JP5601093B2 - Image forming apparatus, image forming method, and process cartridge - Google Patents

Description

  The present invention relates to an electrophotographic photoreceptor and an image forming apparatus. The electrophotographic photosensitive member of the present invention is applied to a copying machine, a facsimile, a laser printer, a direct digital plate making machine, and the like.

In recent years, an organic photosensitive layer containing an organic photoconductive material on a support as an electrophotographic photosensitive member (hereinafter also simply referred to as “photosensitive member” or “image carrier”) mounted on a laser printer or a digital copying machine. A photoconductor provided with is generally used. Among them, a multilayer organic photoreceptor in which a charge generation material and a charge transport material are contained in separate layers is mainly used. This is due to cost, productivity, and freedom of material design.
Since these electrophotographic photoreceptors are exposed to mechanical external force, electrical or chemical hazards in the electrophotographic image forming process, they undergo various deteriorations. In particular, recently, the output of color images has increased, and electrophotographic organic photoreceptors that are used repeatedly over a long period of time are required to have durability against these deteriorations more than ever.

  With regard to mechanical durability, a toner mainly composed of a coloring material and a resin is used with a developer containing hard inorganic fine particles as an additive, and a paper containing an additive composed of hard fibers or clay during transfer is used. Wearing progresses because it is strongly pressed and rubbed, or because it is slid strongly by the cleaning blade during cleaning. For this reason, polycarbonate, polyarylate or the like having high durability is used as the binder resin for the organic photoreceptor. (See Patent Documents 1 and 2).

  Conventionally, various improvements in the mechanical durability have been proposed in which a protective layer is provided on the surface of the photoreceptor. Also in this protective layer, a protective layer in which hard metal oxide fine particles are dispersed, or a layer obtained by crosslinking and hardening the protective layer itself has been studied (see Patent Document 3). In addition, studies have been made to improve the lubricity of the surface of the photoreceptor to prevent the film from being scraped off, and its practical application is also proceeding (see Patent Documents 4 and 5).

As described above, with the increase in output of color images in recent years, higher image quality is required than ever before, but in particular, the cleaning performance of residual toner remaining on the photoconductor for each image formation is higher than before. I found out that it was required. This is due to the fact that a photoconductor with a certain degree of wear durability has been realized but is still unsatisfactory.
In long-term repeated image formation, small scratches and cracks may occur on the surface of the photoconductor, and the surface of the photoconductor slides with the tip of a hard blade for cleaning, so the blade is chipped and fine toner May slip through. In particular, when the latter occurs, black streaks appear in the image and the image quality deteriorates at a stroke. Image degradation due to toner slipping has become an urgent issue for highly durable photoreceptors.

The largest cause of abrasion on the surface of the photoreceptor is the cleaning blade. However, if the transferability of the toner can be improved, residual toner is reduced, pressure applied to the cleaning blade can be reduced, and chipping of the blade can be suppressed. In Patent Document 6, irregularities having a specific shape such as a prism shape, a wave shape, a cone shape, a pyramid shape, or a well shape are formed on the surface of the photosensitive member by a touch roll or a stamper, thereby improving the toner releasability. Consideration has been made.
Further, there is a description that filler particles containing silicon and fluorine are contained in all layers of the charge transport layer to reduce the toner transfer rate and the stress applied to the photoreceptor. However, the photoconductor having the concavo-convex shape in this study, when repeatedly forming an image, the edge of the cleaning blade may be chipped off when the frictional resistance of the photoconductor surface increases. Therefore, there was toner slipping.

  Recently, Patent Document 7 has proposed a method of manufacturing a photoreceptor in which a fine uneven portion shape is transferred to the surface of the photoreceptor. A concave shape having reproducibility is formed on the surface layer by performing molding while maintaining the glass transition point temperature of the charge transport layer, the temperature of the mold, and the temperature of the support in a specific relationship.

  Further, Patent Document 8 describes a method of roughening the surface of the photoreceptor by irradiating the surface layer of the photoreceptor with laser light and forming a plurality of recesses in the surface layer. As a result of examining these, it is said that a resistance adjusting material may be contained in the protective layer, but a residue due to laser light remains in the hole and is not easily discharged, which is not preferable because it interferes with image formation.

  In Patent Document 9, a study has been made to improve the cleaning property by forming a plurality of specific concave portions on the surface of the photoreceptor. The concave hole has a specific major axis diameter and minor axis diameter and depth, and the concave part is present in the surface layer with a specific surface density. It prevents scratches on the surface that grows due to external forces acting in the image forming process such as a cleaning blade. However, there may be a case where a small black spot appears when image formation is repeated due to clogging of the developer additive in the recess. In addition, the formation of the recesses on the surface of the photoreceptor by the conventional laser or mold does not change the formation of fine holes in the surface layer at a high density, and makes the surface layer itself mechanically brittle.

In Patent Document 10, a fine concavo-convex shape having a plurality of concave portions and convex portions formed continuously is formed on the surface of the photosensitive member, and the depth of the concave portion, the height of the convex portion, and the longest axis of the convex portion. The variation in length and the length of the shortest axis are specified. However, this is for the purpose of reducing the discharge caused by the electric memory and is different from the present invention. Further, in the definition of the concavo-convex shape, there is a lack of presentation of a specific size, resulting in a lack of actual use. It has been found that this is not a solution for the problems and purposes of the present invention.
As described above, in the conventional technology, it has been difficult to achieve both prevention of scraping and chatter of the cleaning blade and suppression of toner slipping and filming.

In recent years, there has been a demand for full-color image formation with higher image quality and higher stability, and developers have been designed for higher image quality and higher stability. In order to meet the demand for higher image quality, particularly full-color image quality, toners are increasingly becoming smaller in particle size and are being studied to faithfully reproduce latent images. To reduce the particle size, a toner manufacturing method using a polymerization method has been proposed as a means for controlling the toner to a desired toner shape and surface structure. (For example, Patent Document 11 and Patent Document 12). In the case of the polymerization toner, in addition to controlling the particle size of the toner particles, shape control is possible. In addition, by reducing the particle size together with the spheroidization, the reproducibility of dots and fine lines is improved, the pile height (image layer thickness) can be reduced, and higher image quality can be expected.
However, when a small particle size spherical toner is used for the blade cleaning method, a higher blade pressing pressure is required to remove the toner as compared with the conventional irregularly pulverized toner. However, the present situation is that the demand for high durability for achieving high-quality and high-stable images over a long period of time is not sufficiently met.

  SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide an image forming apparatus using an electrophotographic photosensitive member that is excellent in cleanability of small particle size spherical toner for a long period of time.

The present invention is solved by the following (1) to (6).
(1) “In the image forming apparatus having an electrophotographic photosensitive member having at least a photosensitive layer and a surface layer on a conductive support, the surface of the surface layer of the electrophotographic photosensitive member has a number of convex portions and the respective convex portions. And the toner used in the image forming apparatus has at least an active hydrogen group. The electrophotographic photosensitive member is different from the constituent material of the surface layer. A toner material solution in which a polymer having a site capable of reacting with a compound, polyester, a colorant, and a release agent is dissolved or dispersed in an organic solvent is subjected to at least one of a crosslinking reaction or an extension reaction in an aqueous medium. A spherical toner having a weight average particle diameter of 2 to 6 μm and an average circularity of 0.96 to 0.99 ”,
( 2 ) “Image forming apparatus according to item ( 1 ), wherein the lubricant is a metal soap”,
( 3 ) The item (1) or (2), wherein the toner image formed on the electrophotographic photosensitive member is sequentially transferred onto a transfer medium. The image forming apparatus according to the item ",
( 4 ) "The image forming apparatus according to any one of (1) to ( 3 ) above, wherein the charging unit applies a DC voltage on which an alternating voltage is superimposed",
(5) "Image forming method characterized in that an image is formed using the image forming apparatus according to any one of (1) to ( 4 )",
( 6 ) “It is detachable from the image forming apparatus according to any one of (1) to ( 5 ), and at least the electrostatic latent image carrier and the developing device are detachably integrated. A process cartridge for an image forming apparatus ".

  The surface of the surface layer of the electrophotographic photosensitive member has a large number of convex portions and a mesh-shaped concave portion surrounding each convex portion, and the constituent material of the convex portions is different from the constituent material of the surface layer. The toner used in the image forming apparatus is obtained by dissolving or dispersing at least a polymer having a site capable of reacting with a compound having an active hydrogen group, a polyester, a colorant, and a release agent in an organic solvent. A spherical toner having a weight average particle diameter of 2 to 6 μm and an average circularity of 0.96 to 0.99, obtained by subjecting the toner material liquid to at least one of a crosslinking reaction or an extension reaction in an aqueous medium. Accordingly, it is possible to achieve the cleaning property of the small-diameter spherical toner over a long period of time by the electrophotographic photosensitive member provided with a surface layer having a rough surface with suitable convex portions having high durability. That is, it is possible to provide an image forming apparatus, an image forming method, and a process cartridge that can achieve a high-quality and highly stable image over a long period of time.

FIG. 2 is a cross-sectional view showing a layer structure of an electrophotographic photosensitive member according to the present invention. It is sectional drawing which shows another example of the layer structure of the electrophotographic photoreceptor concerning this invention. It is a figure which shows an example of a structure of the convex part formed in the electrophotographic photoreceptor surface in connection with this invention. It is a figure which shows the definition of the height of the convex part formed in the electrophotographic photoreceptor surface in connection with this invention. It is a conceptual diagram of the spray coating apparatus for forming a convex part in this invention. 1 is a schematic cross-sectional view showing an example of an image forming apparatus according to the present invention. FIG. 6 is a schematic cross-sectional view showing another example of the image forming apparatus according to the present invention. FIG. 6 is a schematic cross-sectional view showing still another example of the image forming apparatus according to the present invention. It is a figure which shows the definition of the arrangement | sequence of the convex part formed in the electrophotographic photoreceptor surface in connection with this invention. It is explanatory drawing of 600 dpi 1by3 dot pattern used for image evaluation in this invention. FIG. 4 is a diagram illustrating the order of colors to be printed and the size (the length in the conveyance direction and the vertical direction of recording paper) when printing is performed using a dot pattern in the present invention. It is the schematic of the continuous type inkjet apparatus for forming a convex part in this invention. It is the schematic of the on-demand type inkjet apparatus (thermal system) for forming a convex part in this invention. 1 is a schematic view of an on-demand type ink jet device (piezo method) for forming convex portions in the present invention.

Hereinafter, the present invention will be described in detail.
The present invention relates to an electrophotographic photosensitive member having a photosensitive layer and a surface layer on at least a conductive support, the surface of the surface layer having a large number of convex portions and a mesh-shaped concave portion surrounding each convex portion. The longest diameter of the convex portion is 10 to 500 μm, the height of the convex portion is 0.5 to 5 μm, and the number of the convex portions is 1 mm square per surface of the surface layer of the photoreceptor. It has the structure which is one or more.

