an airflow classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I). Classification was carried out with appropriate adjustment to obtain toner base particles. Subsequently, 2 types of additives shown below were stirred and mixed with 100 parts by mass of toner base particles with a Henschel mixer.

-Binder resin: Binder resin A: polymer of terephthalic acid, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, softening point: 110 ° C, glass transition temperature: 60 ° C, acid value: 5 , Mn: 2800, Mw: 8000, 50 parts by weight
Binder resin B: terephthalic acid, fumaric acid, trimellitic acid, bisphenol A propylene oxide addition product, bisphenol A ethylene oxide addition polymer, softening point: 200 ° C., glass transition temperature: 66 ° C., acid value: 12, Mn: 2800, Mw: 45000, 50 parts by weight, mold release agent: mold release agent A ... Carnauba wax, melting point 78 ° C 3 parts by weight
Release agent B: ethylene bis-stearic acid amide, melting point 145 ° C. 2 parts by weight, colorant: carbon black 10 parts by weight, additive: inorganic fine particles A: SiO ₂ (surface is hydrophobic with silane coupling agent ), Average particle size 0.01 μm, addition amount 1.0 part by weight
Inorganic fine particle B ... TiO ₂ (surface hydrophobized with silane coupling agent), average particle size 0.02 μm, addition amount 1.0 part by weight

(Manufacture of toner B)
It was carried out in the same manner as in the production of the toner A, using the following two prescription amounts of binder resin, release agent, colorant and additive.

-Binder resin: Binder resin A: polymer of terephthalic acid, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, softening point: 100 ° C, glass transition temperature: 65 ° C, acid value: 5 mgKOH / G, Mn: 2800, Mw: 13000, 50 parts by weight
Binder resin B: terephthalic acid, fumaric acid, trimellitic acid, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide addition polymer, softening point: 140 ° C, glass transition temperature: 65 ° C, acid value: 16, Mn: 2400, Mw: 45000, 50 parts by weight, mold release agent: carnauba wax, melting point 78 ° C 5 parts by weight, colorant: carbon black 10 parts by weight, additive: inorganic fine particles A ... SiO ₂ (The surface is hydrophobized with a silane coupling agent), the average particle diameter is 0.01 μm, and the addition amount is 1.0 part by weight.
Inorganic fine particle B ... TiO ₂ (surface hydrophobized with silane coupling agent), average particle size 0.02 μm, addition amount 1.0 part by weight

  Here, the characteristic values of the polyester resin in the production of the toners A and B were measured as follows.

[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger, and a nozzle with a diameter of 1 mm and a length of 1 mm was applied. Extrude. The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.

[Glass transition point of resin]
Using a differential scanning calorimeter (DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.), 0.01 to 0.02 g of the sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature decreasing rate was 10 ° C. / A sample cooled to 0 ° C in minutes is heated at a rate of temperature increase of 10 ° C / min, and shows the maximum slope from the peak rising portion to the peak apex, and the baseline extension below the maximum endothermic peak temperature. The temperature at the intersection with the tangent line.

[Acid value of the resin]
Measured according to the method of JIS K0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Content of low molecular weight component having resin molecular weight of 500 or less]
The molecular weight distribution is measured by gel permeation chromatography (GPC). Add 10 ml of tetrahydrofuran to 30 mg of toner, mix for 1 hour with a ball mill, and filter using a fluororesin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) with a pore size of 2 μm to remove insoluble components to prepare a sample solution. To do.
Tetrahydrofuran is flowed as an eluent at a flow rate of 1 ml / min, the column is stabilized in a constant temperature bath at 40 ° C., and 100 μl of the sample solution is injected to perform measurement. In addition, “GMHLX + G3000HXL” (manufactured by Tosoh Corp.) is used as an analytical column, and several types of monodisperse polystyrene (2.63 × 103, 2.06 × 104, manufactured by Tosoh Corp.) are used as the molecular weight calibration curve. 0.02 × 105, 2.10 × 103, 7.00 × 103, 5.04 × 104, manufactured by GL Sciences Inc.) are prepared as standard samples.
The content (%) of the low molecular weight component having a molecular weight of 500 or less is the ratio of the area of the corresponding area in the chart area obtained by the RI (refractive index) detector to the total chart area (area of the corresponding area / total chart area). ).

For the analysis of oil and wax on the surface of the transfer paper P, FTIR (Fourier transform infrared spectroscopy) -ATR (Attenuated Total Reflection) method was used. In this FTIR-ATR method, as shown in FIG. 12, infrared light is totally reflected at the interface between the ATR crystal 910 and the sample 911 (transfer paper in this embodiment), and the sample is slightly stained from the reflection surface to the sample 911 side. This is a method for detecting the light to be emitted. The ATR analysis depth (penetration depth) dp is defined as a depth at which the intensity of light incident on the interface becomes 1 / e. When the sample 911 does not absorb, it is expressed by the following equation.

Here, θ is an incident angle (41.5 °), n ₂₁ is n ₂ / n ₁ (n _{1 is} the refractive index of the ATR crystal 910, n _{2 is} the refractive index of the sample 911), and λ ₁ is λ / n _1. (Wavelength of light in the ATR crystal). When the ATR crystal 910 is a Ge crystal, the value of n ₁ is 4.0.

FIG. 13 is a graph showing the wave number dependence of the ATR analysis depth (digging depth) dp when a Ge crystal is used as the ATR crystal 910 and the incident angle θ is 41.5 °. The refractive index n2 of the sample 911 was assumed to be 1.5, which is a general value for organic substances. As shown in the figure, the analysis depth dp becomes shallower as the wave number increases, and becomes 0.8 [μm] at a wave number of 1000 [cm ⁻¹ ] and about 0.3 [μm] at a wave number of 3000 [cm ⁻¹ ]. Here, for example, since the absorption wave number peculiar to wax is 2890 [cm ⁻¹ ], the depth (depth) measured by the FTIR-ATR method is about 0.3 [μm] according to FIG. 13. Therefore, the absorption of infrared rays by wax or oil existing only on the surface of the toner image can be detected by the FTIR-ATR method, and the amount thereof can be measured.

