JP2008096722A - Protective agent supply member, protective agent bar, protective layer forming device, process cartridge and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a protective agent supply member that supplies a protective agent so that protective effect for the surface of an image carrier can be exhibited from the beginning of image formation, and to provide a protective agent bar that supplies the protective agent to the protective agent supply member, and a protective layer forming device that forms a protective layer on the surface of the image carrier by the use of them. <P>SOLUTION: The protective agent supply member 22 has a brush 22a disposed in contact with the protective agent bar 21 and supplies a protective agent, transferred to the brush from the protective agent bar, to the image carrier 1. In the protective agent supply member 22, the area of the leading end of the brush is made 5 to 100% greater than the cross-sectional area of the brush, measured in a place 50 μm away from the leading end of the brush. In addition, a distance from the greatest outer shape of the leading end of the brush to the extremity of the brush in the lengthwise direction of the brush is made 40 μm or less. The protective agent bar 21 for supplying the protective agent to the brush of the protective agent supply member 21 includes the protective agent in the form of a rod. The pencil hardness of the protective agent at 25°C is set to the hardness less than 4B. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is a protective agent supply member for supplying a protective agent for protecting a surface of an image carrier used for image formation using an electrophotographic system, a protective agent bar for supplying a protective agent to the protective agent supply member, The present invention relates to a protective layer forming apparatus that forms a protective layer with a protective agent on the surface of the image carrier using a protective agent supply member and a protective agent bar, a process cartridge having the protective layer forming apparatus, and an image forming apparatus.

  Conventionally, in electrophotographic image formation, a latent image (referred to as an electrostatic latent image) is formed on an image carrier made of a photoconductive substance or the like, and the electrostatic latent image is charged. Toner particles are adhered to form a visible image. The visible image formed by the toner is finally transferred to a transfer medium such as paper, and then fixed to the transfer medium by heat, pressure, solvent gas, or the like, and becomes an output image.

  These image forming methods include a so-called two-component development method that uses friction charging by stirring and mixing toner particles and carrier particles by a method of charging toner particles for visualization, and without using carrier particles. In other words, the toner particles are roughly classified into so-called one-component development systems in which charge is imparted to toner particles. In addition, the one-component development method is classified into a magnetic one-component development method and a non-magnetic one-component development method depending on whether or not a magnetic force is used for holding toner particles on the developing roller.

So far, in copying machines that require high speed and image reproducibility, and multi-function machines based on these, due to demands such as toner particle charging stability, start-up stability, and long-term image quality stability, The two-component development method is often used, and the one-component development method has been often used in small printers, facsimiles, and the like that demand large space savings and low costs.
In particular, in recent years, colorization of output images has progressed, and the demand for higher image quality and stabilization of image quality has become stronger than ever.
In order to improve the image quality, the average particle diameter of the toner is reduced, and the shape of the particles is not rounded and becomes more round.

  These electrophotographic image forming apparatuses are uniformly charged while rotating an image carrier (generally a photoconductive photoreceptor) generally in the form of a drum or a belt, regardless of the development method. Then, a pattern of an electrostatic latent image is formed on the image carrier by laser light or the like, and this is visualized with toner of a developing device, and further transferred onto a transfer medium.

  Further, the toner component that has not been transferred remains on the image carrier after the toner image is transferred to the transfer medium. When these residues are conveyed to the charging process as they are, it is often the case that the uniform charging of the image carrier is hindered. The components and the like are removed in a cleaning process to make the surface of the image carrier sufficiently clean, and then charging is performed again.

As described above, the surface of the image bearing member is subjected to various physical stresses and electrical stresses in various processes such as charging, development, transfer, and cleaning, and the surface state changes as the usage time elapses.
Of these stresses, it is known that the stress due to friction in the cleaning process causes the image carrier to wear and causes scratches. In order to solve this problem, many proposals have been made so far regarding various lubricants and methods for supplying lubricant components and forming films in order to reduce the frictional force between the image carrier and the cleaning member.

  For example, in Patent Document 1 and Patent Document 2, in order to extend the life of the photoreceptor and the cleaning blade, a solid lubricant mainly composed of zinc stearate is supplied to the surface of the photoreceptor to form a lubricant film on the surface of the photoreceptor. Has been proposed.

  When zinc stearate is used as a solid lubricant as in the prior art described above, the zinc stearate is transferred to the brush after rubbing the brush against the protective agent bar made of zinc stearate, and then the stearic acid from the brush to the surface of the photoreceptor. Zinc was being supplied. Since zinc stearate is relatively hard, when it is rubbed with a brush, it becomes a fine powder and adheres to the surface of the photoconductor. By stretching it by broadening or the like, the zinc stearate is present in a film form on the photoconductor.

  However, some of the finely powdered zinc stearate adhering to the photoreceptor maintained the fine powder shape even after passing through the cleaning blade, and easily adhered to the charging device in the charging step. In particular, when a charging roller is used in the charging device, the photosensitive member and the charging roller are in contact with each other or separated by a distance of several hundred μm or less. It was big. Furthermore, when charging is performed by superimposing a DC voltage and an AC voltage on the charging roller, the zinc stearate adhering to the charging roller is dissolved by the charging energy, and the toner component that could not be cleaned is entrained on the charging roller. The film is fixed in the form of a film, which increases the resistance of the portion, and has the disadvantage that uneven charging tends to occur. Therefore, there has been a demand for a lubricant (protective agent) that does not easily become a fine powder even when rubbed with a brush.

Japanese Patent Publication No.51-22380 Japanese Patent Laid-Open No. 2004-333961 JP 52-36016 A

  When supplying the protective agent to the photoconductor by rubbing the brush against the protective agent bar in the form of a rod, to prevent the protective agent bar from becoming fine powder, use a soft material for the protective agent bar. Rather than being powdered by the impact when the brush is rubbed against the bar, a protective agent adheres to the tip of the brush, and when the tip of the brush with the protective agent is rubbed against the photoconductor, It was found that the protective agent should be transferred to the body.

  However, at the initial stage of attaching the protective agent, since the protective agent is not attached to the brush, there is a problem that the protective agent is not easily supplied onto the photoreceptor. If image formation is repeated in the absence of a protective agent on the photoconductor, the portion where the protective agent is not present will be oxidized and deteriorated due to the energy of charging, resulting in a decrease in the cleaning properties of residual toner on the photoconductor. In addition, wear of the cleaning blade end portion and so-called filming in which the toner component adheres in a film form are likely to occur. When such a phenomenon occurs, even if the protective agent can be supplied, the abnormality is hardly eliminated, and a problem that the photosensitive member or the process cartridge has to be replaced occurs.

  The present invention has been made in view of the problems as described above, and exhibits a sufficient protection effect on the surface of the image carrier, particularly a protection effect against stresses in the charging step and the cleaning step, from the initial stage of image formation. Providing a protective agent supply member for supplying the protective agent so that the protective agent supply member can be provided; and providing a protective agent bar suitable for supplying the protective agent to the protective agent supply member; and It is an object of the present invention to provide a protective layer forming apparatus for forming a protective layer with a protective agent on the surface of the image carrier using a member and a protective agent bar. It is another object of the present invention to provide a process cartridge having the protective layer forming apparatus and an image forming apparatus having the protective layer forming apparatus or the process cartridge and capable of forming a high quality image.

In order to achieve the above object, the present invention employs the following technical means.
The first means of the present invention has a brush in contact with the protective agent bar, and in the protective material supply member for supplying the protective agent transferred from the protective agent bar to the brush to the image carrier, the tip of the brush The area is 5 to 100% larger than the cross-sectional area of the brush at a position of 50 μm from the tip of the brush.
Further, according to the second means of the present invention, in the protective agent supply member of the first means, the distance in the longitudinal direction of the brush from the place where the outer shape of the tip of the brush is the largest to the tip of the brush is 40 μm or less. It is characterized by being.

The third means of the present invention is a protective agent bar for supplying a protective agent to the brush of the protective agent supply member of the first or second means, comprising a rod-like protective agent, and the protective agent at 25 ° C. The pencil hardness is set to be softer than 4B.
According to a fourth means of the present invention, in the protective agent bar of the third means, the protective agent contains 50% by weight or more of a hydrophobic substance.
Furthermore, the fifth means of the present invention is characterized in that, in the protective agent bar of the fourth means, the hydrophobic substance is paraffin.

According to a sixth means of the present invention, in the protective agent bar of the third means, the protective agent contains an amphiphilic (hydrophilic and hydrophobic) organic substance, and the amphiphilic substance in the protective agent. The organic substance content is 3% by weight or more.
According to a seventh means of the present invention, in the protective agent bar of the sixth means, the HLB value of the amphiphilic organic substance in the protective agent (a value indicating the affinity of the surfactant for water and oil: Hydrolyhile) -Lipophile Balance) is set to 1.0 to 6.5.
Furthermore, the eighth means of the present invention is characterized in that in the protective agent bar of the sixth or seventh means, the amphiphilic organic substance in the protective agent is a nonionic surfactant.

According to a ninth means of the present invention, in the protective agent bar of any one of the sixth to eighth means, the protective agent contains a hydrophobic organic compound (A) and an amphiphilic organic substance (B). It is characterized by being.
According to a tenth means of the present invention, in the protective agent bar of the ninth means, the weight ratio A / B of the hydrophobic organic compound (A) and the amphiphilic organic substance (B) contained in the protective agent. Is 50/50 to 97/3.
The eleventh means of the present invention is characterized in that, in the protective agent bar of the ninth or tenth means, the hydrophobic organic compound (A) contained in the protective agent is paraffin.
Furthermore, the twelfth means of the present invention is the protective agent bar of any one of the third to eleventh means, wherein the protective agent has at least one endothermic peak temperature at 50 to 130 ° C. And

A thirteenth means of the present invention is a protective layer forming apparatus, comprising the protective agent supply member of the first or second means, and the protective agent bar of any one of the third to twelfth means, The protective agent bar is pressed against the brush of the protective agent supply member, the protective agent is transferred to the brush of the protective agent supply member, and the brush of the protective agent supply member is pressed against the image carrier to perform the protection. An agent is supplied to the image carrier.
According to a fourteenth means of the present invention, in the protective layer forming apparatus of the thirteenth means, the protective agent bar is pressed against the brush of the protective agent supply member, and the protective agent is applied to the brush of the protective agent supply member. And a protective layer forming mechanism for thinning the protective agent supplied onto the image carrier by the protective agent supply member.

The fifteenth means of the present invention is a process cartridge, characterized in that at least the image carrier and the protective layer forming apparatus of the thirteenth or fourteenth means are provided in the cartridge.
According to a sixteenth means of the present invention, there is provided an image forming apparatus comprising at least an image carrier and a protective layer forming apparatus of the thirteenth or fourteenth means.
Further, the seventeenth means of the present invention is an image forming apparatus, characterized by comprising the process cartridge of the fifteenth means.

  According to an eighteenth means of the present invention, in the image forming apparatus of the sixteenth means, a charging means for charging the image carrier and a latent image for irradiating the charged image carrier with light to form an electrostatic latent image. Image forming means, developing means for developing the electrostatic latent image on the image carrier with a toner into a visible image, and transfer means for transferring the toner image on the image carrier to a transfer medium or an intermediate transfer medium And an image forming unit that removes toner remaining on the surface of the image carrier after the transfer, and the protective layer forming apparatus is provided at a portion from the cleaning unit to the charging unit of the image forming unit. It is characterized by having.

  According to a nineteenth means of the present invention, in the image forming apparatus of the seventeenth means, a charging means for charging the image carrier and a latent image for irradiating the charged image carrier with light to form an electrostatic latent image. Image forming means, developing means for developing the electrostatic latent image on the image carrier with a toner into a visible image, and transfer means for transferring the toner image on the image carrier to a transfer medium or an intermediate transfer medium And an image forming unit that removes toner remaining on the surface of the image carrier after the transfer, and the protective layer forming apparatus is provided at a portion from the cleaning unit to the charging unit of the image forming unit. The process cartridge includes an image carrier that constitutes the image forming unit, at least one of the charging unit, the developing unit, and the cleaning unit, and the protective layer forming apparatus. Features.

  According to a twentieth aspect of the present invention, in the image forming apparatus of the eighteenth or nineteenth means, a plurality of the image forming portions are arranged side by side, and images having different toner colors are formed in the plurality of image forming portions. A toner image is superimposed on a transfer medium or an intermediate transfer medium and transferred to form a multicolor or full color image.