[Electrophotographic photoreceptor]
Hereinafter, the electrophotographic photosensitive member of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view schematically showing an example of an electrophotographic photosensitive member having the layer structure of the present invention. A layer (28) is provided. Here, the charge transport layer and the surface layer may be the same.
FIG. 2 is a cross-sectional view schematically showing an example of an electrophotographic photosensitive member having still another layer structure of the present invention, and an undercoat layer between the conductive support (21) and the charge generation layer (25). (24) is provided, and a charge transport layer (26) and a surface layer (28) are provided on the charge generation layer (25). Here, the charge transport layer and the surface layer may be the same.

[Conductive support]
Examples of the conductive support (21) include those having a volume resistance of 10 ¹⁰ Ω · cm or less, such as metals such as aluminum, nickel, chromium, nichrome, copper, silver, gold, platinum, iron, tin oxide, A film or cylindrical plastic or paper coated with an oxide such as indium oxide by vapor deposition or sputtering, or a plate made of aluminum, aluminum alloy, nickel, stainless steel, or the like, and a drawing ironing method, impact It is possible to use a tube that has been surface-treated by cutting, superfinishing, polishing, or the like after being made into a bare pipe by a method such as the Ironing method, the Extruded Ironing method, the Extracted Drawing method, or the cutting method.

[Underlayer]
In the electrophotographic photoreceptor used in the present invention, an undercoat layer (24) can be provided between the conductive support and the photosensitive layer. The undercoat layer is provided for the purpose of improving adhesiveness, preventing moire, improving coatability of the upper layer, and preventing charge injection from the conductive support.
The undercoat layer usually contains a resin as a main component. Usually, since the photosensitive layer is applied on the undercoat layer, the resin used for the undercoat layer is preferably a thermosetting resin that is hardly soluble in an organic solvent. In particular, polyurethane, melamine resin, and alkyd-melamine resin are particularly preferable materials because many of them sufficiently satisfy the above purpose. The resin can be used as a coating material which is appropriately diluted with a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, butanone and the like.
In addition, fine particles such as metal or metal oxide may be added to the undercoat layer in order to adjust conductivity and prevent moire. In particular, titanium oxide is preferably used.
The fine particles are dispersed by a ball mill, an attritor, a sand mill or the like using a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, or butanone to obtain a paint in which the dispersion and the resin component are mixed.
The undercoat layer is formed on the support by dip coating, spray coating, bead coating, or the like. If necessary, it is formed by heat curing.
In many cases, the thickness of the undercoat layer is suitably about 2 to 5 μm. When the accumulation of the residual potential of the photoconductor becomes large, it is preferable to set it to less than 3 μm.
The photosensitive layer in the present invention is preferably a laminated photosensitive layer in which a charge generation layer and a charge transport layer are sequentially laminated.

[Charge generation layer]
Of the layers in the multilayer photoreceptor, the charge generation layer (25) will be described.
The charge generation layer refers to a part of the laminated photosensitive layer and has a function of generating charges by exposure.
This layer is mainly composed of a charge generation substance among the contained material components. For the charge generation layer, a binder resin may be used as necessary. As the charge generation material, inorganic materials and organic materials can be used.
Examples of the inorganic material include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compound, and amorphous silicon. In amorphous silicon, dangling bonds that are terminated with hydrogen atoms or halogen atoms, or those that are doped with boron atoms or phosphorus atoms are preferably used.

  On the other hand, as the organic material, known materials can be used, for example, metal phthalocyanines such as titanyl phthalocyanine and chlorogallium phthalocyanine, metal-free phthalocyanines, azulenium salt pigments, squaric acid methine pigments, and symmetrical types having a carbazole skeleton. Alternatively, an asymmetric azo pigment, a symmetric or asymmetric azo pigment having a triphenylamine skeleton, a symmetric or asymmetric azo pigment having a fluorenone skeleton, a perylene pigment, and the like can be given. Among these, metal phthalocyanines, symmetric or asymmetric azo pigments having a fluorenone skeleton, symmetric or asymmetric azo pigments having a triphenylamine skeleton, and perylene pigments have a high quantum efficiency of charge generation, and thus are suitable for the present invention. It is suitable as a material to be used. These charge generation materials may be used alone or as a mixture of two or more.

The binder resin used as necessary for the charge generation layer includes polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, polyarylate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-. Examples thereof include vinyl carbazole and polyacrylamide. Moreover, the polymeric charge transport material mentioned later can also be used. Of these, polyvinyl butyral is often used and is useful. These binder resins may be used alone or as a mixture of two or more.
Methods for forming the charge generation layer are roughly classified into a vacuum thin film preparation method and a casting method from a solution dispersion system.
Examples of the former method include a vacuum deposition method, a glow discharge decomposition method, an ion plating method, a sputtering method, a reactive sputtering method, and a CVD (chemical vapor deposition) method. Can be formed satisfactorily.

  In addition, in order to provide the charge generation layer by the casting method, the above-described inorganic or organic charge generation material is mixed with a binder resin, if necessary, using a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, butanone, ball mill, attritor. The dispersion may be dispersed by a sand mill or the like, and the dispersion may be diluted appropriately. Among these solvents, methyl ethyl ketone, tetrahydrofuran, and cyclohexanone are preferable because they have a lower environmental impact than chlorobenzene, dichloromethane, toluene, and xylene. The coating can be performed by a dip coating method, a spray coating method, a bead coating method, or the like.

The thickness of the charge generation layer provided as described above is usually about 0.01 to 5 μm.
When it is necessary to reduce the residual potential and increase the sensitivity, these characteristics are often improved by increasing the thickness of the charge generation layer. On the other hand, the chargeability often deteriorates, such as charge charge retention and space charge formation. From these balances, the thickness of the charge generation layer is more preferably in the range of 0.05 to 2 μm.
Further, if necessary, low-molecular compounds such as antioxidants, plasticizers, lubricants and ultraviolet absorbers and leveling agents described later can be added to the charge generation layer. These compounds can be used alone or as a mixture of two or more. When a low molecular weight compound and a leveling agent are used in combination, sensitivity deterioration often occurs. For this reason, the amount of these used is generally 0.1 to 20 phr, preferably 0.1 to 10 phr, and the amount of the leveling agent used is suitably about 0.001 to 0.1 phr.

[Charge transport layer]
The charge transport layer refers to a part of the laminated photosensitive layer that functions to inject and transport charges generated in the charge generation layer and to neutralize the surface charge of the photoreceptor provided by charging. The main component of the charge transport layer can be referred to as a charge transport component and a binder component that binds the charge transport component.
Examples of materials that can be used for the charge transport material include low molecular weight electron transport materials, hole transport materials, and polymer charge transport materials.
Examples of the electron transporting material include electron accepting materials such as asymmetric diphenoquinone derivatives, fluorene derivatives, and naphthalimide derivatives.
These electron transport materials may be used alone or as a mixture of two or more.

As the hole transport material, an electron donating material is preferably used.
Examples thereof include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, butadiene derivatives, 9- (p-diethylaminostyrylanthracene), 1,1-bis- (4-dibenzylaminophenyl) propane, Examples include styryl anthracene, styryl pyrazoline, phenylhydrazones, α-phenyl stilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives.
These hole transport materials may be used alone or as a mixture of two or more.

In addition, the following polymer charge transport materials can be used. For example, a polymer having a carbazole ring such as poly-N-vinylcarbazole, a polymer having a hydrazone structure exemplified in JP-A-57-78402, and the like exemplified in JP-A-63-285552 The polysilylene polymer to be used, and aromatic polycarbonates exemplified by general formula (1) to general formula (6) of JP-A No. 2001-330973. These polymer charge transport materials can be used alone or as a mixture of two or more. In particular, the exemplified compounds disclosed in JP-A-2001-330973 are useful because of their good electrostatic characteristics.
When polymerized cross-linked resin surface layers are laminated, polymer charge transport materials are less likely to ooze out the components constituting the charge transport layer into the cross-linked resin surface layer compared to low molecular charge transport materials, and the cross-linked resin surface layer is cured. It is a material suitable for preventing defects. In addition, since the charge transport material has high heat resistance due to the high molecular weight, there is little deterioration due to the heat of curing when forming the cross-linked resin surface layer.

Examples of the polymer compound that can be used as the binder component of the charge transport layer include polystyrene, polyester, polyvinyl, polyarylate, polycarbonate, acrylic resin, silicone resin, fluorine resin, epoxy resin, melamine resin, urethane resin, and phenol resin. And thermoplastic or thermosetting resins such as alkyd resins. Of these, polystyrene, polyester, polyarylate, and polycarbonate are useful because they have good charge transfer characteristics when used as a binder component of a charge transport component.
In addition, since the charge transport layer has a cross-linked resin surface layer laminated thereon, the charge transport layer is not required to have mechanical strength as compared with the conventional charge transport layer. For this reason, a material such as polystyrene, which is highly transparent but has a low mechanical strength and is difficult to apply in the prior art, can be effectively used as the binder component of the charge transport layer.
These polymer compounds can be used singly or as a mixture of two or more kinds, or as a copolymer composed of two or more of these raw material monomers, and further copolymerized with a charge transport material.

When an electrically inactive polymer compound is used for modifying the charge transport layer, a cardo polymer type polyester having a bulky skeleton such as fluorene, a polyester such as polyethylene terephthalate or polyethylene naphthalate, or a C type polycarbonate is used. Polycarbonate in which the 3,3 ′ portion of the phenol component is alkyl-substituted with respect to a bisphenol-type polycarbonate, polycarbonate in which the geminal methyl group of bisphenol A is substituted with a long-chain alkyl group having 2 or more carbon atoms, biphenyl or biphenyl Polycarbonate having an ether skeleton, polycarbonate having a long chain alkyl skeleton such as polycaprolactone and polycaprolactone (for example, described in JP-A-7-292095), acrylic resin, polystyrene, hydrogenated Tadiene is effective.
Here, the electrically inactive polymer compound refers to a polymer compound that does not include a chemical structure exhibiting photoconductivity such as a triarylamine structure.
When these resins are used in combination with a binder resin as an additive, the addition amount is preferably 50 wt% or less with respect to the total solid content of the charge transport layer due to restrictions on light attenuation sensitivity.

  When a low molecular charge transport material is used, the amount used is 40 to 200 phr, preferably about 70 to 100 phr. When a polymer charge transport material is used, a material in which the resin component is copolymerized in an amount of about 0 to 200 parts by weight, preferably about 80 to 150 parts by weight with respect to 100 parts by weight of the charge transport component is preferably used.

When two or more kinds of charge transport materials are contained in the charge transport layer, it is preferable that the difference in ionization potential is small. Specifically, by setting the difference in ionization potential to 0.10 eV or less, Can be prevented from becoming a charge trap of the other charge transport material.
Regarding the relationship between the ionization potentials, the difference between the charge transporting material contained in the charge transporting layer and the curable charge transporting material described later is also preferably 0.10 eV or less.
In addition, the ionization potential value of the charge transport material in the present invention is a numerical value obtained by measuring by a general method using the atmospheric atmospheric ultraviolet photoelectron analyzer AC-1 manufactured by Riken Keiki Co., Ltd.
In order to satisfy high sensitivity, the charge transport component is preferably added in an amount of 70 phr or more. In addition, α-phenylstilbene compounds, benzidine compounds, butadiene compound monomers, dimers, and polymer charge transport materials having these structures in the main chain or side chain are materials having high charge mobility. Many useful.