Tables 1 and 2 show the oil and wax on the toner image before and after the discharge treatment on the fixed transfer paper X (POD gloss coated paper) on which the toner image (solid image) is formed using the toner A and the toner B. The result of measuring the amount of is shown. The values in Tables 1 and 2 are values obtained by measuring the measured values of oil and wax before the discharge treatment as 1.0, and obtaining the measured values of oil and wax after the discharge treatment based on the measured values. Tables 1 and 2 also show the results of measurement of oil and wax on the toner image of the transfer paper X when left for a predetermined time without performing discharge processing after fixing. The value when left without the discharge treatment is also a value obtained by setting the measured value before the discharge treatment to 1.0.

  As shown in Tables 1 and 2, for both toner A and toner B, the oil and wax on the toner image on the transfer paper are reduced by the discharge treatment. Note that the toner B is reduced in oil even when the toner B is left without being discharged after fixing. This is because after fixing the toner image composed of toner B on the transfer paper X, the oil existing on the surface gradually infiltrated into the toner image while leaving without performing the above discharge treatment. It is thought to be due to.

  14A and 14B are SEM photographs (magnification: 3000 times) of the surface of the fixed transfer paper before and after the discharge treatment, respectively. As shown in FIG. 14A, oil used for fixing remains on the surface of the fixed transfer paper before the discharge treatment. When the discharge treatment is performed on the transfer paper, almost no oil is observed as shown in FIG.

Table 3 shows the result of measuring the contact angle θ on the transfer paper before and after the discharge treatment for each of the fixed transfer paper X (POD gloss coated paper) and transfer paper Y (POD matte coated paper). The contact angle θ was measured by dropping pure water droplets onto the surfaces of the fixed transfer papers X and Y. As shown in Table 3, the transfer paper before the discharge treatment has a contact angle θ of 80 ° or more and is not so good in wettability, but the contact angle θ on the surface of each transfer paper X, Y is 50 ° by the discharge treatment. The wettability was improved as follows.

Table 4 shows the contact angle θ on the toner image before and after the discharge processing for two types of fixed transfer paper X (POD gloss coated paper) on which toner images (solid images) are formed using toner A and toner B, respectively. The measurement result is shown. The contact angle θ was measured by dropping pure water droplets onto the toner image of the fixed transfer paper. As shown in Table 4, for both toner A and toner B, the contact angle θ of the toner image on the transfer paper before the discharge treatment is a large value (a value greater than 90 °) of 100 ° or more, and the wettability is high. Although not good, the contact angle θ became a value of 70 ° or less which is much lower than 90 ° by the discharge treatment, and the wettability was improved.

  FIG. 15 shows a toner image (solid image) after the discharge process, measured on the transfer paper X (POD gloss coated paper) after the fixing process fixed by two types of fixing processes (oil application fixing and oilless fixing). It is a graph which shows the time transition of the upper contact angle (theta). The toner image on each transfer paper is formed using a toner containing wax. The contact angle θ was measured by dropping pure water droplets on the surface of the fixed transfer paper. It should be noted that the contact angle θ before the discharge treatment is a large contact angle θ of 100 ° or more in any case, such as 103 ° in the case of the oil application fixing and 104 ° in the case of the oilless fixing. Value (greater than 90 °) and wettability was not good. As shown in FIG. 15, after performing the above-described discharge treatment, the contact angle θ increases with time in both the oil application fixing and the oilless fixing, but it remains below 90 ° even after 70 hours. Could be maintained.

  FIG. 16 shows one of the factors affecting the contact angle θ measured for the transfer paper X (POD gloss coated paper) after the fixing process fixed by two types of fixing processes (oil application fixing and oilless fixing). 6 is a graph showing the time transition of the pH value of the transfer paper surface that is considered to be a problem. This pH value is considered to change depending on the density of hydrophilic functional groups generated on the transfer paper surface. As the density of the hydrophilic functional group present on the transfer paper surface increases, the pH value decreases and becomes acidic, and the contact angle θ decreases and wettability improves. The pH value of the transfer paper surface before the discharge treatment was 6.8 in both cases of the two types of fixing treatments (oil application fixing and oilless fixing). As shown in FIG. 16, in both cases of the above two types of fixing processes (oil application fixing and oilless fixing), after performing the discharging process, the pH value increases as time passes, After the lapse of time, it returned to the pH value (6.8) before the discharge treatment. Thus, when 48 hours or more have elapsed from the discharge treatment, the pH value (6.8) before the discharge treatment is restored, so that the hydrophilic functional group generated by the discharge treatment is considered to have almost disappeared.

  FIG. 17 is a graph showing the time transition of the contact angle θ of the surface of the transfer paper X (POD gloss coated paper) measured with and without the discharge treatment. The contact angle θ was measured by dropping pure water droplets on the surface of the transfer paper X. As shown in FIG. 17, when the discharge treatment was not performed, the contact angle θ of the transfer paper surface changed from 78 ° to 83 ° of 90 ° or less. On the other hand, the contact angle θ on the surface of the transfer paper when the discharge treatment is performed increases with time from 46.6 ° immediately after the discharge treatment, but is maintained at a value of 65 ° or less. It did not return to the contact angle θ (= 78 ° to 83 °) when the treatment was not performed. From the results of FIG. 17 and the results of FIG. 16, the contact angle θ of the transfer paper surface and the toner image surface is maintained at a low level of 65 ° or less after the discharge process and the wettability is maintained. It is considered that the deterioration does not deteriorate because the contribution of the oil and wax reduction effect by the discharge treatment is large.