In the protective agent supplying member of the first means of the present invention, the brush tip end area is 5 to 100% larger than the cross-sectional area of the brush at a position of 50 μm from the tip of the brush. Since the protective agent can be efficiently held and supplied to the image carrier, the protective agent can be smoothly supplied to the image carrier.
Further, in the protective agent supply member of the second means, the distance in the longitudinal direction of the brush from the place where the outer shape of the tip of the brush is the largest to the tip of the brush is 40 μm or less. On the other hand, since the level difference of the brush is an appropriate height, the protective agent can be smoothly supplied to the image carrier even in the initial stage of image formation (initial stage of using the application brush).
Further, in the protective agent bars of the third to twelfth means, a protective agent having a high protective effect on the image carrier can be efficiently supplied to the image carrier through the brush of the protective agent supply member.
In the protective layer forming apparatuses of the thirteenth and fourteenth means, a protective agent having a high protective effect on the image carrier can be efficiently supplied to the image carrier through the brush of the protective agent supply member. The protective agent can be formed into a film on the image carrier.

In the fifteenth means, the protective layer forming apparatus of the thirteenth or fourteenth means for forming a protective layer on the image carrier together with the image carrier is provided in the cartridge, thereby realizing a long-life process cartridge. can do.
The sixteenth and eighteenth means are provided with the protective layer forming apparatus of the thirteenth or fourteenth means for forming a protective layer on the image carrier together with the image carrier, so that the life of the image carrier is increased. Therefore, it is possible to realize an image forming apparatus that is long and capable of forming a high-quality image.
Further, since the seventeenth and nineteenth means are provided with the process cartridge of the fifteenth means, the process cartridge can have a long life and can form an image with high image quality.
Furthermore, in the twentieth means, an image forming apparatus capable of forming a high-quality multicolor or full-color image with a long life of the image carrier or process cartridge can be realized.

  In the image forming apparatus in which the soft protective agent bar is used for forming the protective layer film, the inventors have been able to quickly supply the protective agent to the image carrier (for example, a photoconductive photosensitive member) at the initial stage of image formation. When the brush tip of the protective agent supply member having the brush for supplying the protective agent was observed in detail, the location where the protective agent is present is as shown in the schematic diagram of FIG. I found that the peripheral part of was the main. For this reason, if the location where the protective agent can be present at the tip of the brush can be provided, it is thought that the protective agent can be quickly supplied to the image carrier, and the brush tip shape has been studied. As a result, as shown in the schematic diagram of FIG. 6, if the tip of the brush is flattened and the area of the brush tip is made larger than the cross-sectional area of the brush, the protective agent is effectively attached to the tip of the brush, The inventors have found that the supply to the carrier can be performed smoothly, and have reached the present invention.

  That is, in the present invention, a protective agent bar in which a relatively soft protective agent is formed into a rod shape is used to form a protective layer film for protecting an image carrier (for example, a photoconductive photoreceptor) of an image forming apparatus, and a protective material is supplied. The member has a brush in contact with the protective agent bar, and supplies the protective agent transferred from the protective agent bar to the brush to the photosensitive member. And this protective agent supply member is comprised so that the area of the front-end | tip of a brush may become 5 to 100% larger than the cross-sectional area of a brush in the position of 50 micrometers from the front-end | tip of this brush. Further, in the protective agent supply member of the present invention, in addition to the above-described configuration, the distance in the longitudinal direction of the brush from the place having the largest outer shape of the brush tip to the most distal end of the brush is configured to be 40 μm or less. is doing. Further, in the present invention, the protective agent bar for supplying the protective agent to the brush of the protective agent supply member is made of a rod-shaped protective agent, and the pencil hardness at 25 ° C. of this protective agent is set to a softer hardness than 4B. ing.

The protective layer forming apparatus of the present invention includes the protective agent supply member and the protective agent bar, and presses the protective agent bar against the brush of the protective agent supply member to transfer the protective agent to the brush of the protective agent supply member. The protective agent supply member is pressed against the image carrier to supply the protective agent to the image carrier.
The process cartridge of the present invention has a configuration in which at least the image carrier and the protective layer forming apparatus are provided in the cartridge.
Furthermore, the image forming apparatus of the present invention has a configuration including at least an image carrier and the protective layer forming device, and may include a process cartridge described above.

Hereinafter, embodiments of the present invention will be described in more detail.
The protective agent supply member of the present invention has a brush that contacts the protective agent bar, and is configured to supply the protective agent transferred from the protective agent bar to the brush to an image carrier (for example, a photoconductor). The area is 5 to 100%, preferably 10 to 80%, more preferably 15 to 60% of the cross-sectional area of the brush at a position 50 μm from the brush tip. When the area of the brush tip is less than 5% of the cross-sectional area of the brush at a position 50 μm from the brush tip, the amount of the protective agent retained is not much different from that of a cylindrical brush, so that the image carrier is protected. Since the supply amount of the agent becomes slow, it is not preferable. On the other hand, if it is larger than 100%, the brushes tend to get tangled with each other and the tip of the brush tends to be chipped. The brush tip does not have to be perfectly flat, and may have irregularities, curved surfaces, or be inclined, but it is preferable that the brush length from the location where the outer shape of the brush tip is the largest to the tip of the brush The distance in the direction is 40 μm or less, preferably 35 μm or less, more preferably 30 μm or less. The part where the protective agent adheres most to the brush is near the place where the outer shape of the brush is the largest, so if the distance in the brush longitudinal direction from the place where the outer shape of the brush tip is the largest to the tip of the brush is 40 μm or more When the brush comes into contact with the image carrier, the amount of the protective agent that comes into contact with the image carrier is reduced. When the brush tip is not completely flat, an area obtained by projecting a place having the largest outer shape of the brush tip is used.

  As a material for the brush of the protective agent supply member of the present invention, the brush is formed of fibers having high durability and flexibility, excellent wear resistance, and good sliding properties. Examples of fibers that satisfy such conditions include regenerated fibers such as rayon fibers and cupra fibers, and synthetic fibers formed from nylon, acrylic, polypropylene, polyester, and the like. In this embodiment, the rayon fiber is used that has good flexibility, has the required slidability, and is low in cost.

  Moreover, as a brush of a protective agent supply member, what has electroconductivity is further more preferable. As a method of imparting conductivity to the fiber, there are a method of kneading a conductive material in the raw yarn stage and a method of coating the fiber surface with a processing liquid containing the conductive material after spinning. In this embodiment, since the fiber is advantageous in that it is conductive, a method of kneading a conductive material in the raw yarn stage is employed.

  Examples of the conductive material as described above include metals such as silver, copper and nickel, metal compounds such as zinc oxide and tin oxide, and fine particles such as carbon. In this embodiment, carbon having stable conductivity and low cost is used.

  In addition, as the fiber forming the brush of the protective agent supply member, one having heat resistance is more preferable. As a method of imparting heat resistance to the fiber, there are a method of kneading a flame retardant at the raw yarn stage and a method of impregnating the fiber with a processing liquid containing the flame retardant after spinning. In this embodiment, since the operation is simple and it can cope with fibers of various materials, a method of kneading a flame retardant at the raw yarn stage is adopted.

  Examples of the above flame retardant include halogen flame retardants such as halogenated diols and halogenated glycidyl ethers, phosphorus flame retardants such as phosphate esters and phosphorus-nitrogen (PN) compounds. As the form of the flame retardant, a phosphorus-based flame retardant is used.

  A protective layer forming apparatus used in the image forming apparatus of the present invention includes the protective agent supply member and the protective agent bar described above, and presses the protective agent bar against the brush of the protective agent supply member so that the protective agent is the protective agent. The brush is moved to the supply member brush, and the protective agent supply member brush is pressed against the image carrier to supply the protective agent to the image carrier. And the hardness of the surface of the protective agent bar used in this protective layer forming apparatus is set so that the pencil hardness at 25 ° C. is softer than 4B, preferably 5B, more preferably softer than 6B. It is good to be. If the hardness of the surface of the protective agent bar is higher than the pencil hardness of 4B, the protective agent is likely to become particles by rubbing the brush of the protective agent supply member, and is liable to adhere to the charging roller and cause uneven charging. Absent. Even if the particles do not become particles, a hard brush must be used, which is not preferable because the image carrier is easily damaged.

In the protective agent used in the protective layer forming apparatus of the present invention, a hydrophobic substance is contained in an amount of 50% by weight or more, preferably 60% by weight or more, and more preferably 70 to 90% by weight. A hydrophobic substance such as a hydrophobic organic compound (A) is applied onto the image carrier to reduce the frictional force between the image carrier and the cleaning blade and prevent the image carrier from being oxidized by charging. This is preferable because the surface resistance of the image carrier can be kept high even under high humidity.
When the hydrophobic organic compound (A) in the protective agent is less than 50% by weight, the surface resistance of the image bearing member is lowered and the image density is liable to be lowered under high humidity.
The hydrophobic organic compound (A) used for the protective agent is classified into aliphatic saturated hydrocarbon, aliphatic unsaturated hydrocarbon, alicyclic saturated hydrocarbon, alicyclic unsaturated hydrocarbon and aromatic hydrocarbon. In addition to hydrocarbons, polytetrafluoroethylene (PTFE), polyperfluoroalkyl ether (PFA), perfluoroethylene-perfluoropropylene copolymer (FEP), polyvinylidene fluoride (PVdF), ethylene-tetrafluoro Examples thereof include fluorine resins such as ethylene copolymer (ETFE) and fluorine waxes, silicone resins such as polymethyl silicone and polymethyl phenyl silicone, and silicone waxes. In particular, aliphatic saturated hydrocarbons are used as oxides that increase the frictional force between the image carrier and the cleaning blade or reduce the surface resistance of the image carrier even when oxidized in the charging step. It is very preferable because it hardly remains on the body. Moreover, since it is economically cheap, it is very preferable.
The protective agent preferably contains a hydrophobic organic compound (A) and an amphiphilic (hydrophilic and hydrophobic) organic substance (B), and the content of the amphiphilic organic substance in the protective agent Is preferably 3 to 50% by weight, preferably 5 to 40% by weight, and more preferably 7 to 35% by weight.
Further, in the protective agent bar of the present invention, the amphiphilic organic substance in the protective agent has an HLB value (a value indicating the affinity between the surfactant water and oil: Hydropile-Lipophile Balance) of 1.0 to 6. It is preferably set to 5.
Furthermore, in the protective agent bar of the present invention, the amphiphilic organic substance in the protective agent is preferably a nonionic surfactant.
Furthermore, in the protective agent bar of the present invention, the protective agent preferably contains a hydrophobic organic compound (A) and an amphiphilic organic substance (B).
Furthermore, in the protective agent bar of the present invention, the weight ratio A / B of the hydrophobic organic compound (A) and the amphiphilic organic substance (B) contained in the protective agent is preferably 50/50 to 97/3. Is preferably 60/40 to 95/5.
Furthermore, in the protective agent bar of the present invention, the hydrophobic organic compound (A) contained in the protective agent is preferably paraffin as described above.
Furthermore, in the protective agent bar of the present invention, the protective agent preferably has at least one endothermic peak temperature at 50 to 130 ° C.

More specifically, the protective agent bar used in the protective layer forming apparatus of the present invention contains a hydrophobic organic compound and an amphiphilic organic substance. Since the amphiphilic organic substance has both a hydrophilic structure and a lipophilic (hydrophobic) structure in one molecule, the hydrophilic part of the molecule is attached to the hydrophilic part of the surface of the image carrier. It is considered that the surface of the image carrier is protected by the action of adsorbing and hydrophobizing the part after adsorption.
Furthermore, it is thought that a homogeneous protective agent layer is formed while the adsorbed amphiphilic organic compound hydrophobic structure portion and the hydrophobic organic compound are combined by intermolecular interaction due to intermolecular forces, etc. It is done.

Since the protective agent layer formed on the surface of the image carrier has a hydrophobic portion directed near the outermost surface, even if a lot of hydrophilic substances are contained in the atmosphere near the surface of the image carrier, The electrostatic latent image charge can be prevented from being dissipated without reducing the resistance of the surface of the image carrier even in a usage state where humidity is high.
In addition, after the protective agent layer is formed on the surface of the image carrier, the electrical stress in the charging step and the transfer step is applied to the image carrier protective agent forming the protective agent layer. The molecular chain is subjected to actions such as cleavage, oxidation, and hydrophilization.
As a result, the protective agent is partially decomposed, but the electrical stress on the image carrier is drastically reduced and the deterioration of the image carrier is suppressed. Is possible.
In addition, the protective agent component deteriorated due to electrical stress becomes hydrophilic, but is surrounded by the hydrophilic portion of the amphiphilic organic compound that is excessively present in the protective agent layer, and is formed on the surface of the image carrier. A reverse micelle state is formed in the formed protective agent layer, and it is no longer affected by the surrounding humidity.