Examples of the dispersion solvent that can be used in preparing the charge transport layer coating material include ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone, ethers such as dioxane, tetrahydrofuran, and ethyl cellosolve, and aromatics such as toluene and xylene. , Halogens such as chlorobenzene and dichloromethane, and esters such as ethyl acetate and butyl acetate. Of these, methyl ethyl ketone, tetrahydrofuran, and cyclohexanone are preferable because they have a lower environmental impact than chlorobenzene, dichloromethane, toluene, and xylene. These solvents can be used alone or in combination.
The charge transport layer can be formed by dissolving or dispersing a mixture or copolymer containing a charge transport component and a binder component as main components in an appropriate solvent, and applying and drying the mixture. As the coating method, a dipping method, a spray coating method, a ring coating method, a roll coater method, a gravure coating method, a nozzle coating method, a screen printing method, or the like is employed.
Furthermore, low-molecular compounds such as antioxidants, plasticizers, lubricants, ultraviolet absorbers and leveling agents described later can be added to the charge transport layer. These compounds can be used alone or as a mixture of two or more. When a low molecular weight compound and a leveling agent are used in combination, sensitivity deterioration often occurs. For this reason, the amount of these used is generally 0.1 to 20 phr, preferably 0.1 to 10 phr, and the amount of the leveling agent used is suitably about 0.001 to 0.1 phr.
This charge transport layer may be employed as the surface layer, and if necessary, a protective layer composed of a crosslinked resin described later may be laminated on the charge transport layer. The film thickness of the charge transport layer is practically about 10 to 40 μm, more preferably about 15 to 30 μm for the purpose of ensuring the required sensitivity and charging ability.

[Composition of convex part]
Further, the surface of the photoreceptor in the present invention has a configuration having a large number of convex portions and a mesh-shaped concave portion surrounding each convex portion.
The shape of the protrusion on the surface of the photoreceptor can be measured using a known laser microscope, optical microscope, or electron microscope. For example, an ultra-deep shape measurement microscope VK-8550 manufactured by Keyence Corporation as a laser microscope, a surface shape measurement system Surface Explorer SX-520DR model manufactured by Ryoka System Co., Ltd., a scanning confocal laser microscope OLS3000 manufactured by Olympus Corporation, Lasertec Corporation For example, 3CCD real color confocal microscope OPTELICS H1200 manufactured by the company can be used. As an optical microscope, a digital microscope VHX-500 manufactured by Keyence Corporation and a 3D digital microscope VC-7700 manufactured by OMRON Corporation can be used. As the electron microscope, a 3D real surface view microscope VE-9800 manufactured by Keyence Corporation can be used. Using these microscopes, it is possible to observe and measure the shape of the projection, the state of the skirt, the arrangement, the height, or the top.

(Basic configuration)
An example of the concavo-convex shape of the present invention is shown in FIG. The black part of FIG. 3 is a convex part, and the white part is a mesh-shaped concave part surrounding the convex part.
In the photoconductor of the present invention, by controlling the height and number of convex portions on the surface of the photoconductor, the toner cleaning property of the photoconductor is improved, and accumulation of foreign matters such as wax on the surface of the photoconductor may occur. And has excellent toner cleaning properties and image stability. The reason for this is not clear, but the large number of protrusions on the surface of the photoconductor reduces the contact area compared to the surface of the smooth photoconductor, thereby suppressing the cleaning blade from being pulled in the driving direction when the photoconductor is driven. In addition, since the reduction of the nip pressure due to the pull-in is suppressed, the toner cleaning property is improved. Furthermore, since the mesh-shaped recessed part surrounding a convex part is connected, it has the path | route through which a foreign material is discharged | emitted, and since it prevents accumulation of a foreign material, it is considered that it has the outstanding image stability. The mesh-shaped recess has a quadrilateral shape in which one of the four sides constituting the mesh is located at the tip of the photoreceptor in the MD (Machine Direction, rotational direction in the cylindrical photoreceptor shown in FIG. 9) direction. It may be.

(Diameter and height of convex part)
The diameter and height of the convex portion are calculated from the profile of the surface on which the convex portion is formed. The calculation method is shown in FIG.
First, the diameter of the convex portion is a lateral distance | x1-x2 | of the surface of x1 and x2, which are the lowest points of both ends of the convex portion, on the profile passing through the apex of the arbitrary convex portion. The measurement was performed at five points in any direction with respect to one convex portion, and the maximum value was taken as the diameter of the convex portion.
Next, the height of the convex portion is a distance (y1 or y2) from the reference line to the top of the convex portion with the lowest point of the hem at the both ends as a reference line on the profile passing through the apex of the arbitrary convex portion. ) As the height of the convex part. In the case where the heights of the skirts do not match, the average height ((y1 + y2) ÷ 2) was taken as the reference line.

The convex diameter suitable for the electrophotographic photosensitive member of the present invention is desirably 10 μm or more and 500 μm or less. When the convex diameter is larger than 500 μm, when the small particle size spherical toner of the present invention is cleaned, it becomes impossible to stop the rotation of the toner at the edge of the cleaning blade, and the toner slips through the cleaning blade, resulting in poor cleaning. It becomes easy to do. Further, at the time of transfer, the points for dispersing the transfer pressure are reduced, the pressure is concentrated, and abnormal images such as worm eaters and dot missing are likely to occur. If the diameter of the convex portion is smaller than 10 μm, the pressing force of the cleaning blade is concentrated, chattering or chipping is likely to occur, and it is not preferable from the viewpoint of life due to blade wear.
The height of the convex portion suitable for the electrophotographic photosensitive member of the present invention is desirably 0.5 μm or more and 5.0 μm or less. If the height of the convex portion is less than 0.5 μm, even if the convex portion diameter is 10 to 500 μm, the rotation of the toner at the edge of the cleaning blade cannot be stopped, and cleaning failure tends to occur. When the height of the convex portion is larger than 5.0 μm, the adhesion between the cleaning blade and the photosensitive member is deteriorated, and cleaning failure is likely to occur. Further, at the time of transfer, the followability of the transfer member to the photosensitive member is deteriorated, so that abnormal images such as worm-eaten and vomit are likely to occur.

(Number of convex parts)
A laser microscope was used to measure the number of protrusions. In the measurement, a drum sample was first placed on a work table, and the tilt was adjusted to adjust the level, and the three-dimensional shape data of the surface of the electrophotographic photosensitive member was captured. At that time, the objective lens used a magnification of 10 times, and the number of convex portions visible in the field of view of the analysis screen was counted per area of 1000 μm square as the number of convex portions.
The number of suitable convex portions of the electrophotographic photosensitive member of the present invention is preferably 2 to 5000 per 1000 μm square.
When the number is less than 2, the cleaning blade pull-in is increased due to an increase in the contact area between the cleaning blade and the photosensitive member, so that the toner cleaning property is deteriorated. If the number is larger than 5000, the convex portions cannot exist independently one by one. Substances that interfere with image formation, such as discharge products, need to be efficiently removed and cleaned from the surface of the photoconductor, so that the protrusions formed on the surface layer are formed independently of each other. The portion is a surface layer portion, and the surface layer portions are continuously connected. This makes it difficult for discharge products and the like to collect. Thus, each convex part needs to exist independently.

(Method for forming protrusions)
Any technique including a known technique may be used as a method for forming a specific protrusion on the photoreceptor of the present invention. As a method for forming the convex portion, a method for forming the convex portion forming coating liquid by atomizing and transferring it from the outside, or applying mechanical or thermal energy to the surface once formed, or destroying the surface material, or There are formation methods that involve alterations such as shape transformation and rearrangement of molecular chains. Examples of the former include a spray coating method, an inkjet method, and a printing method. In the latter, there are a mold processing method using a female mold, and a groove portion around a convex portion by laser ablation using a mask. Further, when processing strain is involved, thermal annealing may be added later.

As one specific example of the method for forming a convex shape of the present invention, a spray coating method in which a convex portion is formed by spraying on the surface of an electrophotographic photoreceptor will be described.
The spray method will be described below.
In order to obtain the convex shape of the present invention, a mask corresponding to a desired pattern is installed on the drum side.
Examples of the mask used include known metal meshes and resin meshes.
A known spray processing (coating) method can be used. FIG. 5 shows an outline of the spray coating apparatus.
A photosensitive drum around which a mask is wound is rotated at a predetermined speed by a rotation driving device (not shown). Next, while supplying the coating liquid and gas to the moving application body having a spray gun at a predetermined pressure, the coating liquid and the gas are oscillated (moved) in the axial direction of the photosensitive drum, and the sprayed coating liquid is sprayed on the photosensitive drum. A coating film can be formed.
Basic coating conditions are the viscosity, solvent and concentration of the coating solution, and the rotational speed of the photoreceptor, the oscillating speed, the form of the discharge port of the spray gun, the pressure of the supplied gas, and the flow rate.

As another specific example of forming the convex shape of the present invention, a method of forming the convex shape on the surface of the photoreceptor by ink jet will be described.
The ink jet method is a method in which a convex forming liquid is atomized and sprayed directly onto the surface layer of the photoreceptor to form a convex portion.
FIG. 12 is a schematic view of a continuous ink jet apparatus. The ink (coating liquid) continuously pushed out from the nozzle by the pump becomes fine droplets by the ultrasonic oscillator.
The droplet is charged by the electrode, and the activation is bent by the deflection electrode as necessary, and reaches the printing surface (photoconductor surface). The coating liquid that has not been bent by the deflection electrode is sucked into a collection port called gutter and returns to the ink tank again. In the formation of the protrusions, the diameter, height, and number per area of the photosensitive member-like protrusions can be adjusted by the coating liquid solid content, pump flow rate, droplet interval, nozzle diameter, head feed speed, and the like.

13 and 14 show an on-demand type ink jet apparatus that ejects a necessary amount of droplets when necessary. FIG. 13 shows a thermal method, and FIG. 14 shows a piezo method.
The thermal method is a principle in which a heater is attached to a part of a fine tube filled with ink, and the heater is instantaneously heated, thereby generating bubbles in the ink and ejecting the ink.
The piezo method is a method in which a piezo element is attached to a part of a fine tube filled with ink, and a voltage is applied to the piezo element to deform the element to eject droplets.
In the formation of the convex portions, the diameter, height, and number per area of the convex portions on the photosensitive member can be adjusted by the coating liquid solid content, deformation amount, fine tube diameter, signal interval, head feed interval, and the like. In order to make the material composition of the convex part different from that of the outermost layer of the photoreceptor, it is necessary to prepare the convex part forming liquid so that the active ingredient other than the solvent differs at least one kind between the outermost layer and the convex part. is there.
In particular, when a curable resin or an inorganic pigment that is not included in the outermost layer is used as the material of the convex portion, the wear resistance is excellent and the sustainability of the effect of the present invention is increased.
When a charge transporting material different from the outermost layer is used as the material of the convex portion, a charge transporting agent having strong gas resistance can be used when the charge transporting agent of the outermost layer has low resistance to the discharge gas.
When resin particles that are not included in the outermost layer are used as the material of the convex portion, it is possible to ensure the lubricity and releasability of the convex portion, and the cleaning property and transferability are further improved.