Table 5 shows the writing properties before and after the discharge process (ballpoint pen, pencil, oiliness, magic, seal, etc.) for the transfer paper after the fixing process in which the toner image was fixed by two types of fixing processes (oil application fixing, oilless fixing). The result of examining a fluorescent pen and a water-based pen) is shown. This writing property was examined for two types of transfer paper: copy paper (Ricoh Co., Ltd., “My Recycle Paper GP”) and POD gloss coated paper (Ricoh Co., Ltd., “Business Coat Gloss 100”). As shown in Table 5, for both of the two types of fixing processes (oil application fixing and oil-less fixing), the above-described discharge process improved the writing performance of a writing instrument (fluorescent pen, aqueous pen) using water-based ink. .

  FIG. 18 is a schematic configuration diagram of a surface treatment apparatus used in a confirmation experiment of the effect of the discharge treatment in the image forming apparatus of the present embodiment. This surface treatment apparatus can be used as the surface treatment apparatus 70 incorporated in the image forming apparatus 1 (see FIG. 1) having the above-described configuration or a transfer material treatment apparatus described later. In FIG. 18, a discharge electrode 710 as a first electrode member is a round bar made of stainless steel having a diameter of 6 mm and a length of 300 mm. The ground electrode 711 as the second electrode member is an aluminum plate having a thickness of 5 mm and a length in the discharge electrode axial direction of 300 mm, and is grounded. A dielectric 712 made of a glass plate having a thickness of 1 mm is provided on the surface side of the ground electrode 711 on which the transfer paper P is placed. The ground electrode 711 and the dielectric 712 are fixed to the insulating frame 713 so that the distance between the discharge electrode 710 and the dielectric 712 is 1 mm, and a speed of 500 [mm / s] by an electric slider (EZ limo manufactured by Oriental Motor) 714. ] To slide under the discharge electrode 710 in a direction perpendicular to the discharge electrode axis. At this time, a high frequency high voltage is applied to the discharge electrode 710 by a high frequency transmitter (CT-0212 manufactured by Kasuga Electric Co., Ltd.) 705 and a high voltage transformer (CT-T02W manufactured by Kasuga Electric Co., Ltd.), and discharged at a power of 500 W. The transfer paper P was processed by placing the transfer paper P of each color 100% solid image output by the electrophotographic image forming apparatus on the dielectric 712. The electrophotographic image forming apparatus includes two types of color image forming apparatuses (image forming apparatus A: on-demand printing apparatus “Pro C900” manufactured by Ricoh Co., Ltd.) and image forming apparatus B: manufactured by Ricoh Co., Ltd. A digital color multifunction machine “image MP MP4000”) was used. Then, a solid image composed of toners of yellow (Y), magenta (M), cyan (C), and black (K) was formed on the transfer paper P to be processed by each of the image forming apparatuses A and B.

Table 6 shows the results of coating the transfer paper P discharged with the above-described experimental apparatus with UV varnish (Dicuacriya UV-1245, manufactured by DIC) with the number 4 wire bar, and the untreated untreated 2 shows the results of a comparative example in which the same transfer paper was coated. As shown in Table 6, when the discharge treatment was performed on the fixed transfer paper P, both of the two types of transfer paper on which the toner images of the respective colors used in the experiment were respectively formed on the transfer paper surface. The varnish could be applied uniformly and good coating results were obtained. On the other hand, in the comparative example in which the discharge treatment was not performed, the above varnish could not be uniformly applied to the transfer paper surface for any of the above transfer papers, resulting in poor coating.

  As described above, according to the present embodiment, the transfer sheet P on which the toner image is fixed using the fixing member to which the release agent made of oil is applied by the surface treatment apparatus 70 or the release agent made of wax is used. The transfer paper P on which the toner image formed using the added toner is fixed is processed so as to generate dielectric barrier discharge on the surface of the fixed transfer paper P or in the vicinity thereof. Thereby, this discharge can reduce the oil present on the surface of the transfer paper P and improve the wettability of the surface of the transfer paper P. Accordingly, it is possible to satisfactorily perform a coating process such as varnish or film on the surface of the fixed transfer paper P, and improve the writing property on the surface of the fixed transfer paper P. In addition, it is not necessary to perform an inefficient operation of leaving the fixed transfer paper P for a long time, and it is not necessary to use a special varnish or adhesive added with a surfactant or alcohol for the coating treatment. Therefore, it is possible to avoid a decrease in work efficiency and an increase in cost.

  In particular, according to the present embodiment, a dielectric barrier discharge is generated between the surface of the first electrode member 703 and the surface of the dielectric layer 704b of the second electrode roller 704 through the fixed transfer paper P. I am letting. By utilizing this dielectric barrier discharge, discharge can be intensively generated in the gap G between the surface of the first electrode member 703 and the surface of the transfer paper P, so that the surface of the transfer paper P or the surface thereof Discharge can be generated efficiently and reliably.

  In the above embodiment, the surface treatment device 70 and the image forming apparatus 1 including the surface treatment device 70 according to the present invention have been described. However, the present invention is not limited to these examples. The surface treatment apparatus of the present invention may be configured as in other embodiments described later, and the present invention can also be applied to an image forming system and a transfer material processing apparatus as described later.

  FIG. 19 is a schematic configuration diagram of a surface treatment apparatus 70 according to another embodiment of the present invention. In the surface treatment apparatus 70 of the present embodiment, an electrode plate 720 made of a conductive material is used as the second electrode member facing the first electrode roller 703. As a material of the electrode plate 720, for example, an aluminum plate can be used. A dielectric belt 721 is stretched between a plurality of rollers 722 and 723 so that the back surface thereof is in contact with the electrode plate 720. Either one of the rollers 722 and 723 rotates and drives the dielectric belt 721 as a driving roller, whereby the transfer paper P to be processed can be held and conveyed on the dielectric belt 721. Also in this surface treatment apparatus 70, a gap between the surface of the transfer paper P conveyed by the dielectric belt 721 and the first electrode roller 703 is applied by applying the predetermined alternating voltage to the first electrode roller 703. The transfer paper P can be surface-treated by generating a discharge in G. In the surface treatment apparatus 70 of FIG. 19, a conductive roller may be disposed instead of the electrode plate 720 as the second electrode member facing the first electrode roller 703. In this case, the dielectric layer may not be provided on the surface of the conductive roller as the second electrode member.