The amphiphilic organic compound (B) in the protective agent of the present invention is preferably a nonionic surfactant.
Amphiphilic organic compounds are classified into anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and composites thereof. Since the protective agent forms a protective agent layer on the image carrier as described above and undergoes an image forming process, it is necessary not to adversely affect the electrical characteristics of the image carrier.
By using a nonionic surfactant as an amphiphilic organic compound, the surfactant itself does not dissociate, so even if the usage environment, especially humidity, changes significantly, air discharge etc. Therefore, the image quality can be maintained at a high level.

The nonionic surfactant is preferably an esterified product of an alkyl carboxylic acid of the following chemical formula (1) and a polyhydric alcohol.
C _n H _{2n + 1} COOH Chemical formula (1)
However, n in a formula shows the integer of 15-35.
By using a linear alkyl carboxylic acid as the alkyl carboxylic acid of the above chemical formula (1), the hydrophobic portion of the amphiphilic organic compound can be easily arranged on the surface of the image carrier on which the amphiphilic organic compound is adsorbed. Thus, the adsorption density on the surface of the carrier is particularly high, which is a preferable mode.

The alkyl carboxylic acid ester in one molecule is hydrophobic, and the larger the number, the more the dissociable substances generated by air discharge are prevented from adsorbing on the surface of the image carrier, and the surface of the image carrier in the charged region. It is effective to reduce the electrical stress on. However, if the proportion of the alkyl carboxylic acid ester is too large, the portion of the polyhydric alcohol that exhibits hydrophilicity is obscured and sufficient adsorption performance may not be exhibited depending on the surface state of the image carrier. .
Therefore, the average number of ester bonds per molecule of the amphiphilic organic compound is preferably 1 to 3.

The average number of ester bonds per molecule of these amphiphilic organic compounds can be adjusted by selecting one or more from a plurality of amphiphilic organic compounds having different numbers of ester bonds.
Examples of the amphiphilic organic compound include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant as described above.

  Examples of anionic surfactants include alkylbenzene sulfonate, α-olefin sulfonate, alkane sulfonate, alkyl sulfate, alkyl polyoxyethylene sulfate, alkyl phosphate, long chain fatty acid salt, α -Anion (anion) at the end of the hydrophobic site, such as sulfo fatty acid ester salt and alkyl ether sulfate, and alkali metal ions such as sodium and potassium, and alkaline earth metal ions such as magnesium and calcium , Compounds in which metal ions such as aluminum and zinc, ammonium ions, and the like are bonded.

  Examples of cationic surfactants include a cation (cation) at the end of a hydrophobic site, such as alkyltrimethylammonium salt, dialkylmethylammonium salt, alkyldimethylbenzylammonium salt, etc., and chlorine, fluorine , Bromine and the like, and compounds in which phosphate ions, nitrate ions, sulfate ions, thiosulfate ions, carbonate ions, hydroxide ions, and the like are bonded.

  Examples of amphoteric surfactants include dimethylalkylamine oxide, N-alkylbetaines, imidazoline derivatives, alkyl amino acids and the like.

  Examples of nonionic surfactants include alcohol compounds such as long-chain alkyl alcohols, alkyl polyoxyethylene ethers, polyoxyethylene alkyl phenyl ethers, fatty acid diethanolamides, alkyl polyglucooxides, polyoxyethylene sorbitan alkyl esters, Examples include ether compounds and amide compounds. Also, long-chain alkyl carboxylic acids such as lauric acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, and melicic acid, and polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, erythritol, and hexitol. And ester compounds with these partial anhydrides are also preferred.

  More specific examples of the ester compound include glyceryl monostearate, glyceryl distearate, glyceryl monopartic acid, glyceryl dilaurate, glyceryl trilaurate, glyceryl dipaltimate, glyceryl tripartinate, glyceryl dimyristate, and glyceryl trimistate. Glyceryl stearate, glyceryl stearate, glyceryl monoarachidate, glyceryl diarachidate, glyceryl monobehenate, glyceryl stearate, glyceryl stearate, glyceryl monomontanate, glyceryl monomelicate, and their substitutes, Sorbitan monostearate, sorbitan tristearate, sorbitan monopartitic acid, sorbitan dipartitic acid, Sorbitan palmitate, sorbitan dimyristate, sorbitan trimistate, sorbitan palmitate, sorbitan monoarachidate, sorbitan diarachidate, sorbitan dibehenate, sorbitan monobehenate, sorbitan stearate, sorbitan monostearate, sorbitan monomontanate, monomelicic acid Examples include, but are not limited to, sorbitans of alkylcarboxylic acids such as sorbitan, and their substitutes.

  In addition, these amphiphilic organic compounds may use a single kind, and may use multiple types together.

  In the protective agent of the protective agent bar used in the image forming apparatus of the present invention, the above-mentioned amphiphilic organic compound (B) is preferably mixed with the hydrophobic organic compound (A). By containing the hydrophobic organic compound, the protective agent bar is provided with flexibility, and the amphiphilic organic compound is easily attached to the entire surface of the image carrier. In addition, since the hydrophobic organic compound is generally soft, the protective agent bar can maintain a softness of 5B or more in pencil hardness. Therefore, even if the protective agent supply member brush is rubbed against the protective agent bar, Particles are hardly generated, and the protective agent is easily transferred to the tip of the brush, which is preferable.

  The content of the hydrophobic organic compound in the protective agent of the protective agent bar used in the image forming apparatus of the present invention is 50% by weight or more, preferably 60% by weight or more, and more preferably 70 to 90% by weight. ing. When the content of the hydrophobic organic compound is less than 50% by weight, the protective agent bar becomes brittle. When the brush is rubbed against the protective agent bar, many particles of the protective agent are easily generated, and the protective agent is formed on the entire surface of the image carrier. It is not preferable because it is difficult to adhere to the shape. On the other hand, when the amount of the hydrophobic organic compound in the protective agent is less than 50% by weight, the surface resistance of the image carrier is lowered and the image density is liable to be lowered under high humidity. On the other hand, when the content of the hydrophobic organic compound is 97% by weight or more, the frictional force between the image carrier and the cleaning blade is increased, which is not preferable. In addition, hydrophobic organic compounds are not preferable because they are oxidatively decomposed by the energy of charging to become ionic conductive substances and the latent image is blurred. However, if the amphiphilic organic compound (B) is contained in an amount of 3% by weight or more, even if the hydrophobic organic compound is oxidatively decomposed to become an ionic conductive substance, the ionic conductive substance is converted to an amphiphilic organic substance. Since the compound wraps and cannot impart conductivity, the occurrence of blurring is extremely reduced.

The hydrophobic organic compound in the protective agent of the protective agent bar used in the image forming apparatus of the present invention is preferably 350 to 850, more preferably 400 to 800, based on the weight average molecular weight Mw.
Specifically, examples of hydrophobic organic compounds are classified into aliphatic saturated hydrocarbons, aliphatic unsaturated hydrocarbons, alicyclic saturated hydrocarbons, alicyclic unsaturated hydrocarbons and aromatic hydrocarbons. In addition to hydrocarbons, polytetrafluoroethylene (PTFE), polyperfluoroalkyl ether (PFA), perfluoroethylene-perfluoropropylene copolymer (FEP), polyvinylidene fluoride (PVdF), ethylene-tetrafluoro Examples thereof include fluorine resins such as ethylene copolymer (ETFE) and fluorine waxes, silicone resins such as polymethyl silicone and polymethyl phenyl silicone, and silicone waxes. In addition, the hydrophobic organic compound is not limited to these, but in particular, the aliphatic saturated hydrocarbon has high compatibility with the amphiphilic organic compound, and the amphiphilic organic compound is used on the entire surface of the image carrier. It is very preferable because it can be attached in a film form and is economically inexpensive. Conventionally, aliphatic saturated hydrocarbons are contained in the toner, and the adhesion of the aliphatic saturated hydrocarbons on the image carrier is called so-called wax filming, and is an aliphatic image that generates abnormal images. A measure was taken to prevent the saturated hydrocarbons from adhering to the image carrier. However, it is a new discovery that, when mixed with an amphiphilic organic compound, an abnormal image does not occur even if it adheres to the image carrier while compensating for the difficult extension of the amphiphilic organic compound. is there.

  As aliphatic saturated hydrocarbons, aliphatic saturated hydrocarbons and alicyclic saturated hydrocarbons, in which the intramolecular bonds consist only of stable saturated bonds with low reactivity are preferred, among which normal paraffins, isoparaffins, cycloparaffins, etc. These paraffins are preferably used in terms of stability over time because they are chemically stable and hardly undergo an addition reaction, and hardly undergo an oxidation reaction in actual air.

  Furthermore, since the hydrophobic organic compound (A) contains normal paraffin, a mild interaction with the lipophilic site in the amphiphilic organic compound (B) is performed, and the protective agent formed on the surface of the image carrier. It is more preferable because the layer can be used while being always refreshed, and the removability of the deteriorated material existing in the reverse micelle state in the protective layer is ensured.

As described above, the protective agent layer formed on the surface of the image carrier is exposed to electrical stress and deteriorates. Therefore, if the molecular weight of the hydrophobic organic compound (A) is too small, a sufficient protective effect cannot be exhibited. There is.
On the other hand, if the molecular weight of the hydrophobic organic compound (A) is too large, sufficient spreadability cannot be obtained at the time of forming the protective layer, and the protective agent component adheres as a powder on the image carrier. May not form. In such a state, the contribution of the hydrophobic organic compound (A) to the protection of the photoreceptor is small, and the protection of the image carrier is carried by the amphiphilic organic compound (B) adsorbed on the surface.

As described above, the molecular weight of the hydrophobic organic compound (A) in the protective agent is preferably 350 to 850, more preferably 400 to 800, based on the weight average molecular weight Mw.
In addition, since the protective agent bar is used in the vicinity of the image carrier disposed in the image forming apparatus, the heat generated from a heat source such as a drive system is used under continuous use. Often exposed underneath. Therefore, in order to maintain the shape of the protective agent bar during use, it is necessary to prevent a phase change such as melting of the protective agent composition from occurring up to a certain temperature.
At the same time, in order to reliably protect the surface of the photoconductor from electrical stress, it is preferable that the protective agent is spread on the surface of the image carrier to form a protective agent layer. It is preferable that the intermolecular interaction force of the agent composition is not too high.

When the intermolecular interaction force is large, a large energy is required to change the once-determined internal structure, and therefore the endothermic peak generation temperature measured by a differential thermal analyzer or the like becomes high.
Therefore, in order to ensure the spreadability when forming the protective agent layer on the surface of the image carrier while maintaining the shape of the protective agent bar, the protective agent of the protective agent bar is at least 50 ° C to 120 ° C. It preferably has one endothermic peak temperature. In addition, the endothermic peak temperature in this invention refers to the temperature of the endothermic peak position in the differential heat profile at the time of temperature rising using a differential thermal analyzer.

  In the protective agent, when the hydrophobic organic compound (A) and the amphiphilic organic compound (B) are in a completely solid solution state, the deterioration component of the protective agent is an amphiphilic organic compound (B ), It is preferable that one of the hydrophobic organic compound (A) and the amphiphilic organic compound (B) is dispersed or partially dissolved in the other. Such a state can be realized with good controllability by taking a large difference in endothermic peak temperature between the hydrophobic organic compound (A) and the amphiphilic organic compound (B) and providing a difference in the solidifying temperature. Therefore, it is preferable that the protective agent for the photoreceptor has at least one endothermic peak temperature in the range of 40 to 70 ° C and in the range of 80 to 130 ° C.

Also, when the bond at the terminal part of the protective agent molecule is broken and deteriorates, the terminal part has a low molecular weight, so it is vaporized by the energy of the charged area, etc., and most of it is discharged out of the image forming part by the air current. Is done. Among the deteriorated protective agent components that have been vaporized, those that have a relatively large molecular weight and condense at the temperature of the peripheral member may adhere to or adsorb to the charging member, etc., but these low molecular weight components are charged continuously. Since it is easily decomposed in the process and discharged out of the image forming portion like other low molecular weight components, accumulation with time in the peripheral members hardly occurs.
Therefore, for example, the lubricant component containing a metal element decomposes and oxidizes to become a metal oxide, accumulates in the charging member, contaminates, and increases in resistance. It can be solved by use.