[Crosslinked resin]
A cross-linked resin may be used as a material constituting the surface convex portion. After coating the paint, a resin having a crosslinked structure is formed by a polymerization reaction or a polycondensation reaction. Since the resin film has a cross-linked structure, the wear resistance is strong. In addition, since a crosslinkable charge transport material is blended, the charge transport property is similar to that of the charge transport layer.
As the charge transport material to be contained in the surface convex portion, a known charge transport compound can be used. Examples of the polymerizable or crosslinkable monomer or oligomer include a chain polymerization compound having an acryloyloxy group and a styrene group, and a sequential polymerization compound having a hydroxyl group, an alkoxysilyl group, and an isocyanate group. From the viewpoint of the obtained electrophotographic characteristics, versatility, material design, and production stability, a combination of a hole transporting compound and a chain polymerization material is preferable. Furthermore, both a hole transporting group and an acryloyloxy group are included in the molecule. Particularly preferred is a system in which a compound having a crosslinking is crosslinked. It can be crosslinked and cured using heat, light and radiation. The crosslinkable resin is preferably three-dimensionally crosslinked.

[Binder material composition of cross-linked resin]
The trifunctional or higher functional binder component may contain caprolactone-modified dipentaerythritol hexaacrylate or dipentaerythritol hexaacrylate. This often improves the wear resistance of the crosslinked film itself or increases the toughness.
The trifunctional or higher functional radical polymerizable monomer having no charge transporting structure is preferably trimethylolpropane triacrylate, caprolactone-modified dipentaerythritol hexaacrylate, or dipentaerythritol hexaacrylate.
These can be obtained from reagent manufacturers such as Tokyo Kasei Co., Ltd., Nippon Kayaku KAYARD DPCA series, DPHA series and the like.
In addition, an initiator such as Ciba Specialty Chemicals Irgacure 184 may be added to the solids in an amount of about 5 to 10 wt% in order to promote or stabilize the curing.
Examples of the crosslinkable charge transport material include a chain polymerization compound having an acryloyloxy group and a styrene group, and a sequential polymerization compound having a hydroxyl group, an alkoxysilyl group, and an isocyanate group. A compound having one or more acryloyloxy groups can be used. Alternatively, the composition may be combined with a monomer or oligomer having one or more (meth) acryloyloxy groups not including a charge transport structure. Such a compound can be contained in at least the coating liquid, and can be crosslinked and cured by applying energy such as heat, light, or radiation such as electron beam or γ-ray. For example, the charge transporting compound in the following general formula (1) can be mentioned.

（式中、ｄ、ｅ、ｆはそれぞれ０または１の整数、Ｒ_１３は水素原子またはメチル基を表わし、Ｒ_１４、Ｒ_１５は水素原子以外の置換基で炭素数１〜６のアルキル基を表わし、複数の場合は異なってもよい。ｇ、ｈは０〜３の整数を表わす。Ｚは単結合、メチレン基、エチレン基または下記構造を表わす。）

(Wherein, d, e and f are each an integer of 0 or 1, R ₁₃ represents a hydrogen atom or a methyl group, and R ₁₄ and R ₁₅ represent a substituent other than a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. (G and h are integers of 0 to 3. Z represents a single bond, a methylene group, an ethylene group, or the following structure.)

または

Or

具体的な化合物群として以下のものが挙げられる。

Specific compounds include the following.

  The dispersion solvent used in preparing the crosslinked resin coating is preferably one that sufficiently dissolves the monomer. In addition to the ethers, aromatics, halogens, esters described above, Cellosolve (registered trademark) such as ethoxyethanol And propylene glycols such as 1-methoxy-2-propanol. Of these, methyl ethyl ketone, tetrahydrofuran, cyclohexanone, and 1-methoxy-2-propanol are preferable because they have a lower environmental impact than chlorobenzene, dichloromethane, toluene, and xylene. These solvents can be used alone or in combination.

  Examples of the coating of the crosslinked resin paint include dipping method, spray coating method, ring coating method, roll coater method, gravure coating method, nozzle coating method, and screen printing method. In many cases, since the pot life of the paint is not long, a means capable of coating the required amount with a small amount of paint is advantageous in terms of environmental consideration and cost. Of these, the spray coating method and the ring coating method are preferred. In order to impart the special shape of the present invention, a method using an ink jet method can also be adopted.

When the crosslinked resin material is formed, a UV irradiation light source such as a high-pressure mercury lamp or a metal halide lamp having a light emission wavelength mainly in ultraviolet light can be used. In addition, a visible light source can be selected in accordance with the absorption wavelength of the radical polymerizable substance or the photopolymerization initiator. Irradiation light amount is 50 mW / cm ² or more, preferably 1000 mW / cm ² or less, it takes time for the curing reaction is less than 50 mW / cm ^2. When it is higher than 1000 mW / cm ² , the reaction progress is uneven, and local wrinkles are generated in the cross-linked resin film, or many unreacted residues and reaction termination ends are generated. In addition, internal stress increases due to rapid crosslinking, which causes cracks and film peeling.

If necessary, low molecular compounds and leveling agents such as antioxidants, plasticizers, lubricants, UV absorbers and the like described in the charge generation layer, and polymer compounds described in the charge transport layer may be added to the crosslinked resin film. it can. These compounds can be used alone or as a mixture of two or more. When a low molecular weight compound and a leveling agent are used in combination, sensitivity deterioration often occurs.
For this reason, the amount used is generally 0.1 to 20 wt%, preferably 0.1 to 10 wt%, and the leveling agent used is about 0.1 to 5 wt% in the total solid content of the paint.

In the present invention, the filler may contain filler fine particles from the viewpoint of wear resistance. As the filler fine particles, the following can be used. Examples of the organic filler material include fluorine resin powder such as polytetrafluoroethylene, silicone resin powder, and carbon fine particles.
The carbon fine particles are particles having a structure mainly composed of carbon. Particles having a structure such as amorphous, diamond, graphite, amorphous carbon, fullerene, zeppelin, carbon nanotube, carbon nanohorn, and the like. Among these structures, particles containing hydrogen-containing diamond-like carbon or amorphous carbon structure have good mechanical and chemical durability. The diamond-like carbon or amorphous carbon film containing hydrogen is a particle in which similar structures such as a diamond structure having an SP3 orbit, a graphite structure having an SP2 orbit, and an amorphous carbon structure are mixed. Diamond-like carbon or amorphous carbon fine particles are not limited to carbon, but may contain other elements such as hydrogen, oxygen, nitrogen, fluorine, boron, phosphorus, chlorine, bromine and iodine. Absent.

Examples of inorganic filler materials include metal powders such as copper, tin, aluminum, and indium, metal oxides such as silicon oxide, tin oxide, zinc oxide, titanium oxide, indium oxide, antimony oxide, and bismuth oxide, and potassium titanate. An inorganic material is mentioned. In particular, from the viewpoint of the hardness of the filler fine particles, it is advantageous to use an inorganic material among them. In particular, metal oxides are good, and silicon oxide, aluminum oxide, and titanium oxide can be used effectively.
Also, fine particles such as colloidal silica and colloidal alumina can be used effectively.
The average primary particle size of the filler fine particles is preferably from 0.1 to 1.0 μm from the viewpoint of light transmittance and wear resistance.
The higher the filler material concentration, the better the wear resistance and the better. However, if the filler material concentration is too high, the residual potential increases and the writing light transmittance of the surface layer decreases, which may cause side effects. Therefore, it is about 50% by weight or less, preferably about 30% by weight or less based on the total solid content.

Furthermore, these filler fine particles can be surface treated with at least one kind of surface treatment agent, which is preferable from the viewpoint of dispersibility of the filler fine particles. Lowering the dispersibility of the filler particles not only increases the residual potential, but also decreases the transparency of the coating film, causes defects in the coating film, and decreases the wear resistance. It can develop into a big problem to hinder. As the surface treatment agent, a conventionally used surface treatment agent can be used, but a surface treatment agent capable of maintaining the insulating properties of the filler fine particles is preferable. For example, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent, a higher fatty acid, etc., or a mixing treatment of these with a silane coupling agent, Al ₂ O ₃ , TiO ₂ , ZrO ₂ , Silicone, aluminum stearate, or the like, or a mixture thereof is more preferable from the viewpoint of dispersibility of filler fine particles and image blur. The treatment with the silane coupling agent is strongly influenced by image blur, but the influence may be suppressed by performing a mixing treatment of the surface treatment agent and the silane coupling agent. The surface treatment amount varies depending on the average primary particle size of the filler fine particles to be used, but is preferably 3 to 30 wt%, and more preferably 5 to 20 wt%. When the surface treatment amount is less than this, the effect of dispersing the filler fine particles cannot be obtained, and when it is too much, the residual potential is significantly increased. These filler fine particle materials may be used alone or in combination of two or more.

[toner]
In order to achieve the object of the present invention, the toner particle diameter is preferably 2 to 6 [mu] m, and particularly preferably 3 to 5 [mu] m. When it is smaller than 2 μm, toner dust is likely to be generated in the primary transfer and the secondary transfer, and a cleaning failure occurs even in the cleaning and the photoconductor of the present invention. On the other hand, when it is larger than 6 μm, the dot reproducibility becomes insufficient, the graininess of the halftone portion is deteriorated, and a high-definition image cannot be obtained.
The average circularity of the toner is preferably 0.96 to 0.99. When the average circularity is lower than 0.96, the image uniformity during development is deteriorated, or the intermediate transfer member or the electrophotographic photosensitive member is used. The toner transfer efficiency from the intermediate transfer member to the transfer material is lowered, and uniform transfer cannot be obtained. Toners with an average circularity greater than 0.99 are virtually impossible to manufacture.
It is preferable that a large particle size silica having a primary average particle size of 80 to 500 nm is added to the surface of the toner. Accordingly, the dam layer is easily formed stably on the edge of the cleaning blade, and the non-electrostatic adhesion force of the toner particles can be reduced by the spacer effect, so that the cleaning is easily performed. Furthermore, since it is difficult for silica to be buried in the surface of the toner even when subjected to mechanical stress over time, it is possible to suppress poor cleaning over a long period of time.
When the primary average particle diameter of silica is smaller than 80 nm, the dam layer is not formed stably, so that the dam layer is easily broken, and the spacer effect cannot be obtained sufficiently, so that the non-electrostatic adhesion force of the toner particles is sufficient. Therefore, the cleaning is difficult.
Furthermore, when subjected to mechanical stress over time, silica tends to be buried in the toner surface, so that it becomes impossible to suppress poor cleaning over a long period of time. On the other hand, when the primary average particle diameter of silica is larger than 500 nm, the silica itself tends to slip through the blade nip, and the toner itself also easily slips from the starting point, resulting in poor cleaning. In addition, the fluidity of the toner itself is extremely deteriorated, causing a problem in toner replenishment.
The proportion of silica added is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the toner base. When the added ratio is less than 0.5 parts by weight, the spacer effect cannot be sufficiently obtained, so that the non-electrostatic adhesion force of the toner particles cannot be reduced, and cleaning failure is likely to occur. If the amount is more than 5 parts by weight, the fluidity of the toner may be deteriorated and uniform transferability may be hindered, or the amount of silica released from the toner may increase, causing the carrier or the photoreceptor to be spent and contaminated. is there.