  FIG. 20 is a schematic configuration diagram of an image forming system according to still another embodiment of the present invention. The image forming system of the present embodiment is a combination of a normal image forming apparatus 1 ′ that does not include the surface processing apparatus and a transfer material processing apparatus 2 that is a peripheral apparatus including the surface processing apparatus. In FIG. 20, various members and devices constituting the image forming apparatus 1 ′ can be the same as those in the image forming apparatus 1 shown in FIG. To do. The image forming apparatus 1 ′ includes a transfer material output unit provided with a post-fixing discharge roller pair 56 so that the fixed transfer paper processed by the fixing device 25 is output to the transfer material processing apparatus 2. . Further, the transfer material processing apparatus 2 constituting the image forming system of the present embodiment includes a transfer material input unit to which a fixed transfer paper output from the image forming apparatus 1 ′ is input, and an input from the transfer material input unit. A surface processing device 70 for processing the surface on which the toner image of the transferred transfer material is fixed, and a paper discharge tray 203 as a transfer material output unit to which the transfer material surface-treated by the surface processing device 70 is output. I have. The transfer material input portion is provided so as to face the transfer material output portion provided with the post-fixing discharge roller pair 56 of the image forming apparatus 1 ′. With such a configuration, the transfer paper transport path 48 is formed from the paper feed position of the paper feed cassette 44 of the image forming apparatus 1 ′ to the paper discharge tray 203 of the transfer material processing apparatus 2. Further, the surface treatment apparatus 70 provided in the transfer material processing apparatus 2 includes discharge means for generating discharge on or near the surface of the transfer paper that has been subjected to the fixing process. For example, FIG. Alternatively, a transfer processing apparatus having the same configuration as that shown in FIG. 19 can be used. In the image forming system of the present embodiment, when the toner image is formed by the image forming apparatus 1 ′ and the fixing process is completed, the fixed transfer paper is transferred from the transfer paper output unit of the image forming apparatus 1 ′ to the transfer material processing apparatus 2. To be introduced. When the discharge processing is completed in the surface treatment device 70 of the transfer material processing device 2, the processed transfer paper P with improved wettability is discharged onto the paper discharge tray 203.

  FIG. 21 is a schematic configuration diagram of a transfer material processing apparatus according to still another embodiment of the present invention. The transfer material processing apparatus 3 of this embodiment is an independent installation type that can be installed independently of the image forming apparatus at a position away from the installation place of the image forming apparatus that forms a toner image on the transfer material to be processed. It is a device. The transfer material processing apparatus 3 includes a paper feed cassette 301 as a transfer material supply unit that supplies a fixed transfer paper P with a toner image formed on the surface thereof, and a transfer paper P supplied from the paper feed cassette 301. A surface processing device 70 that processes the surface on which the toner image is fixed, and a paper discharge tray 311 as a transfer material output unit that outputs the transfer paper P surface-treated by the surface processing device 70 are provided. The paper feed cassette 301 accommodates a bundle of transfer paper P that has been subjected to a fixing process, and the uppermost transfer paper P in the paper bundle of the paper feed cassette 301 is sent out by the rotational drive of the paper feed roller 302. The transfer paper P sent out from the paper feed cassette 301 is transported toward the surface treatment apparatus 70 by the paper feed roller 303 and the transport rollers 304 to 309. The transfer paper P, which has been discharged by the surface treatment device 70 and output, is output onto the paper discharge tray 311 by the paper discharge roller pair 310. With this configuration, the transfer paper conveyance path 300 is formed from the paper feed position of the paper feed cassette 301 to the paper discharge tray 311. Also in the present embodiment, the surface treatment apparatus 70 includes discharge means for generating a discharge on or near the surface of the transfer paper that has been subjected to the fixing process. For example, FIG. 7, FIG. 18 or FIG. A transfer processing apparatus having the same configuration as that shown in FIG. 19 can be used. In the transfer material processing apparatus 3 of the present embodiment, when a plurality of fixed transfer papers are set together in the paper feed cassette 301 and a user operates a process start button on an operation unit (not shown), for example, A plurality of transfer sheets P are automatically fed one by one in order from the top, and a predetermined discharge process is performed by the surface treatment apparatus 70, and the processed transfer sheet P with improved wettability is placed on the discharge tray 301. Continuously discharged.

  FIG. 22 is a schematic configuration diagram of a transfer material processing apparatus according to still another embodiment of the present invention. The transfer material processing apparatus 4 of the present embodiment is an independent installation type apparatus that can be installed independently of the image forming apparatus, similarly to the transfer material processing apparatus 3 of FIG. Unlike the configuration example of FIG. 21, the transfer material processing apparatus 4 of this embodiment includes a manual feed tray 401 instead of a paper feed cassette as a transfer material supply unit that supplies a fixed transfer paper P. The transfer paper P set on the manual feed tray 401 is sent out toward the surface treatment apparatus 70 by the manual feed roller 402 and introduced into the surface treatment apparatus 70 by the conveyance roller 404. Further, the transfer paper P that has been discharged by the surface treatment device 70 and output is output onto a paper discharge tray 405 by a paper discharge roller pair 405. With this configuration, the transfer paper transport path 400 is formed from the manual feed tray 401 to the paper discharge tray 405. Also in the present embodiment, the surface treatment apparatus 70 includes discharge means for generating a discharge on or near the surface of the transfer paper that has been subjected to the fixing process. For example, FIG. 7, FIG. 18 or FIG. A transfer processing apparatus having the same configuration as that shown in FIG. 19 can be used. In the transfer material processing apparatus 4 of this embodiment, a fixed transfer paper is set on the manual feed tray 401, and the manual feed is performed based on, for example, operation of a processing start button of an operation unit (not shown) or detection of the transfer paper on the manual feed tray 401. The transfer paper P on the tray 401 is automatically fed, and a predetermined discharge process is performed by the surface processing apparatus 70, and the processed transfer paper P with improved wettability is continuously discharged onto the paper discharge tray 405. . In particular, in the transfer material processing apparatus 4 of the present embodiment, it is only necessary to place the fixed transfer paper on the manual feed tray 401, so that the fixed transfer paper can be easily processed one by one.