As a method for molding the rod-shaped protective agent bar of the present invention into a certain shape, for example, a prismatic shape or a cylindrical shape, a known method can be used as a method for molding a solid substance.
Examples include, but are not limited to, melt molding, powder molding, hot press molding, cold isostatic pressing (CIP), hot isostatic pressing (HIP), and the like. is not.

Here, taking the melt molding method as an example, as a specific method for molding the protective agent bar, a predetermined amount of the heated and melted protective agent is placed in a mold having a predetermined shape, which is heated in advance to the melting temperature of the protective agent. After pouring and maintaining for a certain period of time at a temperature equal to or higher than the melting point as required, the molded article can be obtained by cooling by standing or cooling. In addition, in order to remove internal distortion of the molded body, after cooling proceeds to a temperature lower than the phase transition temperature of the protective agent component in the middle of cooling, it is gradually reheated to a temperature equal to or higher than the phase transition temperature again. Also good.
After cooling to a temperature close to room temperature, the molded body is removed from the mold to obtain a molded body (protective agent bar) of the protective agent. After that, the shape of the protective agent bar may be further adjusted by cutting or the like.

  As the above-mentioned formwork, metal formwork such as steel, stainless steel (SUS), and aluminum is preferable because of good thermal conductivity and good dimensional accuracy. The inner wall surface of the mold is preferably coated with a release agent such as a fluororesin or a silicone resin in order to improve the releasability.

  As a method of providing the above-mentioned level difference in the protective agent bar, a method of providing a level difference in advance in the molding die, a method of pressing the mold provided with the level difference if necessary after molding the protective agent bar, heated metal, etc. The method of pressing the wire, the method of irradiating with a laser beam, the method of mechanically forming, etc. can be exemplified, but the method of providing a step in the mold in advance is the most preferable because the step can be formed with high productivity.

Specific embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 is a schematic configuration diagram showing a main part of an example of the main part of an image forming unit provided with the protective layer forming apparatus of the present invention.
The protective layer forming apparatus 2 disposed opposite to the drum-shaped photoconductor 1 that is an image bearing member includes a protective agent bar 21 in which a protective agent that protects the photoconductor is made into a rod shape, and a contact with the protective agent bar 21. The protective agent supply member 22 that supplies the photosensitive agent 1 with the protective agent transferred from the protective agent bar 21 to the brush 22a, and the protective agent bar 21 is pressed against the brush 22a of the protective agent supply member 22 for protection. Mainly composed of a pressing force applying mechanism 23 for transferring the agent to the brush 22a of the protective agent supply member 22, and a protective layer forming mechanism 24 for thinning the protective agent supplied onto the photoreceptor by the protective agent supply member 22. Has been.

The protective agent bar 21 according to the present invention is pressed against the brush 22a of the protective agent supply member 22 by a pressing force from a pressing force applying mechanism 23 including a pressing member such as a spring or a spring, and the protective agent bar 21 is applied to the brush 22a. The protective agent is transferred. The protective agent supply member 22 rotates with a linear velocity difference with the photosensitive member 1 and rubs the surface of the photosensitive member with the tip of the brush 22a. At this time, the protective agent held on the surface of the brush 22a of the protective agent supply member 22 is removed. , And supplied to the surface of the photoreceptor 1.
Further, the protective agent supplied to the surface of the photoreceptor 1 may not be a sufficient protective layer at the time of supply depending on the selection of the material type. For this reason, in order to form a more uniform protective layer, the photosensitive agent surface protective agent is, for example, a blade-like member 24a and a spring or spring that presses the blade-like member 24a against the surface of the photosensitive drum 1. And a protective layer on the surface of the photoreceptor.

  The photosensitive member 1 on which the protective layer is formed is brought into contact or proximity with a charging roller 3 to which a DC voltage or a voltage obtained by superimposing an AC voltage is applied by a high voltage power source (not shown) which is a charging means (charging device). Then, the photosensitive member 1 is charged by discharge in a minute gap. At this time, a part of the protective layer is decomposed or oxidized due to electrical stress, and air discharge products adhere to the surface of the protective layer. The above-mentioned decomposition products, oxides, and air discharge products are generally hydrophilic or contain a hydrophilic group.

  The photoconductor protective agent of the present invention contains an amphiphilic organic compound (B) having a hydrophilic part and a hydrophobic part in one molecule as its composition. Moreover, the hydrophobic organic compound (A) is also included as one composition. Therefore, the surface of the photoreceptor becomes hydrophilic by electrical stress, and the amphiphilic organic compound (B) is adsorbed to make the surface hydrophobic and the surrounding hydrophobic organic compound (A). Therefore, it is possible to prevent electrical stress from being directly applied to the surface of the photoreceptor.

  Instead, a part of the photoconductor protective agent is deteriorated by exposure to electrical stress, and partially becomes hydrophilic, but is present in excess, an amphiphilic organic compound (B) having an appropriate HLB value. At the same time, it becomes a form similar to a reverse micelle and is dispersed in the hydrophobic organic compound (A), so that it is possible to achieve both the effect of protecting the photoreceptor by the protective layer and the removability of the deteriorated protective agent.

  The deteriorated protective agent is removed together with other components such as the toner remaining on the photosensitive member 1 by a cleaning device 4 as a cleaning unit by a normal cleaning mechanism. Although the cleaning device 4 may be used also as the protective layer forming mechanism 24 described above, the function of removing the residue on the surface of the photoreceptor and the function of forming the protective layer are different in the rubbing state of appropriate members. Therefore, it is preferable that the functions are separated and provided upstream of the protective layer forming apparatus 2 in the rotation direction of the photosensitive member as shown in FIG. In other words, the protective layer forming device 2 is preferably provided in a portion from the cleaning device 4 as the cleaning unit to the charging roller 3 as the charging unit. In the example of FIG. 1, the cleaning device 4 includes a blade-shaped cleaning member (cleaning blade) 41, a cleaning pressing mechanism 42 that presses the cleaning member 41 against the surface of the photosensitive member, and the like. A cleaning member such as a brush or a roller may be used instead.

  The material of the blade-like member 24a used for the protective layer forming mechanism 24 is not particularly limited. For example, an elastic body such as urethane rubber, hydrin rubber, silicone rubber, or fluorine rubber, which is generally known as a cleaning blade material, is used alone. Or it can be blended and used. In addition, these rubber blades may be coated or impregnated with a low friction coefficient material at the contact portion with the photoreceptor 1. Further, in order to adjust the hardness of the elastic body, fillers represented by other organic fillers and inorganic fillers may be dispersed.

These blade-like members 24a are fixed to the blade support 24c by an arbitrary method such as adhesion or fusion so that the tip portion can be pressed against the surface of the photoreceptor. The thickness of the blade-like member 24a is not uniquely defined in consideration of the force applied by pressing, but is preferably about 0.5 to 5 mm, more preferably about 1 to 3 mm. Can be used.
Further, the length of the blade-like member 24a that protrudes from the support 24c and can be deflected, that is, the so-called free length, is similarly applied by pressing, but cannot be uniquely defined in terms of the force, About 1 to 15 mm can be preferably used, and about 2 to 10 mm can be further preferably used.

As another configuration of the blade-like member 24a for forming the protective layer, the surface of the elastic metal blade such as a spring plate is coated with a layer of resin, rubber, elastomer or the like, if necessary, via a coupling agent or a primer component, It may be formed by a method such as dipping, heat-cured or the like if necessary, and further subjected to surface polishing if necessary.
The thickness of the elastic metal blade is preferably about 0.05 to 3 mm, and more preferably about 0.1 to 1 mm.
Moreover, in an elastic metal blade, in order to suppress the twist of a braid | blade, you may perform processes, such as a bending process, in the direction substantially parallel to a spindle after attachment.
As a material for forming the surface layer, fluorine resin such as PFA, PTFE, FEP, PVdF, silicone elastomer such as fluorine rubber, methylphenyl silicone elastomer, and the like can be used together with a filler, if necessary. It is not limited to this.

  Further, the force for pressing the blade-like member 24a against the photoconductor by the pressing member 24b of the protective layer forming mechanism 24 is sufficient as the force that the protective agent on the surface of the photoconductor extends to form a protective layer or a protective film, The linear pressure is preferably 5 gf / cm or more and 80 gf / cm or less, and more preferably 10 gf / cm or more and 60 gf / cm or less.

In addition, a brush-like member 22a is preferably used as the protective agent supply member 22. In this case, the brush fiber is preferably flexible in order to suppress mechanical stress on the surface of the photoreceptor.
As a specific material of the flexible brush fiber, one or more kinds can be selected and used from generally known materials. Specifically, polyolefin resins (eg, polyethylene, polypropylene); polyvinyl and polyvinylidene resins (eg, polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, and Polyvinyl chloride); vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; styrene-butadiene resin; fluorine resin (for example, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene); Polyester; Nylon; Acrylic; Rayon; Polyurethane; Polycarbonate; Phenol resin; Amino resin (eg urea-formaldehyde resin, melamine) Fat, benzoguanamine resins, urea resins, polyamide resins); Among such, may be a resin having flexibility.
Also, in order to adjust the degree of bending, diene rubber, styrene-butadiene rubber (SBR), ethylene propylene rubber, isoprene rubber, nitrile rubber, urethane rubber, silicone rubber, hydrin rubber, norbornene rubber, etc. are used in combination. Also good.

The support 22b of the protective agent supply member 22 includes a fixed type and a rotatable roll. As the roll-shaped supply member, for example, there is a roll brush in which a tape having brush fibers piled is wound around a metal core in a spiral shape. The brush fiber has a fiber diameter of about 10 to 500 μm, the length of the brush fiber is 1 to 15 mm, and the brush density is 10,000 to 300,000 per square inch (1.5 × 10 ^{7 to} 4.5 × 10 per square meter). ^Eight ) are preferably used.

  The protective agent supply member 22 is preferably made of a material having a very high brush density in terms of supply uniformity and stability, and one fiber is made from several to several hundreds of fine fibers. Is also preferable. For example, bundling 50 fine fibers of 6.7 decitex (6 denier), such as 333 decitex = 6.7 decitex × 50 filament (300 denier = 6 denier × 50 filament), and implanting as one fiber Is also possible.

  In addition, a coating layer may be provided on the surface of the brush 22a as necessary for the purpose of stabilizing the surface shape, environmental stability, and the like of the brush 22a. As a component constituting the coating layer, it is preferable to use a coating layer component that can be deformed according to the bending of the brush fiber, and these are not limited as long as the material can maintain flexibility. Polyolefin resins such as polyethylene, polypropylene, chlorinated polyethylene, chlorosulfonated polyethylene, etc .; polystyrene, acrylic (for example, polymethyl methacrylate), polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, Polyvinyl and polyvinylidene resins such as polyvinyl carbazole, polyvinyl ether, and polybiliketones; vinyl chloride-vinyl acetate copolymers; silicone resins composed of organosiloxane bonds or modified products thereof (for example, alkyd resins, Modified products by reester resin, epoxy resin, polyurethane, etc.); Fluororesin such as perfluoroalkyl ether, polyfluorovinyl, polyfluorovinylidene, polychlorotrifluoroethylene; polyamide; polyester; polyurethane; polycarbonate; urea-formaldehyde resin, etc. Amino resins; epoxy resins, composite resins of these, and the like.

Next, FIG. 2 is a schematic sectional view for explaining a configuration example of an image forming unit (image forming station) using a process cartridge provided in the image forming apparatus of the present invention.
An image forming unit (image forming station) 10 shown in FIG. 2 includes a drum-shaped photoconductor 1 as an image carrier, and a charging device (charging roller in the illustrated example) 3 as a charging unit that charges the photoconductor 1. A latent image forming means (not shown) for forming an electrostatic latent image by irradiating the charged photosensitive member 1 with a laser beam L or the like, and developing the electrostatic latent image on the photosensitive member 1 with toner. A developing device 5 which is a developing means for visualizing, a transfer means 6 for transferring a toner image on the photoconductor 1 to a transfer medium (or an intermediate transfer medium) 7, and a toner remaining on the surface of the photoconductor 1 after transfer. The cleaning device 4 is a cleaning means that removes the protective layer, and the protective layer forming device 2 is disposed in a portion from the cleaning device 4 to the charging device 3. The image forming unit 10 uses a process cartridge 11 in which a protective layer forming device 2, a charging device 3, a developing device 5, and a cleaning device 4 are provided in a cartridge together with the photoreceptor 1.