The color toner of the present invention is preferably produced in an aqueous medium, and is particularly effective for obtaining a small particle size and shape in the toner of the present invention.
Examples of the production method include, but are not limited to, a suspension polymerization method, an emulsion association method, and a dissolution suspension method.

<Suspension polymerization method>
A colorant, a release agent and the like are dispersed in an oil-soluble polymerization initiator and a polymerizable monomer, and then emulsified and dispersed by an emulsification method described later in an aqueous medium containing a surfactant and other solid dispersants. Thereafter, a polymerization reaction is performed to form particles, and excess surfactant and the like are washed away to obtain toner particles.
Polymerizable monomers such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, acrylamide, methacrylamide, diacetone Functional groups can be introduced on the surface of toner particles by using a part of acrylate or methacrylate such as acrylamide or these methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate and other amino groups. .
Further, by selecting a dispersant having an acid group or a basic group as a dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

<Emulsion polymerization aggregation method>
A water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by an ordinary emulsion polymerization technique. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer that can be used in the suspension polymerization method.

<Polymer suspension method>
As an aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination.
Examples of the water-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.
In the oil phase of the toner composition, a colorant such as resin, prepolymer and pigment, a release agent, a charge control agent and the like are dissolved or dispersed in a volatile solvent.
An oil phase composed of a toner composition is dispersed in an aqueous medium in the presence of a surfactant, a solid dispersant and the like, and a prepolymer is reacted to form particles.
In order to introduce a functional group into the toner particles, a copolymer with a monomer having a functional group used in the suspension polymerization method, or a functional group of an acid group as an acid monomer in the case of a polyester resin is used. It can be obtained by using one having three or more or esterifying the terminal hydroxyl group of the obtained polyester resin with a compound having a plurality of acid groups. Further, as a dispersion stabilizer in an aqueous medium, which will be described later, an acid group-containing surfactant, polar polymer, organic or inorganic resin fine particles can be used, and an acid group can be introduced by remaining on the toner particle surface. Examples of the acid group include a carboxyl group, a sulfone group, a sulfonic acid group, and a phosphoric acid group.

(Toner characteristic evaluation method)
<Weight average particle diameter (D4), volume average particle diameter (Dv), and number average particle diameter (Dn)>
The weight average particle diameter (D4), volume average particle diameter (Dv), and number average particle diameter (Dn) of the toner are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm. It measured and analyzed with the analysis software (Beckman Coulter Multisizer 3 Version3.51). Specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a glass 100 ml beaker, 0.5 g of each toner was added, and the mixture was stirred with a micropartel. Subsequently, 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

<Average circularity>
The average circularity of the toner is defined by the average circularity SR = (peripheral length of a circle having the same area as the particle projection area / perimeter length of the particle projection image) × 100%. Measurement was performed using a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation), and analysis was performed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). Specifically, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and each toner 0.1 to 0 is added. 0.5 g was added and stirred with a micropartel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the density of the dispersion was 5000 to 15000 / μl. In this measurement method, it is important that the concentration of the dispersion liquid is 5000 to 15000 / μl from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above, and if it is added in a large amount, noise due to bubbles is generated. If the amount is too small, the toner cannot be sufficiently wetted and dispersion is not achieved. It will be enough. The amount of toner added varies depending on the particle size, and it is small for small particle sizes and needs to be increased for large particle sizes. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0.3. By adding 5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.

Hereinafter, an example of a method for producing a toner and an example of a constituent material according to the present embodiment will be described.
The toner to which the present invention is applied is not limited to the toner exemplified here.
The base coloring particles of the toner according to the exemplary embodiment include at least a binder resin, a chromatic colorant, and a release agent. Can be obtained. In particular, the base colored particles of the toner according to the exemplary embodiment are close to a polymer suspension method, and include at least a polymer having a site capable of reacting with a compound having an active hydrogen group, an unmodified polyester, a colorant, and a release agent. A toner obtained by cross-linking and / or elongation reaction of a toner material solution, each of which is dissolved or dispersed in an organic solvent, in an aqueous medium is preferable.
The polymer having a site capable of reacting with a compound having an active hydrogen group is preferably a polyester prepolymer having a site capable of reacting with a compound having an active hydrogen group. This polyester prepolymer undergoes crosslinking and / or elongation reaction in an aqueous medium and is contained in the toner as a modified polyester (i).
The modified polyester (i) refers to a state in which a bonding group other than an ester bond is present in the polyester resin, and resin components having different configurations are bonded to the polyester resin by a covalent bond, an ionic bond, or the like. Specifically, the polyester terminal is modified by introducing a functional group such as an isocyanate group that reacts with a carboxylic acid group or a hydroxyl group into a polyester terminal and further reacting with a compound having an active hydrogen group.

[Toner Production Method (1) to (5)]
(1) A toner material solution is prepared by dissolving or dispersing at least a polymer having a site capable of reacting with a compound having an active hydrogen group, an unmodified polyester, a colorant, and a release agent in an organic solvent. As the polymer having a site capable of reacting with a compound having an active hydrogen group, a polyester prepolymer having a site capable of reacting with a compound having an active hydrogen group is preferred, for example, a polyester prepolymer (A) having an isocyanate group. Can be mentioned.

  As the polyester prepolymer (A) having an isocyanate group, a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and a polyester having an active hydrogen group, and a polyvalent isocyanate compound (PIC) And those reacted with. Examples of the active hydrogen group possessed by such a polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). Dihydric alcohol (DIO) alone or dihydric alcohol (DIO) and a small amount of 3 A mixture with a polyhydric alcohol (TO) having a valence higher than that is preferred.
Examples of the dihydric alcohol (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts.
Among these, 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 polyhydric alcohol (TO) 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 polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) and a small amount of (TC) Mixtures are preferred.
Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.
As the polyhydric alcohol compound (PO) and polyvalent carboxylic acid (PC), in addition to those exemplified above, other substances may be used as long as they can form a polyester having an active hydrogen group by polycondensation. It is also possible to do.

Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) ); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.
The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. %. 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 polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. 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.
Further, the toner according to the present embodiment is not limited to the above-described modified polyester (i) (polyester prepolymer (A)) alone, but also the modified polyester (i) and unmodified polyester (ii) as a binder resin component. It can also be contained. By using the unmodified polyester (ii) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to the single use.

(Unmodified polyester)
Examples of the unmodified polyester (ii) include polycondensates of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) similar to the polyester component of the modified polyester (i). Same as i). The unmodified polyester (ii) may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. The modified polyester (i) and the unmodified polyester (ii) are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, the polyester component of the modified polyester (i) and the unmodified polyester (ii) preferably have similar compositions. When the unmodified polyester (ii) is contained, the weight ratio of (i) to (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25 / 75, particularly preferably 7/93 to 20/80. When the weight ratio of the modified polyester (i) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

The above-mentioned unmodified polyester (ii) has a peak molecular weight of usually 1000 to 10,000, preferably 2000 to 8000, and more preferably 2000 to 5000. 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 the unmodified polyester (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 the unmodified polyester (ii) is preferably 1 to 5, and more preferably 2 to 4. Since a high acid value wax is used for the wax, the binder resin is easily matched with the toner used for the two-component developer because the low acid value binder resin leads to charging and high volume resistance.
The glass transition temperature Tg of the binder resin is usually 35 to 70 ° C., preferably 55 to 65 ° C. If it is less than 35 ° C., the heat resistant storage stability of the toner is deteriorated, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner tends to have good heat-resistant storage stability even at a low glass transition temperature Tg, as compared with known polyester-based toners. .

(Coloring agent)
As the colorant used in the toner according to the exemplary embodiment, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium Mu yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG) ), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu , Permanent red 4R, para red, phi -Red, Parachlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil red, kina Redon Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue , Indanthrene Blue (RS, BC), Indigo, Ultramarine, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian , Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake Malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

The colorant used in the toner according to the exemplary embodiment can be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Len-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like can be used alone or in combination. .
This master batch can be obtained by mixing and kneading a master batch resin and a colorant under a high shear force to obtain a master batch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method called an aqueous paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
In addition, the toner according to the exemplary embodiment can contain a binder resin and a colorant as well as a wax as a release agent. Known waxes can be used as the wax used in the present embodiment, and examples thereof include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long-chain hydrocarbons (paraffin wax, sasol wax, etc.); carbonyl group-containing waxes.
Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, 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 the wax 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.

(Charge control agent)
Further, the toner according to the exemplary embodiment may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.
Specifically, Nitronine dye Bontron 03, quaternary ammonium salt quotient Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E -84, phenolic condensate E-89 (above, trade name, manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, trade name, Hodogaya Chemical Co., Ltd.) Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, trade name, manufactured by Hoechst), LRA-901, LR-147 (trade name, manufactured by Nippon Carlit Co., Ltd.), a copper complex, copper complex Roshianin, perylene, quinacridone, azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

The amount of the 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, but is not uniquely limited. Preferably, it is 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 of course, may be added when directly dissolving or dispersing in an organic solvent, or may be fixed on the toner surface after preparation of toner particles. May be.
Further, it is preferable that the organic solvent used for preparing the toner material liquid is volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, 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. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

(2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone, alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolve (registered trademark) (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), etc. An organic solvent may be included. The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid 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 toner material liquid is poorly dispersed, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.

  Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added. As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, fatty acid amide derivatives, polyhydric alcohols Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium 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 fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6-C16 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C16-C20) carvone Acids 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) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.
Moreover, as anionic surfactant, Surflon S-111, S-112, S-113 (above, a brand name, Asahi Glass Co., Ltd. product), Florard FC-93, FC-95, FC-98, FC-129 ( Above, trade name, manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (above, trade name, manufactured by Daikin Industries), MegaFuck F-110, F-120, F-113, F-191, F -812, F-833 (above, trade name, manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204, (above, trade name) , Manufactured by Tochem Products Co., Ltd.), Fantent F-100, F150 (above, trade name, manufactured by Neos), and the like.

  In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like. As cationic surfactants, Surflon S-121 (trade name, manufactured by Asahi Glass Co., Ltd.), Florard FC-135 (trade name, manufactured by Sumitomo 3M), Unidyne DS-202 (trade name, manufactured by Daikin Industries), Mega Fax F-150, F-824 (trade name, manufactured by Dainippon Ink, Inc.), Xtop EF-132 (trade name, manufactured by Tochem Products), Footgent F-300 (trade name, manufactured by Neos) Etc.

The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. Examples thereof include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin, 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. For example, vinyl resins are polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, (meth) acrylic acid-acrylic acid esters. Examples thereof include resins such as a polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer. The average particle size of the resin fine particles is 5 to 200 nm, preferably 20 to 300 nm. In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

  As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, 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 acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, polyoxyp Pyrene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene Polyoxyethylenes such as nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  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. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. 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.