  In each of the above-described embodiments, an example in which dielectric barrier discharge is used for the surface treatment of the fixed transfer paper has been described. However, the present invention provides “atmospheric pressure plasma”, “atmospheric pressure glow discharge”, and “corona discharge”. Other discharges by high voltage under atmospheric pressure expressed by “atmospheric pressure streamer discharge” may be used.

  In each of the above embodiments, the transfer material to be processed by the surface treatment device 70 is an example of a transfer paper based on a fibrous material. However, the processing of the transfer device according to the present invention is not limited to this. The target may be a transfer material other than transfer paper, such as a plastic sheet for OHP, as long as a toner image can be formed and fixed, and the same effect can be obtained.

  Further, as the toner constituting the toner image on the transfer material that can be processed by the surface treatment apparatus of each of the above embodiments, for example, an electrophotographic toner containing at least a resin and a colorant as shown below can be used. . Further, the toner may contain other components such as a carrier and a wax as necessary.

〔resin〕
Examples of the resin include at least a binder resin. The binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, a styrene monomer, an acrylic monomer, a methacrylic monomer, etc. Vinyl polymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins , Coumarone indene resin, polycarbonate resin, petroleum resin, and the like. In consideration of mechanical strength and the like, a polyester resin is preferable.
Examples of the styrene monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-amyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, Examples thereof include styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.

  Examples of the acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic. Examples include 2-ethylhexyl acid, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid such as phenyl acrylate, or esters thereof.

  Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid. And methacrylic acid or esters thereof such as 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

  The following (1)-(18) is mentioned as an example of the other monomer which forms the said vinyl polymer or a copolymer. (1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8), vinyl naphthalenes; (9) acrylonitrile, Such as methacrylonitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic anhydride and alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid, etc. (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; 16) Monomers having a carboxyl group such as anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof; ) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1 -Hydroxy-1-methylhexyl) monomers having a hydroxy group such as styrene.

  In the toner of the exemplary embodiment, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure that is crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic vinyl vinyl compounds such as divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6. And xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of these compounds with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.

  Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds in place of methacrylate, triallyl cyanide. Examples include nurate and triallyl trimellitate.
These crosslinking agents are preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, with respect to 100 parts by mass of other monomer components. Among these crosslinkable monomers, diacrylates bonded to a toner resin by a bond chain containing one aromatic divinyl compound (especially divinylbenzene), one aromatic group and an ether bond from the viewpoint of fixability and offset resistance. Preferred examples include compounds. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  Examples of the polymerization initiator used in the production of the vinyl polymer or copolymer include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2,4-dimethylvalero). Nitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1 '-Azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2', 4 '-Dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide Ketone peroxides such as oxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di- -Tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl per Oxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaurate, tert-butyl-oxybenzoate, tert-butylperoxy Isopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-tert-butyl Kisa Hydro terephthalate to Okishi, tert- butylperoxy azelate, and the like.

  When the binder resin is a styrene-acrylic resin, it has a molecular weight distribution by GPC that is soluble in the resin component tetrahydrofuran (THF), and has at least one peak in the molecular weight range of 3,000 to 50,000 (in terms of number average molecular weight). And a resin having at least one peak in a region having a molecular weight of 100,000 or more is preferable in terms of fixing property, offset property and storage property. Further, as the THF soluble component, a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90% is preferable, and a binder resin having a main peak in a molecular weight region of 5,000 to 30,000 is more preferable. A binder resin having a main peak in the region of 5,000 to 20,000 is most preferable.

  The acid value when the binder resin is a vinyl polymer such as styrene-acrylic resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, and preferably 0.1 mgKOH / g to 70 mgKOH / g. Is more preferable, and most preferably 0.1 mgKOH / g to 50 mgKOH / g.

The following are mentioned as a monomer which comprises the said polyester-type polymer.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.

  In order to crosslink the polyester resin, it is preferable to use a trihydric or higher alcohol together. Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , Etc.

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, and alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid. Or its anhydride, unsaturated dibasic acid such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides. Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

  When the binder resin is a polyester resin, the molecular weight distribution of the THF soluble component of the resin component has at least one peak in the molecular weight region of 3,000 to 50,000. Moreover, as THF-soluble matter, a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100% is preferable, and at least one peak is present in a region having a molecular weight of 5,000 to 20,000. The binder resin present is more preferred. The molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.

  When the binder resin is a polyester resin, the acid value thereof is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / G to 50 mgKOH / g is most preferred.

In addition, as the binder resin that can be used in the toner of the exemplary embodiment, a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component is also used. be able to. Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin has 0.1-50 mgKOH / g is preferable.

The acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation is in accordance with JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The amount of KOH solution used at this time is S (ml), a blank is measured at the same time, and the amount of KOH solution used at this time is B (ml), which is calculated by the following equation (1). However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (1)

  The toner binder resin and the composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 to 80 ° C., more preferably 40 to 75 ° C. from the viewpoint of toner storage stability. preferable. When Tg is lower than 35 ° C., the toner is likely to be deteriorated in a high temperature atmosphere, and an offset is likely to occur during fixing. On the other hand, when Tg exceeds 80 ° C., fixability may be deteriorated.

  The toner may contain a magnetic material. Examples of magnetic materials include (1) iron oxide containing magnetic iron oxide such as magnetite, maghemite, and ferrite, and other metal oxides, and (2) metals such as iron, cobalt, nickel, or these metals. Alloys with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium. (3) and mixtures thereof are used.

Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O _4. , PbFe ₁₂ O, NiFe ₂ O ₄ , NdFe ₂ O, BaFe ₁₂ O ₁₉ , MgFe ₂ O ₄ , MnFe ₂ O ₄ , LaFeO ₃ , iron powder, cobalt powder, nickel powder, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly preferable.

  Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Is preferably contained as an oxide.

  The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grains production | generation, or adding salt of each element and adjusting pH.

  As the usage-amount of the said magnetic body, 10-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of binder resin, and 20-150 mass parts is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm. The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like. Further, as the magnetic properties of the magnetic material, those having a coercive force of 20 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g are preferable, respectively. The magnetic material can also be used as a colorant.

[Colorant]
The colorant contained in the toner is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow ( 10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cadmium Mercury Red , Antimon Zhu, Permanent Red 4R Parared, Faisered, Parachlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue , Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, a Cid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.

  The content of the colorant is preferably 1 to 15% by mass and more preferably 3 to 10% by mass with respect to the toner.

  In addition, the colorant used in the toner of the present exemplary embodiment can be used as a master batch combined with a resin. As the binder resin kneaded together with the production of the master batch or the master batch, in addition to the above-mentioned modified and unmodified polyester resins, for example, polystyrene, poly p-chlorostyrene, polyvinyltoluene and other styrene and its substitutes Polymer: Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene 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 Polymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, Styrene copolymers such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl Examples include butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. There is also a method of removing water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.
As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.
The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and a colorant dispersed therein. The acid value is 20 mgKOH / g or less and the amine value is 10 It is more preferable that the colorant is dispersed and used at ˜50. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered, and the pigment dispersibility may be insufficient. Also, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility may be insufficient. The acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237.

  The toner dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific commercial products include “Azisper PB821”, “Azisper PB822” (Ajinomoto Fine Techno Co., Ltd.). Product), “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like.

  The dispersant is preferably blended in the toner at a ratio of 0.1 to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it is more than 10% by mass, the chargeability under high humidity may be deteriorated.

  The weight average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene conversion weight in gel permeation chromatography, preferably 500 to 100,000, and more preferably 3000 to 100,000 from the viewpoint of pigment dispersibility. In particular, 5000 to 50000 is preferable, and 5000 to 30000 is most preferable. When the molecular weight is less than 500, the polarity becomes high and the dispersibility of the colorant may be lowered. When the molecular weight exceeds 100,000, the affinity with the solvent is increased and the dispersibility of the colorant is lowered. There is.

  The addition amount of the dispersant is preferably 1 to 200 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 200 parts by mass, the chargeability may be lowered.

<Wax>
Further, as described above, the toner constituting the toner image on the transfer material that can be processed by the surface treatment apparatus of the above embodiment may be a toner containing wax together with the binder resin and the colorant.

  The wax is not particularly limited and can be appropriately selected from those usually used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sazol wax Aliphatic hydrocarbon wax such as oxide wax, oxide of aliphatic hydrocarbon wax such as polyethylene oxide wax or block copolymer thereof, plant wax such as candelilla wax, carnauba wax, wood wax, jojoba wax, beeswax Waxes based on fatty acid esters such as animal waxes such as lanolin and whale wax, mineral waxes such as ozokerite, ceresin and petrolatum, montanic acid ester wax and castor wax. Deoxidized carnauba wax and other fatty acid esters that have been partially or wholly deoxidized are included.

  Examples of the wax further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, and valinal acid. Unsaturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnupyl alcohol, seryl alcohol, mesyl alcohol, or long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acids Fatty acid amides such as amide and lauric acid amide, methylene biscapric acid amide, ethylene bis lauric acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide, hexamethylene bis stearic acid amide and other saturated fats Unsaturated fatty acid amides such as acid bisamide, ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepacic acid amide, m-xylene bis Aromatic bisamides such as stearamide, N, N-distearylisophthalamide, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate, aliphatic hydrocarbon wax, styrene and acrylic acid Examples include waxes grafted using vinyl monomers such as, partial ester compounds of fatty acids such as behenic monoglyceride and polyhydric alcohols, and methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats. .

  More preferable examples include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fitzscher Tropsch wax, Jintole method, hydrocol method, age method Synthetic hydrocarbon waxes synthesized by the above, synthetic waxes having a compound having one carbon atom, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and hydrocarbons having functional groups Mixture of system wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.

  In addition, these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.

  The melting point of the wax is preferably 70 to 140 ° C., and more preferably 70 to 120 ° C., in order to balance the fixability and the offset resistance. If it is less than 70 degreeC, blocking resistance may fall, and if it exceeds 140 degreeC, an offset-proof effect may become difficult to express.

Further, by using two or more different types of waxes in combination, the plasticizing action and the releasing action which are the actions of the wax can be expressed simultaneously.
Examples of the types of wax having a plasticizing action include waxes having a low melting point, those having a branch on the molecular structure, and those having a polar group.
Examples of the wax having a releasing action include a wax having a high melting point, and the molecular structure includes a linear structure and a non-polar one having no functional group. Examples of use include a combination of two or more different waxes having a melting point difference of 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.

  When selecting two types of wax, in the case of a wax having the same structure, a wax having a relatively low melting point exhibits a plasticizing action, and a wax having a high melting point exhibits a releasing action. At this time, when the difference in melting point is 10 to 100 ° C., functional separation is effectively expressed. If it is less than 10 ° C., the function separation effect may be difficult to appear, and if it exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one of the waxes is preferably 70 to 120 ° C, and more preferably 70 to 100 ° C, because the function separation effect tends to be easily exhibited.