In FIG. 2, the charging device 3 is, for example, a charging roller to which a DC voltage or a voltage obtained by superimposing an AC voltage is applied by a high voltage power source (not shown). The developing device 5 includes a developing sleeve 51 which is a developer carrying member that carries and conveys toner particles or a mixture of toner particles and carrier particles, and a developer stirring and conveying member that conveys the developer while stirring. 52, 53 and the like.
As in FIG. 1, the protective layer forming apparatus 2 disposed facing the photosensitive member 1 mainly includes a protective agent bar 21, a protective agent supply member 22, a pressing force applying mechanism 23, a protective layer forming mechanism 24, and the like. Composed.
The photosensitive member 1 has a surface on which partially deteriorated protective agent, toner component, and the like remain after the transfer process, but the surface residue is cleaned and cleaned by the cleaning member 41 of the cleaning device 4. In FIG. 2, the blade-like cleaning member 41 is in contact with an angle similar to a so-called counter type (leading type).

  The protective agent of the protective agent bar 21 is supplied by the protective agent supply member 22 to the surface of the photosensitive member from which the residual toner and the deteriorated protective agent have been removed by the cleaning device 4, and the protective agent supplied to the photosensitive member surface. Is thinned by the protective layer forming mechanism 24 to form a film-like protective layer. At this time, the protective agent used in the present invention has a better adsorptivity to the portion of the photoreceptor surface that is highly hydrophilic due to electrical stress. Therefore, even if the surface of the photoconductor starts to deteriorate partially, the progress of deterioration of the photoconductor itself can be prevented by adsorption of the protective agent.

  The photosensitive member 1 on which the protective layer is formed is charged by the charging roller 3 and then an electrostatic latent image is formed by exposure with a laser beam L or the like, and is developed with the toner of the developing device 5 as a developing unit to be visualized. Then, the image is transferred to a transfer medium (or intermediate transfer medium) 7 by a transfer device (transfer roller or the like) 6 which is a transfer means outside the process cartridge.

Next, FIG. 3 is a schematic configuration diagram illustrating a configuration example of the image forming apparatus 100 including the protective layer forming apparatus of the present invention.
The image forming apparatus 100 includes an image forming apparatus main body (printer unit) 110 that performs image formation, a document reading unit (scanner unit) 120 installed on the upper part of the main unit 110, and an automatic document supply unit installed thereon. A paper device (ADF) 130 and a paper feed unit 200 installed at the lower part of the image forming apparatus main body 110 are provided, and have a function of a copying machine. The image forming apparatus 100 has a communication function with an external device, and can be used as a printer or a scanner by connecting to a personal computer or the like outside the device. Further, it can be used as a facsimile by connecting to a telephone line or an optical line.

  In the image forming apparatus main body 110, four image forming units (image forming stations) 10 having the same configuration and different toner colors of the developing device 5 are arranged in parallel, and the four image forming units 10 have different toner colors. An image (for example, an image of yellow (Y), magenta (M), cyan (C), and black (K)) is formed, and a toner image of each color is superimposed on a transfer medium or an intermediate transfer medium and transferred to obtain multiple colors or A full color image can be formed. In the example of FIG. 3, the four image forming units 10 are juxtaposed along the endless belt-shaped intermediate transfer medium 7 stretched around a plurality of rollers, and each color formed in each image forming unit. The toner images are temporarily superimposed on the intermediate transfer medium 7 and primarily transferred, and then transferred to a sheet-like transfer medium such as paper by the secondary transfer device 12.

  The image forming unit 10 for each color has the same configuration as that shown in FIG. 2, and the protective layer forming device 2, the charging device 3, and the latent image forming device 8 are disposed around the drum-shaped photoconductor 1 (1Y, 1M, 1C, 1K). An exposure unit such as a laser beam from the laser beam, a developing device 5, a primary transfer device 6, and a cleaning device 4 are arranged. Similarly to FIG. 2, the image forming unit 10 for each color uses a process cartridge 11 in which a protective layer forming device 2, a charging device 3, a developing device 5, and a cleaning device 4 are provided in a cartridge together with the photoreceptor 1. ing.

Next, the operation of the image forming apparatus shown in FIG. 3 will be described. Here, a series of processes for image formation will be described using a negative-positive process. Since the operations of the image forming units 10 are the same, the operation of one image forming unit will be described here.
The drum-shaped photoreceptor 1, which is an image carrier represented by an organic photoreceptor (OPC) having an organic photoconductive layer, is neutralized by a neutralizing lamp (not shown) or the like, and a charging member (for example, a charging roller) is used. The charging device 3 is uniformly charged negatively.
When the charging device 3 charges the photoreceptor 1, a voltage of an appropriate magnitude suitable for charging the photoreceptor 1 to a desired potential from a voltage application mechanism (not shown) to the charging member or A charging voltage in which an AC voltage is superimposed on this is applied.

The charged photoreceptor 1 is a laser beam irradiated by a laser scanning type latent image forming apparatus 8 including, for example, a plurality of laser light sources, a coupling optical system, an optical deflector, a scanning imaging optical system, and the like. Then, a latent image is formed (the absolute value of the exposed portion potential is lower than the absolute value of the non-exposed portion potential).
That is, laser light emitted from a laser light source (for example, a semiconductor laser) is deflected and scanned by an optical deflector composed of a polygonal polygonal mirror (polygon) that rotates at high speed, thereby forming a scanning image formed of a scanning lens, a mirror, and the like. The surface of the photoconductor 1 is scanned in the rotation axis direction (main scanning direction) of the photoconductor 1 via the optical system.

The latent image formed in this manner is developed with a developer made of toner particles or a mixture of toner particles and carrier particles supplied onto the developing sleeve 51 which is a developer carrying member of the developing device 5, and toner A visual image is formed.
At the time of developing the latent image, a voltage applying mechanism (not shown) is applied to the developing sleeve 51 with a voltage of an appropriate magnitude between the exposed portion and the non-exposed portion of the photoreceptor 1 or an AC voltage superimposed thereon. A bias is applied.

The toner image formed on the photoreceptor 1 of the image forming unit 10 corresponding to each color by the above operation is sequentially superimposed on the intermediate transfer medium 7 by the primary transfer device 6 composed of a transfer roller or the like for primary transfer. Is done. On the other hand, in synchronization with the image forming operation and the primary transfer operation, the paper feed roller 202 and the separation roller are selected from the paper feed cassettes selected from the multi-stage paper feed cassettes 201a, 201b, 201c, and 201d of the paper feed unit 200. A transfer medium such as paper is fed by a paper feed mechanism 203, and is conveyed to a secondary transfer unit through conveyance rollers 204, 205, 206 and a registration roller 207. In the secondary transfer unit, the toner image on the intermediate transfer medium 7 is secondarily transferred to the transferred transfer medium by a secondary transfer device (for example, a secondary transfer roller) 12. In the above transfer process, it is preferable that a potential having a polarity opposite to the toner charging polarity is applied to the primary transfer device 6 and the secondary transfer device 12 as a transfer bias.
After the secondary transfer, the transfer medium is separated from the intermediate transfer medium 7 to obtain a transfer image. Further, the toner particles remaining on the photoreceptor 1 after the primary transfer are collected into the toner collection chamber in the cleaning device 4 by the cleaning member 41 of the cleaning device 4. Further, the toner particles remaining on the intermediate transfer medium 7 after the secondary transfer are collected into the toner collection chamber in the cleaning device 9 by the cleaning member of the belt cleaning device 9.

  The image forming apparatus 100 shown in FIG. 3 is a so-called tandem type intermediate transfer type image forming apparatus in which a plurality of the above-described image forming units 10 are arranged along the intermediate transfer medium 7. A plurality of toner images having different colors sequentially formed on the respective photoreceptors 1 (1Y, 1M, 1C, and 1K) are once transferred onto the intermediate transfer medium 7 and then transferred like a paper at a time. Transfer to media. The transfer medium onto which the toner image has been transferred is sent to the fixing device 14 by the conveying device 13 and the toner is fixed by heat or the like. The fixed transfer medium is discharged to a paper discharge tray 17 by a transport device 15 and a paper discharge roller 16. The image forming apparatus 100 also has a double-sided printing function. During double-sided printing, the conveyance path downstream of the fixing device 9 is switched, and the transfer medium on which the image on one side is fixed is transferred to the front and back sides via the double-sided conveyance apparatus 210. The paper is reversed, and is fed again to the secondary transfer unit by the transport roller 206 and the registration roller 207, and the image is transferred to the back side. The transfer medium after transfer is conveyed to the fixing device 9 in the same manner as described above to fix the image, and the transfer medium after fixing is discharged to the discharge tray 17.

  In the above configuration, the intermediate transfer medium can be used without using an intermediate transfer medium, and a tandem type direct transfer image forming apparatus can be used. In the case of this direct transfer system, the transfer medium is supported instead of the intermediate transfer medium. Using a transfer belt or the like that transports, a plurality of toner images of different colors, which are sequentially created on each photoreceptor 1 (1Y, 1M, 1C, 1K) by each image forming unit 10, are directly transported by the transfer belt. Alternatively, the toner may be transferred to a fixing device after being sequentially transferred to the transfer medium, and the toner is fixed by heat or the like.

In the image forming apparatus as described above, it is preferable that the charging device 3 is a charging device in which a charging member is disposed in contact with or close to the surface of the photosensitive member, thereby using a so-called discharge wire. Compared to a corona discharger called corotron or scorotron, the amount of ozone generated during charging can be greatly suppressed.
However, in the charging device 3 that charges the charging member in contact with or close to the surface of the photosensitive member, since the discharge is performed in the region near the surface of the photosensitive member as described above, the electrical stress on the photosensitive member 1 increases. Tend to.
Therefore, by using the protective layer forming apparatus 2 using the photoconductor protective agent of the present invention, the photoconductor can be maintained for a long time without deteriorating. Can be significantly suppressed, and stable image quality can be ensured.

Next, a photoconductor preferably used in the present invention will be described.
In the photoreceptor, which is an image carrier used in the image forming apparatus of the present invention, a photosensitive layer is provided on a conductive support. The photosensitive layer is composed of a single layer type in which a charge generation material and a charge transport material are mixed, a forward layer type in which a charge transport layer is provided on the charge generation layer, or a charge generation layer provided on the charge transport layer. There is a reverse layer type. In addition, a protective layer can be provided on the photosensitive layer in order to improve the mechanical strength, abrasion resistance, gas resistance, cleaning property, and the like of the photoreceptor. An undercoat layer may be provided between the photosensitive layer and the conductive support. In addition, an appropriate amount of a plasticizer, an antioxidant, a leveling agent and the like can be added to each layer as necessary.

  As the conductive support of the photosensitive member, one having a volume resistance of 10 ^ 10 Ω · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, oxidation A metal oxide such as indium is deposited or sputtered on a film or cylindrical plastic or paper, or a plate of aluminum, aluminum alloy, nickel, stainless steel, etc. After forming the tube into a drum shape, it is possible to use a tube that has been surface-treated by cutting, superfinishing, polishing, or the like. A drum-shaped support having a diameter of 20 to 150 mm, preferably 24 to 100 mm, and more preferably 28 to 70 mm can be used. If the diameter of the drum-shaped support is 20 mm or less, it is physically difficult to arrange the charging, exposure, development, transfer, and cleaning steps around the drum. If the diameter of the drum-shaped support is 150 mm or more, image formation is performed. The apparatus becomes undesirably large. In particular, when the image forming apparatus is a tandem type as shown in FIG. 3, it is necessary to mount a plurality of photoconductors, and therefore the diameter is preferably 70 mm or less, and preferably 60 mm or less. The endless nickel belt and the endless stainless steel belt disclosed in Patent Document 3 can also be used as the conductive support.

  As the undercoat layer of the photosensitive member used in the image forming apparatus of the present invention, a resin or a material mainly composed of a white pigment and a resin, a metal oxide film obtained by chemically or electrochemically oxidizing the surface of a conductive substrate, etc. However, those containing a white pigment and a resin as main components are preferable. Examples of the white pigment include metal oxides such as titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide. Among them, it is most preferable to contain titanium oxide that is excellent in preventing charge injection from the conductive substrate. As the resin used for the undercoat layer, thermoplastic resins such as polyamide, polyvinyl alcohol, casein, and methyl cellulose, thermosetting resins such as acrylic, phenol, melamine, alkyd, unsaturated polyester, and epoxy, one or various kinds of these Mixtures can be exemplified.