(3) At the same time as the preparation of the emulsion, the amines (B) are added to react with the polyester prepolymer (A) having an isocyanate group. This reaction involves at least one of a molecular chain crosslinking reaction and / or an elongation reaction. The polyester prepolymer (A) undergoes a crosslinking reaction and / or elongation reaction in an aqueous medium, and is contained in the toner as a modified polyester (i).

  The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. 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.

The above-mentioned modified polyester (i) has a weight average molecular weight of usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10000, and if it is less than 1000, the elongation reaction hardly occurs and the elasticity of the toner is small, and as a result, the hot offset resistance deteriorates. On the other hand, when it exceeds 10,000, the problem in production becomes high in the deterioration of fixability, particle formation and pulverization. The number average molecular weight of the modified polyester (i) is not particularly limited when the above-described unmodified polyester (ii) is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. . In the case of the modified polyester (i) alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.
In the crosslinking reaction or elongation reaction between the polyester prepolymer (A) and the amines (B) for obtaining the urea-modified polyester, a reaction terminator can be used as necessary to adjust the molecular weight of the resulting urea-modified polyester. . Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).
As amines (B) to be reacted with the polyester prepolymer (A), divalent amine compounds (B1), trivalent or higher polyvalent amine compounds (B2), amino alcohols (B3), amino mercaptans (B4), amino acids (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.). Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the compound (B6) obtained by blocking the amino group of B1 to B5 include ketimine compounds and oxazolidine 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.
The ratio of the amines (B) is equivalent to the equivalent ratio [NCO] / [NHX] of the isocyanate group [NCO] in the polyester prepolymer (A) having an isocyanate group and the amino group [NHX] in the amine (B). 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 becomes low, and the hot offset resistance deteriorates.
The urea-modified polyester 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.

(4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the whole system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent-based toner base particles can be produced by removing the solvent. . When a dispersion stabilizer that is soluble in an acid or alkali such as calcium phosphate is used, the calcium phosphate is dissolved from the toner base particles by a method such as dissolving the calcium phosphate with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

(5) A charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner.
The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained.
Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the true spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to.

(General considerations for external additives)
Although important matters of the large particle size external additive according to the present embodiment are as described above, the matters that should be generally considered will be described below. As an external additive for assisting the fluidity, developability and chargeability of the obtained colored particles, inorganic fine particles, hydrophobized inorganic fine particles and the like can be used. Any of them can be used as long as the conditions are satisfied. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide) may be contained. 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. Particularly suitable external additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles.

  Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H 1303 (trade name, manufactured by Hoechst), R972, R974, RX200, RY200, R202, R805, R812 (and above). , Trade name, manufactured by Nippon Aerosil Co., Ltd.). Further, as titania fine particles, P-25 (trade name, manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (above, trade name, manufactured by Titanium Industry Co., Ltd.), TAF-140 (trade name, Fuji Titanium). Manufactured by Kogyo Co., Ltd.), MT-150W, MT-500B, MT-600B, MT-150A (above, trade name, manufactured by TEIKA). In particular, as hydrophobized titanium oxide fine particles, T-805 (trade name, manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (above, trade name, manufactured by Titanium Industry Co., Ltd.), TAF-500T, There are TAF-1500T (the trade name, manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (the trade name, manufactured by Teica), IT-S (made by Ishihara Sangyo Co., Ltd.), and the like.

  In order to obtain hydrophobized inorganic fine particles, silica fine particles, titania fine particles, and alumina fine particles, hydrophilic fine particles are treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. In addition, silicone oil-treated inorganic fine particles obtained by treating the silicone oil with heat if necessary to treat the inorganic fine particles are also suitable.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone. Oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil and the like can be used.

  The toner of the present invention preferably contains 0.05 to 0.5 parts by weight of a lubricant as an external additive with respect to 100 parts by weight of the toner. As a result, the coefficient of friction on the surface of the photosensitive member can be reduced, and the edge of the cleaning blade is reduced, so that it is possible to maintain a good cleaning property for a long period in combination with the effect of the convex shape. When the amount of the lubricant is more than 0.5 parts by weight, the lubricant moves to and adheres to the charging member, which may prevent the uniform charging of the photoreceptor, or may adhere to the surface of the photoreceptor and cause filming or medaka. It becomes easy to induce. If the amount of the lubricant is less than 0.05 parts by weight, the coefficient of friction on the surface of the photoreceptor cannot be sufficiently reduced, and the edge of the cleaning blade is drawn more easily, and cleaning failure tends to occur. Furthermore, since the protective function of the photosensitive member cannot be exhibited, wear of the photosensitive member surface layer due to charging or a cleaning blade is promoted, and the effect of the convex shape described above cannot be exhibited over a long period of time.

  Examples of the lubricant include fatty acid metals such as lead oleate, zinc oleate, copper oleate, zinc stearate, cobalt stearate, iron stearate, copper stearate, zinc palmitate, copper palmitate and zinc linolenate. Fluorine such as salts, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polytrifluorochloroethylene, dichlorodifluoroethylene, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-oxafluoropropylene copolymer Based resins. Among these, the lubricant is preferably a metal soap. This is because the effect of reducing the friction coefficient of the photoreceptor is great. Furthermore, among them, stearic acid metal salts and zinc stearate are more preferable from the viewpoint of applicability to a photoreceptor.

[Career]
Next, the carrier used in the image forming apparatus of the present invention will be described. First, the important point (weight average particle diameter) of the carrier in the present invention will be described, and the constituent material of the carrier and the production method will be described later.

(Carrier characteristics evaluation method)
<Weight average particle size>
The weight average particle diameter Dw of the carrier is calculated based on the particle diameter distribution (relationship between the number frequency and the particle diameter) of the particles measured on the basis of the number. The weight average particle diameter Dw in this case is represented by the formula (3).
Dw = {1 / Σ (nD3)} × {Σ (nD4)} Expression (3)
In formula (3), D represents the representative particle size (μm) of the particles present in each channel, and n represents the total number of particles present in each channel. The channel indicates a length for equally dividing the particle size range in the particle size distribution diagram, and 2 μm is adopted in the present invention. In addition, as the representative particle size of the particles present in each channel, the lower limit value of the particle size of the particles stored in each channel was adopted.

Further, the number average particle diameter Dp of the carrier and the core material particles of the carrier is calculated based on the particle diameter distribution of the particles measured on the basis of the number. The number average particle diameter Dp in this case is represented by the formula (4).
Dp = (1 / ΣN) × (ΣnD) (4)
In Equation (4), N represents the total number of particles measured, n represents the total number of particles present in each channel, and D represents the lower limit of the particle size of the particles stored in each channel (2 μm). Show.

In the present invention, a microtrack particle size analyzer model HRA9320-X100 (manufactured by Honeywell) can be used as a particle size analyzer for measuring the particle size distribution. The measurement conditions are as follows.
[1] Particle size range: 8 to 100 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

(Constituent materials and manufacturing method of carriers)
As the carrier in the present invention, conventionally known carriers such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 15 to 45 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoropropylene resins , Copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinyl fluoride Fluoro such as terpolymers of isopropylidene and a non-fluorinated monomer, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

<Image forming apparatus>
Next, the electrophotographic method and the image forming apparatus of the present invention will be described in detail with reference to the drawings.
FIG. 6 is a schematic diagram for explaining the electrophotographic process and the image forming apparatus of the present invention, and the following examples also belong to the category of the present invention.
The photoconductor (10) rotates in the direction of the arrow in FIG. 6, and there are a charging member (11), an image exposure member (12), a developing member (13), and a transfer member (16) around the photoconductor (10). ), A cleaning member (17), a charge removal member (18), and the like are disposed. The cleaning member (17) and the charge removal member (18) may be omitted.

  The operation of the image forming apparatus is basically as follows. The charging member (11) charges the surface of the photoreceptor (10) almost uniformly. Subsequently, image light writing corresponding to the input signal is performed by the image exposure member (12) to form an electrostatic latent image. Next, the electrostatic latent image is developed by the developing member (13), and a toner image is formed on the surface of the photoreceptor. The formed toner image is transferred onto the transfer paper (15) sent to the transfer site by the transport roller (14) by the transfer member. This toner image is fixed on the transfer paper by a fixing device (not shown). Part of the toner that has not been transferred to the transfer paper is cleaned by the cleaning member (17). Subsequently, the charge remaining on the photoreceptor is neutralized by the neutralizing member (18), and the process proceeds to the next cycle.

As shown in FIG. 6, the photoconductor (10) has a drum shape, but may have a sheet shape or an endless belt shape. As the charging member (11) and the transfer member (16), in addition to corotron, scorotron, solid state charger (solid state charger), a roller-shaped charging member or a brush-shaped charging member is used. Are all usable.
On the other hand, light sources such as the image exposure member (12) and the charge removal member (18) include fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LEDs), semiconductor lasers (LD), and electroluminescence (EL). ) And other luminescent materials can be used. Among these, a semiconductor laser (LD) and a light emitting diode (LED) are mainly used.
Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
The light source or the like irradiates the photoconductor (10) with light by providing a transfer process, a static elimination process, a cleaning process, or a pre-exposure process using light irradiation together. However, the exposure of the photoconductor (10) in the static elimination process has a large influence of fatigue on the photoconductor (10), and may cause a decrease in charge and an increase in residual potential.
Therefore, there is a case where it is possible to eliminate static electricity by applying a reverse bias in the charging process or cleaning process instead of static elimination by exposure, which may be effective from the viewpoint of enhancing the durability of the photoreceptor.

When the electrophotographic photosensitive member (10) is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.
A known method is applied to the developing unit, and a known method is also used for the charge eliminating unit.

Among the contaminants that adhere to the surface of the photoconductor, discharge substances generated by charging and external additives contained in the toner are easy to pick up the effects of humidity and cause abnormal images. Paper powder is one of the causative substances, and when they adhere to the photoreceptor, abnormal images are more likely to occur, as well as a tendency to reduce wear resistance and cause uneven wear. Is seen. Therefore, it is more preferable from the viewpoint of high image quality that the photoconductor and the paper are not in direct contact for the above reason.
The toner developed on the photoreceptor (10) by the developing member (13) is transferred to the transfer paper (15), but not all is transferred, and the toner remaining on the photoreceptor (10). Also occurs. Such toner is removed from the photoreceptor (10) by the cleaning member (17).
As the cleaning member, a known member such as a cleaning blade or a cleaning brush is used. Moreover, both may be used together.

  The photoconductor according to the present invention can be applied to a small-diameter photoconductor because high photosensitivity and high stability are realized. Therefore, as an image forming apparatus or method for using the above photoreceptor more effectively, each developing unit corresponding to a plurality of colors of toner is provided with a plurality of corresponding photoreceptors, thereby performing parallel processing. It is very effectively used in a so-called tandem type image forming apparatus. The tandem image forming apparatus includes at least four color toners of yellow (C), magenta (M), cyan (C), and black (K) required for full-color printing and a developing unit that holds them. Further, by providing at least four photoconductors corresponding to them, full-color printing can be performed at a very high speed as compared with a conventional image forming apparatus capable of full-color printing.