As for the wax, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exhibit a plastic action, and those having a more linear structure or functional group Nonpolar or non-denatured straight materials that do not have a mold exhibit a releasing action. Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or ester waxes. And hydrocarbon wax combinations, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax combination, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, Carnauba Wax, Can Delila wax, rice wax or montan wax and hydrocarbon wax Combinations thereof.
In any case, since it becomes easy to balance the toner storage stability and the fixing property, the peak top temperature of the maximum peak is in the region of 70 to 110 ° C. in the endothermic peak observed in the DSC measurement of the toner. It is more preferable that it has a maximum peak in the region of 70 to 110 ° C.

  The total content of the wax is preferably 0.2 to 20 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

  In the wax contained in the toner of the present exemplary embodiment, the melting point of the wax is defined as the temperature at the peak top of the maximum endothermic peak of the wax measured in differential scanning calorimetry (DSC).

  The wax or toner DSC measuring device is preferably measured with a high-precision internal heat input compensation type differential scanning calorimeter. As a measuring method, for example, a method according to JIS K7121 is adopted. For the DSC curve, for example, the one measured when the temperature is raised at a temperature rate of 10 ° C./min after once raising and lowering the temperature and taking a previous history is used.

<Charge control agent>
The toner charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since the color tone may change when a colored material is used, the material is colorless to nearly white. For example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds thereof, tungsten Or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. These may be used individually by 1 type and may use 2 or more types together.

  In addition, the charge control agent added to the toner, for example, adjusts the charging characteristics of the toner to suppress differences in charging characteristics in an environment where the charging characteristics such as high temperature and high humidity or low temperature and low humidity can fluctuate greatly. It is used to suppress variation in charge amount between toner particles.

Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (all manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (all manufactured by Hodogaya Chemical Co., Ltd.), No. Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, boron complex LR-147 (made by Nippon Carlit Co., Ltd.); quinacridone, azo pigment, other Acid group, a carboxyl group, and the like and polymeric compounds having a functional group such as a quaternary ammonium salt.
The charge control agent may be melted and kneaded together with the master batch and then dissolved and / or dispersed, or may be added together with each component of the toner when directly dissolving and / or dispersing in the organic solvent. Alternatively, it may be fixed to the toner surface after the toner particles are produced.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of the additive, the dispersion method, and the like, and cannot be generally defined. For example, 0.1-10 mass parts is preferable and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

<Fluidity improver>
A fluidity improver may be added to the toner of this embodiment. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.

  Examples of the fluidity improver include, for example, carbon black, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder unoxidized titanium, Fine powder non-alumina, treated silica obtained by subjecting them to surface treatment with a silane coupling agent, titanium coupling agent or silicone oil, treated titanium oxide, treated alumina, and the like can be mentioned. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.

  The particle size of the fluidity improver is preferably 0.001 to 2 μm, more preferably 0.002 to 0.2 μm, as an average primary particle size.

  The fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.

  Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include, for example, AEROSIL (trade name of Nippon Aerosil Co., Ltd., hereinafter the same) -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84: Ca-O-SiL (trade name of CABOT)-M-5, -MS-7, -MS-75, -HS-5, -EH-5, Wacker HDK (trade name of WACKER-CHEMIE)- N20 V15, -N20E, -T30, -T40: D-CFineSi1ica (trade name of Dow Corning): Franco1 (trade name of Franci1), and the like.

  Furthermore, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is more preferable. In the treated silica fine powder, it is particularly preferred to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is preferably 30 to 80%. Hydrophobization is imparted by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, a method of treating a silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferable.

  Examples of the organosilicon compound include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and dimethylvinylchlorosilane. , Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchloro Silane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, Examples include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to Si. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The number average particle diameter of the fluidity improver is preferably 5 to 100 nm, more preferably 5 to 50 nm.

The specific surface area by measuring nitrogen adsorption by the BET method, preferably at least ^{30m 2 / g, 60~400m 2 /} g is more preferable.

The surface-treated fine powder, preferably at least ^{20m 2 / g, 40~300m 2 /} g is more preferable. The application amount of these fine powders is preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the toner particles.

  In addition, the toner of the present embodiment includes, as other additives, protection of the electrostatic latent image carrier / carrier, improvement of cleaning properties, adjustment of thermal characteristics / electrical characteristics / physical characteristics, resistance adjustment, softening point adjustment, Various metal soaps, fluorine surfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, titanium oxide, aluminum oxide, alumina, etc. Inorganic fine powder or the like can be added as necessary. These inorganic fine powders may be hydrophobized as necessary. In addition, lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agents, white particles and black particles having opposite polarity to the toner particles, Can also be used in small amounts as a developability improver.

  These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or various treating agents.

  Further, when preparing the developer, inorganic fine particles such as the above-mentioned hydrophobic silica fine powder may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the developer. . For mixing external additives, a general powder mixer can be appropriately selected and used. However, it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually, and the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. The load may then be given a relatively weak load and vice versa.

  Examples of the mixer include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.

  The method for further adjusting the shape of the toner is not particularly limited and may be appropriately selected depending on the intended purpose.For example, a toner material composed of a binder resin and a colorant is melt-kneaded and then finely pulverized. A method of mechanically adjusting the shape using a hybridizer, mechano-fusion, etc., or a so-called spray drying method, after dissolving and dispersing the toner material in a solvent in which the toner binder is soluble, the solvent is removed using a spray drying device. For example, a method for obtaining a spherical toner, and a method for forming a spherical toner by heating in an aqueous medium.

As the external additive, inorganic fine particles can be preferably used. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, more preferably 5 mμ to 500 mμ. The specific surface area according to the BET method is preferably 20 to 500 m ² / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 to 2.0% by mass.

  Other external additives include polymer-based fine particles such as soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization obtained by polycondensation such as polystyrene, methacrylic acid ester, acrylate ester copolymer, silicone, benzoguanamine, and nylon. And polymer particles made of a thermosetting resin.

  Such an external additive can be made hydrophobic by the surface treatment agent and prevent deterioration of the external additive itself even under high humidity. Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, a modified silicone oil, Etc. are preferable.