  Examples of the charge generating material for the photoreceptor used in the image forming apparatus of the present invention include azo pigments such as monoazo pigments, bisazo pigments, trisazo pigments, and tetrakisazo pigments, triarylmethane dyes, thiazine dyes, and oxazines. Dyes, xanthene dyes, cyanine dyes, styryl dyes, pyrylium dyes, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, indanthrone pigments, squarylium pigments Inorganic materials such as pigments, organic pigments and dyes such as phthalocyanine pigments, selenium, selenium-arsenic, selenium-tellurium, cadmium sulfide, zinc oxide, titanium oxide, and amorphous silicon can be used. It can be used alone or in combination. The undercoat layer may be a single layer or a plurality of layers.

  Examples of the charge transport material for the photoreceptor used in the image forming apparatus of the present invention include anthracene derivatives, pyrene derivatives, carbazole derivatives, tetrazole derivatives, metallocene derivatives, phenothiazine derivatives, pyrazoline compounds, hydrazone compounds, styryl compounds, styryl hydrazone compounds, Enamine compounds, butadiene compounds, distyryl compounds, oxazole compounds, oxadiazole compounds, thiazole compounds, imidazole compounds, triphenylamine derivatives, phenylenediamine derivatives, aminostilbene derivatives, triphenylmethane derivatives, etc. can do.

  The binder resin used to form the photosensitive layer of the charge generation layer and the charge transport layer is electrically insulating and is a known thermoplastic resin, thermosetting resin, photocurable resin, and photoconductive material. Suitable binder resins include, for example, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, Ethylene-vinyl acetate copolymer, polyvinyl butyral, polyvinyl acetal, polyester, phenoxy resin, (meth) acrylic resin, polystyrene, polycarbonate, polyarylate, thermoplastic resin such as polysulfone, polyethersulfone, ABS resin, phenol resin , Epoxy resin, urethane resin, melamine resin, isocyanate resin, alkyd resin, Examples thereof include a thermosetting resin such as a ricone resin, a thermosetting acrylic resin, a type of binder resin such as a photoconductive resin such as polyvinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene, or a mixture of various types of binder resins. In particular, it is not limited to these.

As antioxidant, the following are used, for example.
Monophenol compounds 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di- t-butyl-4-hydroxyphenyl) propionate, 3-t-butyl-4-hydroxynisol and the like.

Bisphenol compounds 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4 ′ -Thiobis- (3-methyl-6-t-butylphenol), 4,4'-butylidenebis- (3-methyl-6-t-butylphenol) and the like.

-High molecular phenol compound 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3 '-Bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, tocophenols, and the like.

Paraphenylenediamines N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine and the like.

Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2- ( 2-octadecenyl) -5-methylhydroquinone and the like.

Organic sulfur compounds Dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like.

Organic phosphorus compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

  As the plasticizer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is about 0 to 30 parts by weight with respect to 100 parts by weight of the binder resin. Is appropriate.

  A leveling agent may be added to the charge transport layer. As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the chain are used, and the amount used is 100 parts by weight of binder resin. 0 to 1 part by weight is suitable.

  As described above, the surface layer is provided to improve the mechanical strength, abrasion resistance, gas resistance, cleaning property, etc. of the photoreceptor. Examples of the surface layer include a polymer having a mechanical strength higher than that of the photosensitive layer and a polymer in which an inorganic filler is dispersed. The polymer used for the surface layer may be either a thermoplastic polymer or a thermosetting polymer, but the thermosetting polymer has a high mechanical strength and does not wear due to friction with the cleaning blade. It is very preferable because of its extremely high ability to suppress. If the surface layer has a thin film thickness, there is no problem even if it does not have the charge transport capability. However, if the surface layer without the charge transport capability is formed thick, the sensitivity of the photoreceptor decreases, the potential increases after exposure, and the residual layer remains. Since the potential rise is likely to occur, it is preferable to use the above-mentioned charge transporting substance in the surface layer or to use a polymer having a charge transporting capability for the protective layer. When the surface layer is provided, the mechanical strength of the photosensitive layer and the surface layer is generally greatly different, and therefore the protective layer is worn away due to friction with the cleaning blade. It is important that the surface layer has a sufficient film thickness, and is 0.01 to 12 μm, preferably 1 to 10 μm, more preferably 2 to 8 μm. If the film thickness of the surface layer is 0.1 μm or less, it is not preferable because it is too thin and easily disappears due to friction with the cleaning blade, and wear of the photosensitive layer proceeds from the disappeared portion. When the film thickness of the surface layer is 12 μm or more, the sensitivity is lowered, the potential after exposure is increased, and the residual potential is easily increased. In particular, when a polymer having charge transport capability is used, the cost of the polymer having charge transport capability is high. This is not preferable.

  The polymer used for the surface layer is preferably a material that is transparent to the writing light during image formation and has excellent insulation, mechanical strength, and adhesiveness. ABS resin, ACS resin, olefin-vinyl monomer copolymer , Chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethyl Examples include resins such as bentene, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy resin. . These polymers may be thermoplastic polymers, but in order to increase the mechanical strength of the polymers, they are crosslinked with a crosslinking agent having a polyfunctional acryloyl group, carboxyl group, hydroxyl group, amino group, etc. By using a curable polymer, the mechanical strength of the surface layer is increased, and wear due to friction with the cleaning blade can be greatly reduced.

As described above, it is preferable that the surface layer has a charge transport capability. In order to provide the surface layer with a charge transport capability, a polymer used for the surface layer and the above-described charge transport material are mixed. A method of using a polymer having a charge transporting capability for the surface layer is conceivable, and the latter method is preferable because it can obtain a photoconductor with high sensitivity and little increase in potential after exposure and little increase in residual potential.
Examples of the polymer having the charge transport layer ability include a group having the charge transport ability (the following chemical formula (2)) in the polymer.

In the above chemical formula (2), Ar ₁ represents a substituted or unsubstituted arylene group. Ar ₂ and Ar ₃ represent a substituted or unsubstituted aryl group, and may be the same or different.

The group having the charge transporting ability is preferably added to a side chain of a polymer having high mechanical strength such as a polycarbonate resin or an acrylic resin, and the monomer can be easily produced, and the acrylic having excellent coatability and curability. It is preferable to use a resin.
An acrylic resin having a charge transporting ability can form a surface layer having high mechanical strength, excellent transparency, and high charge transporting ability by polymerizing an unsaturated carboxylic acid having a group of the chemical formula (2). The acrylic resin forms a crosslinked structure by mixing a polyfunctional unsaturated carboxylic acid, preferably a tri- or higher functional unsaturated carboxylic acid, with the unsaturated carboxylic acid having a monofunctional chemical formula (2) group. It becomes a thermosetting polymer, and the mechanical strength of the surface layer becomes extremely high. Although the group of the chemical formula (2) may be added to the polyfunctional unsaturated carboxylic acid, since the production cost of the monomer becomes high, the polyfunctional unsaturated carboxylic acid has a group of the chemical formula (2). Usually, it is preferable to use a photocurable polyfunctional monomer.

  Examples of the monofunctional unsaturated carboxylic acid having a group represented by the chemical formula (2) include the following chemical formula (3) and chemical formula (4).

In the chemical formulas (3) and (4), R ₁ may have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Good aryl group, cyano group, nitro group, alkoxy group, —COOR ₇ (R ₇ has a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Aryl group which may be substituted), halogenated carbonyl group or CONR ₈ R ₉ (R ₈ and R ₉ are a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent) Or an aryl group which may have a substituent, which may be the same or different from each other), Ar ₁ and Ar ₂ represent a substituted or unsubstituted arylene group, and may be the same May be different. Ar ₃ and Ar ₄ represent a substituted or unsubstituted aryl group, and may be the same or different. X represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group. Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether divalent group, or an alkyleneoxycarbonyl divalent group. m and n represent an integer of 0 to 3.

  The proportion of the polyfunctional unsaturated carboxylic acid is 5 to 75% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% by weight, based on the entire surface layer. When the ratio of the polyfunctional unsaturated carboxylic acid is 5% by weight or less, the mechanical strength of the surface layer is insufficient, and when it is 75% or more, cracks are likely to occur when a strong force is applied to the surface layer, resulting in sensitivity deterioration. Is also not preferable because it is likely to occur.

  When an acrylic resin is used for the surface layer, the surface layer is formed by applying the unsaturated carboxylic acid to the photoreceptor and then irradiating with an electron beam or actinic rays such as ultraviolet rays to cause radical polymerization. Can do. When performing radical polymerization with actinic rays, a solution obtained by dissolving a photopolymerization initiator in an unsaturated carboxylic acid is used. As the photopolymerization initiator, materials used for photocurable paints can be used.

  In the surface layer, fine particles of metal or metal oxide can be dispersed in order to increase the mechanical strength of the surface layer. Examples of the metal oxide include titanium oxide, tin oxide, potassium titanate, TiO, TiN, zinc oxide, indium oxide, and antimony oxide. In addition, for the purpose of improving wear resistance, fluorine resins such as polytetrafluoroethylene, silicone resins, and those obtained by dispersing inorganic materials such as these resins can be added.

  In the above embodiments, the image carrier has been described as a photoconductor. However, the image carrier according to the present invention primarily transfers a toner image formed on the photoconductor to perform color superposition, and further transfers the image onto a transfer medium. It may be an intermediate transfer medium used when performing image formation by the so-called intermediate transfer method.

  As the intermediate transfer medium, a medium having a volume resistance of 10 ^ 5 to 10 ^ 11 Ω · cm 2 is preferable. When the surface resistance is less than 10 ^ 5Ω / □, when transferring the toner image from the photoconductor onto the intermediate transfer medium, so-called transfer dust may be generated in which the toner image is disturbed due to discharge. If it exceeds 11Ω / □, after the toner image is transferred from the intermediate transfer medium to a transfer medium such as paper, the counter charge of the toner image remains on the intermediate transfer medium and appears as a residual image on the next image. is there.

  As an intermediate transfer medium, for example, a metal oxide such as tin oxide or indium oxide, or conductive particles such as carbon black or a conductive polymer, alone or in combination, kneaded with a thermoplastic resin, and then extruded into a belt shape Alternatively, a cylindrical plastic can be used. In addition to this, the above-mentioned conductive particles and conductive polymer are added to a resin solution containing a thermal crosslinking reactive monomer or oligomer, if necessary, and subjected to centrifugal molding while heating to obtain an intermediate transfer medium on an endless belt. You can also

  When providing a surface layer on the intermediate transfer medium, among the surface layer materials used for the above-mentioned photoreceptor surface layer, the composition excluding the charge transport material is appropriately adjusted in combination with a conductive substance, Can be used.

Next, the toner suitably used in the image forming apparatus of the present invention will be described.
First, the toner used in the image forming apparatus of the present invention preferably has an average circularity of 0.93 to 1.00. In the present invention, the value obtained from the following formula (1) is defined as circularity. This circularity is an index of the degree of unevenness of the toner particles, and indicates 1.00 when the toner is a perfect sphere, and the circularity becomes smaller as the surface shape becomes more complicated.
Circularity SR = perimeter of a circle having the same area as the particle projection area / perimeter of the particle projection image: Formula (1)

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

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

The toner used in the image forming apparatus of the present invention preferably has a weight average diameter D4 of 3 to 10 μm in addition to the above circularity. In this range, since the toner particles have a sufficiently small particle size with respect to the minute latent image dots, the dot reproducibility is excellent.
When the weight average diameter D4 is less than 3 μm, phenomena such as a decrease in transfer efficiency and a decrease in blade cleaning properties tend to occur. Moreover, when the weight average diameter D4 exceeds 10 μm, it is difficult to suppress scattering of characters and lines.

Further, the toner according to the present invention preferably has a ratio (D4 / D1) of the weight average diameter D4 and the number average diameter D1 of 1.00 to 1.40. The closer the value of (D4 / D1) is to 1, the sharper the particle size distribution of the toner. Therefore, when (D4 / D1) is in the range of 1.00 to 1.40, the selective development due to the toner particle size does not occur, and the stability of the image quality is excellent.
Since the toner particle size distribution is sharp, the triboelectric charge amount distribution is also sharp, and fogging is suppressed. In addition, when the toner particle diameters are uniform, the latent image dots are developed so as to be densely and orderly arranged, so that the dot reproducibility is excellent.

Next, a method for measuring the particle size distribution of toner particles will be described.
As an apparatus for measuring the particle size distribution of toner particles by the Coulter Counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.