FIG. 7 is a schematic diagram for explaining the tandem-type full-color electrophotographic apparatus of the present invention, and the following modifications also belong to the category of the present invention.
In FIG. 7, photoconductors (10C (cyan)), (10M (magenta)), (10Y (yellow)), and (10K (black)) are drum-like photoconductors (10), and these photoconductors. (10C, 10M, 10Y, 10K) rotate in the direction of the arrow in the figure, around which at least the charging members (11C, 11M, 11Y, 11K), the developing members (13C, 13M, 13Y, 13K), Cleaning members (17C, 17M, 17Y, 17K) are arranged.
From the back side of the photoreceptor (10) between the charging member (11C, 11M, 11Y, 11K) and the developing member (13C, 13M, 13Y, 13K), laser light (12C, 12M, 12Y, 12K) is irradiated, and electrostatic latent images are formed on the photoconductors (10C, 10M, 10Y, 10K).
Then, four image forming elements (20C, 20M, 20Y, 20K) centering on such a photoreceptor (10C, 10M, 10Y, 10K) are along a transfer conveyance belt (25) which is a transfer material conveyance unit. Are juxtaposed.
The transfer / conveying belt (19) is disposed between the developing member (13C, 13M, 13Y, 13K) of each image forming unit (20C, 20M, 20Y, 20K) and the cleaning member (17C, 17M, 17Y, 17K). A transfer member (16C) for applying a transfer bias to the surface (rear surface) which is in contact with the photoconductor (10C, 10M, 10Y, 10K) and contacts the back side of the photoconductor (10) side of the transfer conveyance belt (19). , 16M, 16Y, 16K). Each of the image forming elements (20C, 20M, 20Y, 20K) is different in toner color inside the developing device, and the other components have the same configuration.

In the color electrophotographic apparatus having the configuration shown in FIG. 7, the image forming operation is performed as follows. First, in each of the image forming elements (20C, 20M, 20Y, and 20K), the charging member (11C, 11M, 11Y, and 11K) in which the photosensitive member (10C, 10M, 10Y, and 10K) rotates along with the photosensitive member 10 is rotated. ), And then an electrostatic image corresponding to the image of each color to be created by laser light (12C, 12M, 12Y, 12K) by an exposure unit (not shown) arranged outside the photoconductor (10). A latent image is formed.
Next, the latent image is developed by a developing member (13C, 13M, 13Y, 13K) to form a toner image. The developing members (13C, 13M, 13Y, and 13K) are developing members that perform development with toners of C (cyan), M (magenta), Y (yellow), and K (black), respectively. 10M, 10Y, and 10K) are overlaid on the transfer belt (19).
The transfer paper (15) is sent out from the tray by the paper supply roller (21), temporarily stopped by the pair of registration rollers (22), and sent to the transfer member (23) in synchronization with the image formation on the photosensitive member. It is done. The toner image held on the transfer belt (19) is transferred onto the transfer paper (15) by an electric field formed by a potential difference between the transfer bias applied to the transfer member (23) and the transfer belt (19). . The toner image transferred onto the transfer paper is conveyed, the toner is fixed onto the transfer paper by the fixing member (24), and is discharged to a paper discharge unit (not shown). Further, residual toner that is not transferred by the transfer unit and remains on the photosensitive members (10C, 10M, 10Y, and 10K) is collected by cleaning members (17C, 17M, 17Y, and 17K) provided in the respective units. The

The intermediate transfer method as shown in FIG. 7 is particularly effective for an image forming apparatus capable of full-color printing. By forming a plurality of toner images once on an intermediate transfer body and transferring them to paper at once, It is easy to control the color shift and is effective for high image quality.
The intermediate transfer member includes various materials or shapes such as a drum shape and a belt shape. In the present invention, any conventionally known intermediate transfer member can be used. It is effective and useful for achieving high quality or high image quality.
In the example of FIG. 7, the image forming elements are arranged in the order of C (cyan), M (magenta), Y (yellow), and K (black) from the upstream side to the downstream side in the transfer paper conveyance direction. However, it is not limited to this order, and the color order is arbitrarily set. Further, when a black-only document is created, it is particularly effective to use the present invention to provide a mechanism that stops the image forming elements (20C, 20M, 20Y) other than black.

  The image forming means as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, but may be incorporated in these apparatuses in the form of a process cartridge.

As shown in FIG. 8, the process cartridge includes a photoconductor (10), a charging member (11), an image exposure member (12), a developing member (13), a transfer member (16), a cleaning member. It is one apparatus (part) including the member (17) and the charge removal member.
The above-described tandem image forming apparatus can transfer a plurality of toner images at a time, so that high-speed full-color printing is realized.
However, since at least four photoconductors are required, an increase in the size of the apparatus is unavoidable, and depending on the amount of toner used, there is a difference in the wear amount of each photoconductor, thereby reproducing the color. There are many problems such as a decrease in performance and occurrence of abnormal images.
On the other hand, the photosensitive member according to the present invention can be applied to a small-diameter photosensitive member by realizing high photosensitivity and high stability, and the influence of increase in residual potential, sensitivity deterioration, etc. is reduced. Even if the amount of the photoconductor used is different, the difference in residual potential and sensitivity over time is small, and a full color image having excellent color reproducibility can be obtained even when used repeatedly for a long time.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example. Note that “parts” used in the examples all represent parts by weight.

First, tests and measurement methods related to the present invention will be described.
(1) Measurement of photoconductor surface shape The surface of the photoconductor was observed using a 3CCD real color confocal (confocal) microscope OPTELICS H1200 (Lasertec). The height, diameter, number of convex portions, and the angle at which the straight line connecting the vertices of the nearest convex portions intersects the photosensitive member rotation direction were measured according to the contents described in the text. Moreover, a measured value is an average value of 10 measurements, respectively.
(2) Durability Test The electrophotographic photosensitive member and developer thus prepared were set in an image forming apparatus (Imagio MP C7500 manufactured by Ricoh Co., Ltd.), and a running test was performed.
The initial potential of the photoconductor was set so that Vd (dark portion potential) of the photoconductor was −800 V and Vl (light portion potential) was −200 V at room temperature and normal humidity (25 ° C., 60% RH).
The paper used was Ricoh Co., Ltd. 6200 paper (A4, T-th). The test chart is a mixture of photographic images and characters, and can evaluate the background portion, solid black portion, and halftone.
The evaluation items are evaluation of toner cleaning properties (toner slipping), photoconductor state (scratches and wear), and output image in the durability test. In both cases, the normal part was compared with the deteriorated part by visual observation and an optical microscope. In the durability test, continuous image output of 1000K sheets was performed. The evaluation rank is shown below.

<Toner slip-through>
Five halftone patterns and blank paper patterns depicting 4 dots x 4 dots in an 8 x 8 matrix with a pixel density of 600 dpi x 600 dpi are printed alternately and continuously, and the background standard of the blank paper pattern is visually checked as follows. It was evaluated with.
○: No problem △: Rank: Streaks or density unevenness due to toner slipping are clearly in the output image ×: Streaks or density unevenness due to toner slipping are clearly present at multiple positions in the output image

<Observation of photoreceptor surface>
The surface of the photoreceptor after the test was observed with a laser microscope (Keyence VK-8500). Evaluation was performed according to the following criteria.
○: No problem Δ: Slight filming is observed or scratches are observed on the surface ×: Large filming occurs or many scratches are observed on the surface

<Image evaluation>
(Chile, dot defect, color shift evaluation)
FIG. 10 is an explanatory diagram of a 600 dpi 1-by-3 dot pattern used for image evaluation.
FIG. 11 is a diagram illustrating the order of colors to be printed and the size (the length in the conveyance direction and the vertical direction of the recording paper) when printing is performed using a dot pattern.
As an evaluation image, the 600 dpi 1-by-3 dot pattern shown in FIG. 10 is yellow, magenta, cyan, black, blue (cyan + magenta), green (yellow + cyan), red (yellow + magenta), three-color black (yellow + Select 100 out of 1,000 continuous prints in the order (cyan + magenta) in the order of 2 cm in the recording paper transport direction and 15 cm in the direction perpendicular to the recording paper transport direction (see FIG. 11). Each image was observed with 10 loupes for each image, and a comparative evaluation was performed using a limit sample to comprehensively evaluate the image quality rank of the minute dots.
Further, as another evaluation image, three dots of 600 dpi are 10 cm long in the direction perpendicular to the recording paper conveyance direction, and yellow, magenta, cyan, black, blue (cyan + magenta), green (yellow + cyan), red ( Yellow + magenta) and three-color black (yellow + cyan + magenta) are arranged in the order of 1,000 sheets printed from 1,000 consecutive sheets, and the image quality rank of fine lines is visually evaluated using limit samples. evaluated.
The image quality rank was five, and a good image having no dust or dot defects was set to 5, and one having no dust or dot defects that could not be established as an image was set to 1. Evaluate each color of yellow, magenta, cyan, black, blue (cyan + magenta), green (yellow + cyan), red (yellow + magenta), three-color black (yellow + cyan + magenta), and final comprehensive evaluation The average value is shown.
(Solid uniformity)
An A3 all-solid image was output, the image density at four corners and one center of the A3 paper was measured, the solid uniformity was calculated by the following formula, and the rank was given according to the following criteria.
Solid uniformity = (maximum value of image density−minimum value of image density) × 100 (%)
The image density was measured using a gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. under the condition of an incident angle of 60 °.
Average image density at 5 locations Rank 5: Less than 15% Rank 4: 15-30%
Rank 3: 31-50%
Rank 2: 51-70%
Rank 1: 71% or more

<Photoconductor>
A specific example of producing the photoreceptor used for the evaluation is shown below.
(Photoreceptor 1)
An undercoat layer was formed on an Al support (outer diameter: 40 mmφ) by an immersion method so that the film thickness after drying was 3.5 μm.
・ Coating liquid alkyd resin for undercoat layer 6 parts (Beckosol 1307-60-EL, manufactured by Dainippon Ink & Chemicals, Inc.)
Melamine resin 4 parts (Super Becamine G-821-60, manufactured by Dainippon Ink & Chemicals, Inc.)
Titanium oxide 40 parts (CR-EL: Ishihara Sangyo)
50 parts of methyl ethyl ketone

On this undercoat layer, it was dip-coated in a charge generation layer coating solution containing a bisazo pigment having the following structure and dried by heating at 120 ° C. for 25 minutes to form a charge generation layer having a thickness of 0.2 μm.
-Coating solution for charge generation layer 2.5 parts of bisazo pigment with the following structure

ポリビニルブチラール（ＸＹＨＬ、ＵＣＣ製） ０．５部
シクロヘキサノン ２００部
メチルエチルケトン ８０部

Polyvinyl butyral (XYHL, manufactured by UCC) 0.5 part cyclohexanone 200 parts methyl ethyl ketone 80 parts