  Examples of cleaning improvers to be added to the toner in order to remove the transferred developer remaining on the transfer belt as a latent image carrier or a primary transfer member include zinc stearate, calcium stearate, and stearic acid. And polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 μm to 1 μm.

  The developing method using the toner made of various materials can use all the electrostatic latent image carriers used in the conventional electrophotography. For example, organic electrostatic latent image carriers, amorphous silica electrostatic latent members can be used. An image carrier, a selenium electrostatic latent image carrier, a zinc oxide electrostatic latent image carrier, and the like can be suitably used.

1, 1 ′ Image forming apparatus 2, 3, 4 Transfer material processing device 70 Surface processing device 700 Discharge processing unit 701, 702 Conveying roller 703 First electrode roller 704 Second electrode roller 705 High-frequency transmitter 706 High-pressure transformer 268 Oil P Transfer Paper W Wax T Toner T 'Toner image

JP-A-62-100775 Japanese Patent Laid-Open No. 3-91864 JP-A-3-168649 JP-A-8-334919

Electrophotographic Society, “Basics and Applications of Electrophotographic Technology”, first edition, Corona Co., Ltd., June 15, 1988, p. 321-324

Claims (10)

A surface treatment apparatus for treating the surface of a transfer material,
The transfer material to be processed is a transfer material on which the toner image is fixed using a fixing member on which a toner image is formed and a release agent made of oil is applied,
Comprising conveying means for conveying the transfer material the toner image fixing has been that the fixing is performed is formed, and discharge means for generating a dielectric barrier discharge in the vicinity of the surface or the surface of the transfer material, the ,
The discharging means includes
A conductive outer peripheral surface having a roller shape that faces the surface of the transfer material conveyed by the conveying means on which the toner image is formed and that extends in a direction intersecting the moving direction of the transfer material. A first electrode member exposed;
A second electrode member provided so that a dielectric layer is formed on the entire outer peripheral surface of the roller-shaped conductive member and is opposed to the first electrode member with the transfer material interposed therebetween;
Voltage applying means for applying a voltage between the first electrode member and the conductive member of the second electrode member;
Drive means for rotationally driving the second electrode member,
The conveying means does not wind the transfer material around the outer peripheral surfaces of the first electrode member and the second electrode member, so that the first electrode member and the second electrode member face each other and the dielectric barrier Transporting the transfer material so that the transfer material moves linearly in the area where the discharge occurs,
The release agent composed of the oil applied to the surface of the transfer material while the toner image formed on the surface of the fixed transfer material is left is reduced by the dielectric barrier discharge. Surface treatment equipment. A surface treatment apparatus for treating the surface of a transfer material,
The transfer material to be processed is a transfer material in which a toner image is formed on the surface using toner to which a release agent made of wax is added, and the toner image is fixed.
Comprising conveying means for conveying the transfer material the toner image fixing has been that the fixing is performed is formed, and discharge means for generating a dielectric barrier discharge in the vicinity of the surface or the surface of the transfer material, the ,
The discharging means includes
A conductive outer peripheral surface having a roller shape that faces the surface of the transfer material conveyed by the conveying means on which the toner image is formed and that extends in a direction intersecting the moving direction of the transfer material. A first electrode member exposed;
A second electrode member provided so that a dielectric layer is formed on the entire outer peripheral surface of the roller-shaped conductive member and is opposed to the first electrode member with the transfer material interposed therebetween;
Voltage applying means for applying a voltage between the first electrode member and the conductive member of the second electrode member;
Drive means for rotationally driving the second electrode member,
The conveying means does not wind the transfer material around the outer peripheral surfaces of the first electrode member and the second electrode member, so that the first electrode member and the second electrode member face each other and the dielectric barrier Transporting the transfer material so that the transfer material moves linearly in the area where the discharge occurs,
The dielectric barrier discharge reduces the release agent composed of the wax existing on the surface of the toner image of the transfer material while leaving the toner image formed on the surface of the fixed transfer material. A surface treatment apparatus characterized by the above. In the surface treatment apparatus of Claim 1 or 2,
A surface treatment apparatus, wherein a contact angle of water with respect to a portion present in the toner image in a surface of the transfer material treated by the discharge is 90 ° or less. In the surface treatment apparatus of Claim 1 or 2,
A contact angle of water with respect to each of a portion present in the toner image and a portion not present in the toner image of the surface of the transfer material treated by the discharge is 90 ° or less. Processing equipment . In any of the surface treatment apparatus 請 Motomeko 1 to 4,
The surface treatment apparatus according to claim 1, wherein the voltage is an AC voltage having a frequency of 20 [kHz] or more and 500 [kHz] or less. In the surface treatment apparatus of Claim 5 ,
The surface treatment apparatus characterized in that the peak-to-peak voltage value of the AC voltage is not less than 5 [kV _p-p ] and not more than 30 [kV _p-p ] per unit length [mm] of the thickness of the gap. In the surface treatment apparatus in any one of Claims 1 thru | or 6 ,
A material for the first electrode member is stainless steel. In the surface treatment apparatus in any one of Claims 1 thru | or 7 ,
Surface treatment apparatus the diameter of the second electrode member may be greater than the diameter of said first electrode member. In the surface treatment apparatus in any one of Claims 1 thru | or 8 ,
The dielectric constant of the dielectric layer of the second electrode member is 2 or more and 10 or less,
The surface treatment apparatus, wherein the dielectric layer has a thickness of 0.1 [mm] or more and 5 [mm] or less. A transfer material processing apparatus for processing a transfer material,
A transfer material supply unit for supplying a fixed transfer material on which a toner image is formed and the toner image is fixed;
A surface treatment apparatus for treating a surface on which the toner image of the transfer material supplied from the transfer material supply unit is fixed;
A transfer material output unit for outputting the transfer material surface-treated by the surface treatment apparatus,
The surface treatment apparatus, the transfer material processing device which is a one of a surface treatment apparatus according to claim 1 to 9.