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

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

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

  Examples of the prepolymer comprising a modified polyester resin that can be used for toner preparation include a polyester prepolymer (A) having an isocyanate group, and examples of a compound that extends or crosslinks with the prepolymer include amines (B). Can be mentioned.

  Examples of the polyester prepolymer (A) having an isocyanate group include a product obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3), which is a polycondensate of polyol (1) and polycarboxylic acid (2). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and tri- or higher valent polycarboxylic acid (2-2), and dicarboxylic acid (2-1) alone and dicarboxylic acid (2-1). And a small amount of a trivalent or higher polycarboxylic acid (2-2) mixture.
Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); aromatic aliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

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

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

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

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

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

  In the present invention, not only the polyester (i) modified with a urea bond but also the polyester (ii) not modified can be contained as a binder resin component together with the (i). By using (ii) in combination, the low-temperature fixability and glossiness when used in a full-color apparatus are improved, which is preferable to single use. Examples of (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (i) above, and preferred ones are also the same as (i). (Ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions. When (ii) is contained, the weight ratio of (i) and (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. If the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

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

  In the present invention, the glass transition point (Tg) of the binder resin is usually 50 to 70 ° C., preferably 55 to 65 ° C. If it is less than 50 ° C., the blocking of the toner during high temperature storage deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the urea-modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners. As the storage elastic modulus of the binder resin, the temperature (TG ′) at which 10000 dyne / cm 2 is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the binder resin, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or less, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or more. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

  The binder resin can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group. Further, (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond. When (3) is reacted and (A) and (B) are reacted, a solvent can be used as necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to the isocyanate (3), such as tetrahydrofuran (such as tetrahydrofuran). When polyester (ii) not modified with urea bond is used in combination, (ii) is produced by the same method as polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of (i) and mixed. To do.

In addition, the toner used in the present invention can be produced generally by the following method, but is not limited thereto.
As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.

  The toner particles may be formed by reacting a dispersion composed of a prepolymer (A) having an isocyanate group in an aqueous medium with (B), or using a urea-modified polyester (i) produced in advance. good. As a method for stably forming a dispersion comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium, a toner raw material comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium is used. And a method of dispersing by shearing force. The prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials), a colorant masterbatch, a release agent, a charge control agent, an unmodified polyester resin, etc. are dispersed in an aqueous medium. It may be mixed at the time of formation, but it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion made of urea-modified polyester (i) or prepolymer (A) has a low viscosity and is easy to disperse.

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

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

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphates, alkylamines as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water Amine salts such as salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl N, amphoteric surfactants such as N- dimethyl ammonium betaine and the like.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11). ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid And metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned,

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F-150 (manufactured by Neos).

  Cationic surfactants include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts that are right on the fluoroalkyl group, benzalkco Nitrogen salts, benzethonium chloride, pyridinium salts, imidazolinium salts, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries), Megafac F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos) are listed.

As an inorganic compound dispersant that is hardly soluble in water, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, and the like can also be used.
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Of methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and carboxyl group Esters such as pinyl acetate, pinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinyl pyridine, vinyl pyrrolidone, vinyl imidazole, Homopolymers or copolymers such as those having a nitrogen atom such as ethyleneimine or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, polyethylene Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

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

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

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

When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting the mixture into a high-speed air stream, accelerating the particles, and causing the particles or composite particles to collide with an appropriate collision plate, etc. There is. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to lower the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

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

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

The number average diameter of the colorant in the toner used in the present invention is desirably 0.5 μm or less, preferably 0.4 μm or less, more preferably 0.3 μm or less.
When the number average diameter of the colorant in the toner is larger than 0.5 μm, the dispersibility of the pigment does not reach a sufficient level, and preferable transparency may not be obtained.
A colorant having a fine particle diameter of less than 0.1 μm is sufficiently smaller than a half wavelength of visible light, and thus is considered not to adversely affect light reflection and absorption characteristics. Therefore, the colorant particles of less than 0.1 μm contribute to good color reproducibility and transparency of the OHP sheet having a fixed image. On the other hand, if there are many colorants having a particle size larger than 0.5 μm, the transmission of incident light is hindered or scattered, and the brightness and color of the projected image of the OHP sheet tend to decrease. There is.
Further, if there are many colorants having a particle size larger than 0.5 μm, the colorant is detached from the surface of the toner particles, and various problems such as fogging, drum contamination, and poor cleaning are liable to occur. In particular, the colorant having a particle size larger than 0.7 μm is preferably 10% by number or less of the total colorant, and more preferably 5% by number or less.

Also, by mixing the colorant together with part or all of the binder resin in advance after adding a wetting liquid, the binder resin and the colorant are initially sufficiently adhered, In the toner production process, the colorant is dispersed more effectively in the toner particles, the dispersed particle diameter of the colorant is reduced, and better transparency can be obtained.
As the binder resin used for kneading in advance, the resins exemplified as the binder resin for toner can be used as they are, but are not limited thereto.

As a specific method for kneading the mixture of the binder resin and the colorant with the wetting liquid in advance, for example, the binder resin, the colorant and the wetting liquid are obtained after mixing with a blender such as a Henschel mixer. The obtained mixture is kneaded at a temperature lower than the melting temperature of the binder resin by a kneader such as a two-roll or three-roll to obtain a sample.
In addition, as the wetting liquid, a general one can be used in consideration of the solubility of the binder resin and the paintability with the colorant, but in particular, an organic solvent such as acetone, toluene, butanone, or water, It is preferable from the viewpoint of dispersibility of the colorant.
Among these, the use of water is more preferable from the viewpoint of environmental considerations and maintaining the dispersion stability of the colorant in the subsequent toner production process.
According to this manufacturing method, not only the particle diameter of the colorant particles contained in the obtained toner is reduced, but also the uniformity of the dispersion state of the particles is increased, so that the color reproducibility of the projected image by OHP is further improved. Get better.

In addition, as long as the configuration of the present invention is adopted, a release agent represented by wax can be contained in the toner together with the binder resin and the colorant.
Known release agents can be used, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbons (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. .

  Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecandiol diol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone).

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

In addition, a charge control agent may be contained in the toner as necessary in order to accelerate the toner charge amount and its rise. Here, since a color change occurs when a colored material is used as the charge control agent, a material that is colorless and close to white is preferable.
Any known charge control agent can be used. Examples include triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkyls. Amide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like. Specifically, Bontron P-51 of a quaternary ammonium salt, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex, E-89 of a phenol condensate (above, Orient Chemical Co., Ltd.) Manufactured), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, Quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, boron complex LR-147 (manufactured by Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups Of polymers with functional groups such as carboxylic groups and quaternary ammonium salts Thing, and the like.

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

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

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

Further, inorganic fine particles can be preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner particles.
The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylate esters, acrylate copolymers, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting Examples thereof include polymer particles made of a resin.

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

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

By using these toners, a high-quality toner image having excellent development stability can be formed as described above. However, the toner that is not transferred to the transfer medium or intermediate transfer medium by the transfer device and remains on the image carrier is difficult to remove by the cleaning device due to its fineness and good rolling properties. May end up. In order to completely remove the toner from the image carrier, it is necessary to strongly press a toner removing member such as a cleaning blade against the image carrier. Such a load not only shortens the life of the image carrier and the cleaning device, but also uses extra energy.
When the load on the image carrier is reduced, the toner and the small-diameter carrier on the image carrier are not sufficiently removed, and these damage the surface of the image carrier when passing through the cleaning device. It becomes a factor which fluctuates performance.

As described above, the image forming apparatus of the present invention has an excellent tolerance for fluctuations in the surface state of the photoreceptor, particularly the presence of a low-resistance portion, and has a configuration in which fluctuations in charging performance to the photoreceptor are highly suppressed. For this reason, when used in combination with the toner having the above-described configuration, an extremely high-quality image can be stably obtained over a long period of time.
In addition, the image forming apparatus of the present invention can be applied not only to the use of the toner having a configuration suitable for obtaining a high quality image as described above, but also to an irregular shaped toner by a pulverization method, and the life of the apparatus. Needless to say, it will be greatly extended.

As a material constituting such a pulverized toner, those usually used as an electrophotographic toner can be applied without particular limitation.
Examples of general binder resins used in the toner include homopolymers of styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and the like; styrene / p-chlorostyrene copolymers; Styrene / propylene copolymer, styrene / vinyl toluene copolymer, styrene / vinyl naphthalene copolymer, styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, Styrene / octyl acrylate copolymer, styrene / methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer, styrene / α-chloromethyl methacrylate copolymer, styrene / Acrylonitrile copolymer, styrene / vinyl methyl ketone copolymer, Styrene copolymers such as tylene / butadiene copolymers, styrene / isoprene copolymers, styrene / maleic acid copolymers; polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate, etc. Acrylic ester-based homopolymers and copolymers thereof; polyvinyl derivatives such as polyvinyl chloride and polyvinyl acetate; polyester-based polymers, polyurethane-based polymers, polyamide-based polymers, polyimide-based polymers, polyol-based polymers, Examples thereof include an epoxy polymer, a terpene polymer, an aliphatic or alicyclic hydrocarbon resin, an aromatic petroleum resin, and the like. These can be used alone or in combination, but are not particularly limited thereto. Among these, at least one selected from styrene-acrylic copolymer resins, polyester resins, and polyol resins is more preferable from the viewpoint of electrical characteristics, cost, and the like. Furthermore, it is more preferable to use a polyester-based resin and / or a polyol-based resin as having good fixing characteristics.

  For the reasons described above, the same resin component as the binder resin of the toner contained in the coating layer of the charging member includes a linear polyester resin composition, a linear polyol resin composition, and a linear styrene acrylic resin. At least one of the compositions or these cross-linked products can be preferably used.

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

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples.

[Production method of protective agent bar (1)]
In a glass container with a lid, 72 parts by weight of normal paraffin (average molecular weight 640) and 28 parts by weight of sorbitan monostearate (HLB: 5.9) were stirred with a hot stirrer whose temperature was controlled at 120 ° C. Melted.
Pour the composition of the melted protective agent formulation (1) so as to fill an aluminum mold with an internal dimension of 12 mm x 8 mm x 350 mm heated in advance to 83 ° C, let cool to 50 ° C in a room temperature atmosphere, and set the temperature It was reheated to 60 ° C. in a constant temperature bath and kept at that temperature for 20 minutes, and then allowed to cool to room temperature.
After cooling, the solid material was removed from the mold, and the protective bar that was in contact with the surface of the mold provided with the diamond-shaped grooves had diamond-shaped protrusions. With this surface as the upper side, both ends in the longitudinal direction were cut, and the bottom surface was cut to prepare a protective agent bar (1) of 7 mm × 8 mm × 310 mm. A double-sided tape was affixed to the bottom surface of the protective agent bar (1) and fixed to a metal support.

When the surface of this protective agent bar (1) was scratched with a 6B pencil, streaks were formed, and it was found that this protective agent bar (1) was softer than 6B.
Further, 10 mg of this protective agent bar (1) was sampled and the endothermic peak was measured using a differential thermal analyzer DSC-60 (manufactured by Shimadzu Corporation), and an endothermic peak was obtained at 53 ° C and 88 ° C.

[Method for producing protective agent bar (2)]
In the manufacturing method of the protective agent bar (1), only zinc stearate is used as the protective agent, zinc stearate is put in a glass container with a lid, and the mixture is melted with stirring by a hot stirrer whose temperature is controlled at 165 ° C. A protective agent bar (2) was prepared in the same manner except that. When this protective agent bar (2) was scratched with a 4B pencil, no streaks occurred in the protective agent bar (2), but when it was scratched with a 2B pencil, streaks occurred. That is, it was found that the surface hardness of the protective agent bar (2) was between pencil hardnesses 4B to 2B.

[Brush of protective agent supply member]
As a brush for the protective agent supply member, the end of the polyester fiber is pressed against a heated metal plate, and the area of the end is 0%, 8%, 26 on average than the cross-sectional area of the brush at a position of 50 μm from the brush tip. %, 64%, 87%, and 140% larger brushed fibers were made.

[Examples 1 and 2 and Comparative Example 1]
An undercoat layer, a charge generation layer, a charge transport layer, and a protective layer were applied in this order on an aluminum drum (conductive support) having a diameter of 30 mm, and then dried, and a 3.6 μm undercoat layer, about 0 mm. A photoreceptor comprising a 14 μm charge generation layer, a 23 μm charge transport layer, and a protective layer of about 3.5 μm was prepared. At this time, the coating of the protective layer was performed by a spray method, and the others were performed by a dip coating method. For the protective layer, a charge transporting layer having a formulation in which 23.8% by mass of alumina having an average particle size of 0.18 μm was added was used.

  As the photoconductor 1 and the protective agent bar 22 of the black photoconductor unit configured as shown in FIG. 4 of the tandem type color image forming apparatus (manufactured by Ricoh: imagio Neo C385), the above-prepared photoconductor and protective agent bar ( 1) was set. The brush 22a of the protective agent supply member 22 has an average area of 0% (Comparative Example 1), 8% (Example 1), and 26% of the cross-sectional area of the brush at a position of 50 μm from the brush tip. The photosensitive member 1 is used while applying a DC voltage of −600 V, an AC voltage Peak-to-Peak of 1250 V, and a frequency of 900 Hz to the charging roller 3 without using the photosensitive unit in the image forming apparatus. Rotate for 60 minutes at 130 rpm.

  Each photoconductor unit was set in a black image forming station of a tandem type color image forming apparatus (manufactured by Ricoh: imagio Neo C385), and a black halftone image was output. An average of 8% (Example 1) and 26% (Example 2) of the cross-sectional area of the brush at the position where the end portion is 50 μm from the brush tip gave a high-quality image. Further, the image of the photoconductor unit whose area of the end portion of the brush 22a of the protective agent supply member 22 is 0% on average (cross-sectional area of the brush at a position of 50 μm from the brush tip) (Comparative Example 1) is an abnormal image. I couldn't say it, but when I observed the image with a magnifying glass, a part of the image was observed.

The photosensitive unit of Example 1 and Comparative Example 2 was taken out from the image forming apparatus, and the photosensitive member was further rotated at 130 rpm while applying a DC voltage of −600 V and an AC voltage Peak-to-Peak of 1250 V and a frequency of 900 Hz to the charging roller 3. Rotated for 60 minutes.
Each photoconductor unit was set in a black image forming station of a tandem type color image forming apparatus (manufactured by Ricoh: imagio Neo C385), and when a black halftone image was output, the image of the photoconductor unit of Example 1 was high. Although an image having an image quality was obtained, the portion of the image of the photosensitive unit of Comparative Example 1 where the image partially flowed was observed with the naked eye.

[Comparative Example 2]
The charging roller 3 was applied with a DC voltage of −600 V and an AC voltage Peak-to-Peak in the same manner as described above, except that the protective agent bar (1) of the photoconductor unit of Example 1 was replaced with the protective agent bar (2). While applying 1250 V and a frequency of 900 Hz, the photosensitive member was further rotated at 130 rpm for 120 minutes. When this photoconductor unit was set in a black station of a tandem type color image forming apparatus (Ricoh: imagio Neo C385) and a black halftone image was output, many black streak images were generated.

[Method for producing protective agent bar (3)]
Protective agent bar (1), except that 55 parts by weight of microcrystalline wax (average molecular weight 700) and 45 parts by weight of sorbitan tristearate (HLB: 1.5) are used in the production method of protective agent bar (1). A protective agent bar (3) was produced in the same manner as in the production method.
When the surface of this protective agent bar (3) was scratched with a 6B pencil, streaks were formed, and it was found that this protective agent bar (3) was softer than 6B.
Further, 10 mg of this protective agent bar (3) was sampled and the endothermic peak was measured using a differential thermal analyzer DSC-60 (manufactured by Shimadzu Corporation). As a result, endothermic peaks were obtained at 56 ° C and 95 ° C.

[Production method of protective agent bar (4)]
In the production method of the protective agent bar (1), except that 71 parts by weight of normal paraffin (average molecular weight 640) and 29 parts by weight of glyceryl monostearate (HLB: 3.5) were used, A protective agent bar was produced in the same manner as in the production method.
When the surface of this protective agent bar (4) was scratched with a 6B pencil, streaks were formed, and it was found that this protective agent bar (4) was softer than 6B.
Further, 10 mg of this protective agent bar (4) was sampled and the endothermic peak was measured using a differential thermal analyzer DSC-60 (manufactured by Shimadzu Corporation). As a result, endothermic peaks were obtained at 53 ° C and 88 ° C.

[Example 3 and Comparative Example 3]
A black image forming station of a tandem type color image forming apparatus (Ricoh: imagio Neo C385) was modified to have the configuration shown in FIG. 1 (or FIG. 2), and a protective agent bar (3) was set (Example 3). ). For the other color stations, the protective agent bar produced by the manufacturing method of the protective agent bar (2) was used (Comparative Example 3). In each of the stations, the brush 22a of the protective agent supply member 22 had an end area of 64% on average than the cross-sectional area of the brush at a position of 50 μm from the brush tip.
With this image forming apparatus, five color charts each having an image area of 5% were formed on a total of 50000 sheets. When a black halftone image was output, a high-quality image was obtained. In addition, when cyan and magenta halftone images were output, streaky abnormal images were observed in both images.

[Example 4]
In the same manner as in Example 3, all color stations were modified to the configuration shown in FIG. 1 (or FIG. 2), and the protective agent bar (3) was set. In each station, the brush 22a of the protective agent supply member 22 had an end area of 26% on average than the cross-sectional area of the brush at a position of 50 μm from the brush tip.
With this image forming apparatus, five color charts each having an image area of 5% were formed on a total of 50000 sheets. When a halftone image of each color was output, a high-quality image was obtained.

[Example 5]
An image forming apparatus was produced in the same manner as in Example 4 except that an acrylic thermosetting resin was used for the protective layer of the photoreceptor and the protective agent bar (4) was used.
With this image forming apparatus, five color charts each having an image area of 5% were formed on a total of 100,000 sheets. When a halftone image of each color was output, a high-quality image was obtained.

It is a schematic principal part block diagram which shows the principal part structural example of the image forming part provided with the protective layer forming apparatus of this invention. FIG. 3 is a schematic cross-sectional view for explaining a configuration example of an image forming unit (image forming station) using a process cartridge provided in the image forming apparatus of the present invention. It is a schematic block diagram which shows the structural example of the image forming apparatus 100 which comprises the protective layer forming apparatus of this invention. It is a schematic principal part block diagram which shows another example of a protective layer forming apparatus. It is a figure which shows typically the adhesion state of a protective agent at the time of making the brush of a protective agent supply member cylindrical. It is a figure which shows typically the adhesion state of a protective agent when the brush of a protective agent supply member is made into a column shape, the front-end | tip of a brush is made flat, and the area of a brush front-end | tip is made larger than the cross-sectional area of a brush.

Explanation of symbols

1 (1Y, 1M, 1C, 1K): photoconductor (image carrier)
2: Protection layer forming device 3: Charging device (charging means)
4: Cleaning device (cleaning means)
5: Developing device (developing means)
6: Primary transfer device (transfer means)
7: Intermediate transfer medium (or transfer medium)
8: Latent image forming device 9: Belt cleaning device 10: Image forming unit (image forming station)
11: Process cartridge 12: Secondary transfer device 13: Conveying device 14: Fixing device 15: Conveying device 16: Paper discharge roller 17: Paper discharge tray 21: Protective agent bar 22: Protective agent supply member 22a: Brush 22b: Support 23: pressing force applying mechanism 24: protective layer forming mechanism 24a: blade-like member 24b: pressing member 41: cleaning member 42: cleaning pressing mechanism 51: developing sleeve 52, 53: developer stirring and conveying member 100: image forming apparatus 110: Image forming device (printer)
120: Document reading unit (scanner unit)
130: Automatic document feeder (ADF)
200: paper feed unit 201a-201d: paper feed cassette 202: paper feed roller 203: separation roller 204, 205, 206: transport roller 207: registration roller 210: transport device for both sides

Claims (20)

In a protective material supply member that has a brush in contact with the protective agent bar and supplies the protective agent transferred from the protective agent bar to the brush to the image carrier,
The protective agent supply member, wherein an area of a tip of the brush is 5 to 100% larger than a cross-sectional area of the brush at a position of 50 µm from the tip of the brush. In the protective agent supply member according to claim 1,
The distance in the longitudinal direction of the brush from the place with the largest outer shape of the tip of the brush to the forefront of the brush is 40 μm or less. In the protective agent bar for supplying a protective agent to the brush of the protective agent supply member according to claim 1 or 2,
A protective agent bar comprising a rod-shaped protective agent, wherein the protective agent has a pencil hardness at 25 ° C. set to a hardness softer than 4B. The protective agent bar according to claim 3,
The protective agent bar according to claim 1, wherein the protective agent contains 50% by weight or more of a hydrophobic substance. The protective agent bar according to claim 4,
A protective agent bar, wherein the hydrophobic substance is paraffin. The protective agent bar according to claim 3,
The protective agent bar contains an amphiphilic (hydrophilic and hydrophobic) organic substance, and the content of the amphiphilic organic substance in the protective agent is 3% by weight or more. . The protective agent bar of claim 6,
The HLB value of the amphiphilic organic substance in the protective agent (value indicating the affinity of the surfactant for water and oil: Hydropile-Lipophile Balance) is set to 1.0 to 6.5. Protective agent bar. The protective agent bar according to claim 6 or 7,
The protective agent bar, wherein the amphiphilic organic substance in the protective agent is a nonionic surfactant. In the protective agent bar according to any one of claims 6 to 8,
The protective agent bar, wherein the protective agent contains a hydrophobic organic compound (A) and an amphiphilic organic substance (B). The protective agent bar of claim 9,
A protective agent bar, wherein the weight ratio A / B of the hydrophobic organic compound (A) and the amphiphilic organic substance (B) contained in the protective agent is 50/50 to 97/3. The protective agent bar according to claim 9 or 10,
The protective agent bar, wherein the hydrophobic organic compound (A) contained in the protective agent is paraffin. In the protective agent bar according to any one of claims 3 to 11,
The protective agent bar according to claim 1, wherein the protective agent has at least one endothermic peak temperature at 50 to 130 ° C.   A protective agent supply member according to claim 1 or 2 and a protective agent bar according to any one of claims 3 to 12, wherein the protective agent bar is pressed against a brush of the protective agent supply member. Forming a protective layer, wherein the protective agent is transferred to a brush of the protective agent supply member, and the brush of the protective agent supply member is pressed against the image carrier to supply the protective agent to the image carrier. apparatus. The protective layer forming apparatus according to claim 13, wherein
A pressing force applying mechanism that presses the protective agent bar against the brush of the protective agent supply member to transfer the protective agent to the brush of the protective agent supply member, and is supplied onto the image carrier by the protective agent supply member. A protective layer forming apparatus comprising a protective layer forming mechanism for thinning the protective agent.   15. A process cartridge comprising at least an image carrier and a protective layer forming apparatus according to claim 13 or 14 in the cartridge.   15. An image forming apparatus comprising at least an image carrier and a protective layer forming apparatus according to claim 13 or 14.   An image forming apparatus comprising the process cartridge according to claim 15. The image forming apparatus according to claim 16.
A charging unit for charging the image carrier, a latent image forming unit for irradiating the charged image carrier with light to form an electrostatic latent image, and developing the electrostatic latent image on the image carrier with toner Developing means for visualizing the image, transfer means for transferring the toner image on the image carrier to a transfer medium or intermediate transfer medium, and cleaning for removing the toner remaining on the surface of the image carrier after the transfer. An image forming apparatus comprising: the protective layer forming device in a portion from the cleaning unit to the charging unit of the image forming unit. The image forming apparatus according to claim 17.
A charging unit for charging the image carrier, a latent image forming unit for irradiating the charged image carrier with light to form an electrostatic latent image, and developing the electrostatic latent image on the image carrier with toner Developing means for visualizing the image, transfer means for transferring the toner image on the image carrier to a transfer medium or intermediate transfer medium, and cleaning for removing the toner remaining on the surface of the image carrier after the transfer. An image forming unit having the protective layer forming device in a portion from the cleaning unit to the charging unit of the image forming unit, and forming the image forming unit, An image forming apparatus comprising: at least one of a charging unit, a developing unit, and a cleaning unit, and the protective layer forming device provided in the process cartridge. The image forming apparatus according to claim 18 or 19,
A plurality of the image forming units are arranged side by side, images having different toner colors are formed by the plurality of image forming units, and a toner image of each color is superimposed on a transfer medium or an intermediate transfer medium and transferred to form a multicolor or full color image. An image forming apparatus that forms the image.

Images