On this charge generation layer, a charge transport layer coating liquid having the following structure was dip-coated, and heated and dried at 120 ° C. for 25 minutes to obtain a charge transport layer having a thickness of 22 μm.
・ Coating liquid for charge transport layer 10 parts of bisphenol Z type polycarbonate 10 parts of low molecular charge transport material with the following structure

テトラヒドロフラン ８０部
１％シリコーンオイルのテトラヒドロフラン溶液 ０．２部
電荷輸送層を形成後、感光体ドラム周面に１インチにおける網目の数が１００の金属メッシュ（開口率３６．５％）を撒きつけた。このときの撒きつける向きは、メッシュの網目が感光体の回転方向に対して４５度になるように設定した（図９参照）。その上から下記構成の凸部形成用塗工液を用いて、ドラム回転速度；８０ｒｐｍ、スプレーガン送り速度；１５．５ｍｍ／ｓ、吐出量５．０ｍｌ／ｍｉｎ、吹きつけ圧力；２．５ｋｇｆ／ｃｍ^２、吹きつけ回数；１回の条件でスプレー塗工を行ない、１０分間の指触乾燥を行なった。
続いて、感光体ドラムから金属メッシュを取り外して、このドラムとＵＶ硬化ランプから１２０ｍｍ距離を置いて、ドラムを回転させながらＵＶ硬化を施した。この位置でのＵＶ硬化ランプ照度は５５０ｍＷ／ｃｍ^２（紫外線積算光量計ＵＩＴ−１５０、ウシオ社製による測定値）であった。また、ドラムの回転速度は２５ｒｐｍとした。ＵＶ硬化を行なう際、アルミニウムドラム内に３０℃の水を循環させて連続３分間、ＵＶ硬化した。その後、１３０℃にて３０分間加熱乾燥した。凸部の径が２５０μｍ、凸部の高さが３．０μｍ、凸部の１ｍｍ四方あたりの個数が１６個の凹凸形状を持つ感光体が得られた。
・凸部形成用塗料
電荷輸送性構造を有さない３官能以上のラジカル重合性モノマー ９部
トリメチロールプロパントリアクリレート
（ＫＡＹＡＲＡＤ ＴＭＰＴＡ、日本化薬製）
分子量：３８２、官能基数：３官能、分子量／官能基数＝９９
電荷輸送性構造を有するラジカル重合性化合物 ９部
（アクリル酸２−［４’−（ジ−ｐ−トリル−アミノ）−ビフェニル−４−イル］−エチル）

Tetrahydrofuran 80 parts 1% silicone oil tetrahydrofuran solution 0.2 parts After forming the charge transport layer, a metal mesh (opening ratio of 36.5%) with 100 meshes per inch was applied to the peripheral surface of the photoreceptor drum. . At this time, the meshing direction was set so that the mesh mesh was 45 degrees with respect to the rotation direction of the photosensitive member (see FIG. 9). From there, using the convex forming liquid having the following constitution, drum rotation speed: 80 rpm, spray gun feed speed: 15.5 mm / s, discharge amount: 5.0 ml / min, spraying pressure: 2.5 kgf / cm ² , Number of sprays: Spray coating was performed under the conditions of one time, and touch-and-drying was performed for 10 minutes.
Subsequently, the metal mesh was removed from the photosensitive drum, and a UV curing was performed while rotating the drum at a distance of 120 mm from the drum and the UV curing lamp. The illuminance of the UV curing lamp at this position was 550 mW / cm ² (UV integrated light meter UIT-150, measured value by Ushio Inc.). The drum rotation speed was 25 rpm. When performing UV curing, UV curing was performed continuously for 3 minutes by circulating water at 30 ° C. in an aluminum drum. Then, it heat-dried at 130 degreeC for 30 minutes. A photosensitive member having an uneven shape with a convex portion diameter of 250 μm, a convex portion height of 3.0 μm, and the number of convex portions per 1 mm square of 16 was obtained.
-Trifunctional or higher-functional radical polymerizable monomer that does not have a charge transporting structure for forming convex parts 9 parts Trimethylolpropane triacrylate (KAYARAD TMPTA, manufactured by Nippon Kayaku)
Molecular weight: 382, number of functional groups: trifunctional, molecular weight / number of functional groups = 99
9 parts of radically polymerizable compound having a charge transporting structure (2- [4 ′-(di-p-tolyl-amino) -biphenyl-4-yl] -ethyl acrylate)

光重合開始剤 ２部
１−ヒドロキシ−シクロヘキシル−フェニル−ケトン
（イルガキュア１８４、チバ・スペシャルティ・ケミカルズ製）
テトラヒドロフラン １００部
（ＫＦ５０−１００ＣＳ、信越化学工業製）

Photoinitiator 2 parts 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Tetrahydrofuran 100 parts (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Photoreceptor 2)
In the photoreceptor 1, an electrophotographic photoreceptor was prepared in the same manner as the photoreceptor 1 except that the conditions for forming the convex portions were changed as follows.
・ Spray gun feed speed: changed to 12.5 mm / s

(Photoreceptor 3)
In the photoreceptor 1, an electrophotographic photoreceptor was prepared in the same manner as the photoreceptor 1 except that the conditions for forming the convex portions were changed as follows.
・ Spray gun feed speed: 19.5 mm / s, spray discharge rate changed to 5.5 ml / min

(Photoreceptor 4)
In the photoreceptor 1, an electrophotographic photoreceptor was prepared in the same manner as the photoreceptor 1 except that the conditions for forming the convex portions were changed as follows.
・ Changed the spray discharge rate to 3.0ml / min

(Photoreceptor 5)
In the photoreceptor 1, an electrophotographic photoreceptor was prepared in the same manner as the photoreceptor 1 except that the conditions for forming the convex portions were changed as follows.
・ 10 parts of bisphenol-type polycarbonate for forming convex parts 10 parts of low molecular charge transport material with the following structure

テトラヒドロフラン ８０部
１％シリコーンオイルのテトラヒドロフラン溶液 ０．２部
・スプレーの吐出量を６．０ｍｌ／ｍｉｎに変更

Tetrahydrofuran 80 parts 1% silicone oil tetrahydrofuran solution 0.2 parts ・ Spray discharge rate changed to 6.0 ml / min

(Photoreceptor 6)
In the photoreceptor 1, an electrophotographic photoreceptor was prepared in the same manner as the photoreceptor 1 except that the conditions for forming the convex portions were changed as follows.
-Changed the mask attached to the photoconductor to a mesh with 50 meshes per inch (aperture ratio 39.2%)

(Photoreceptor 7)
An electrophotographic photosensitive member was prepared in the same manner as the photosensitive member 1 except that the conditions for forming the convex portions were changed as follows.
The convex forming liquid having the following prescription is put into a continuous ink jet coating apparatus nozzle diameter of 50 μm shown in FIG. It was allowed to drip on the surface and dried for 10 minutes.
・ Trifunctional or higher-functional radical polymerizable monomer having no liquid charge transporting structure for convex formation 10 parts Trimethylolpropane triacrylate (KAYARAD TMPTA, Nippon Kayaku)
Molecular weight: 382, number of functional groups: trifunctional, molecular weight / number of functional groups = 99
10 parts of radically polymerizable compound having a charge transporting structure (2- [4 ′-(di-p-tolyl-amino) -biphenyl-4-yl] -ethyl acrylate)

光重合開始剤 ２部
１−ヒドロキシ−シクロヘキシル−フェニル−ケトン
（イルガキュア１８４、チバ・スペシャルティ・ケミカルズ製）
テトラヒドロフラン １００部
（ＫＦ５０−１００ＣＳ、信越化学工業製）

Photoinitiator 2 parts 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Tetrahydrofuran 100 parts (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Photoreceptor 8)
In the photoreceptor 1, an electrophotographic photoreceptor was prepared in the same manner as the photoreceptor 1 except that the conditions for forming the convex portions were changed as follows.
-Drum rotation speed: 75 rpm, spray gun feed speed: changed to 20.0 mm / s

(Photoreceptor 9)
In the photoreceptor 1, an electrophotographic photoreceptor was prepared in the same manner as the photoreceptor 1 except that the conditions for forming the convex portions were changed as follows.
・ Spray gun feed speed: 19.5 mm / s, spray discharge rate changed to 6.0 ml / min

(Photoreceptor 10)
In the photoconductor 7, an electrophotographic photoconductor was prepared in the same manner as the photoconductor 7, except that the conditions for forming the convex portions were changed as follows.
Continuous type ink jet coating apparatus Nozzle diameter 50 μm, convex formation liquid is deposited on the photosensitive member formed up to the above-mentioned charge transport layer at regular intervals of 13 μm pitch, and touch drying for 10 minutes Was done.
Table 2 shows the shapes of the protrusions of the photoreceptors 1 to 10 produced as described above.

<Toner>
Specific examples of the toner used for the evaluation are shown below.
(Toner A)
~ Synthesis of organic fine particle emulsion ~
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of a sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, butyl acrylate When 110 parts and 1 part of ammonium persulfate were charged and stirred at 3800 rpm for 30 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and an aqueous dispersion of vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). [Fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component.
The Tg of the resin was 58 ° C., and the weight average molecular weight was 130,000.

~ Preparation of aqueous phase ~
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7) manufactured by Sanyo Kasei Kogyo Co., Ltd., and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This is designated as [Aqueous Phase 1].

-Preparation of aqueous solution of fluorinated activator-
N, N, N, -trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, 10 parts of iodide product name Aftergent 310 (manufactured by Neos) and 297 parts of methanol are placed in a container and brought to 50 ° C. Heat and stir until clear. The obtained fluorine-based activator methanol solution was added dropwise to 693 parts of stirred ion-exchanged water, and stirred at 50 ° C. for 30 minutes after completion of the addition to obtain [Fluorine-based activator aqueous solution 1].

~ Synthesis of low molecular weight polyester ~
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 7 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Then 44 parts of trimellitic anhydride was added to the reaction vessel, and 3 parts at 180 ° C. and normal pressure. The reaction was performed for a while to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, Tg of 43 ° C., and an acid value of 25.

~ Synthesis of intermediate polyester and prepolymer ~
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 7 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

~ Synthesis of ketimine ~
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 hours and half to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

~ Synthesis of master batch (MB) ~
1200 parts of water, 600 parts of carbon black (manufactured by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin are added and mixed with a Henschel mixer (manufactured by Mitsui Mining). Was kneaded for 1 hour at 120 ° C. using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].
1200 parts of water, C.I. I. Pigment Yellow 180 (PV Fast Yellow HG (Clariant)) 1000 parts, polyester resin 1200 parts are added, mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), and the mixture is kneaded at 120 ° C. for 1 hour using two rolls. Rolled and cooled and pulverized with a pulverizer to obtain [Masterbatch 2].
1200 parts of water, C.I. I. 950 parts of Pigment Blue 15: 3 (Lionol Blue FG-7351 (Toyo Ink)) and 1200 parts of polyester resin are added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). After kneading for a time, rolling and cooling and pulverizing with a pulverizer to obtain [Masterbatch 3].
1200 parts of water, C.I. I. Pigment Red 122 Hostaperm Pink E (Clarint)) 1000 parts and polyester resin 1200 parts are added, mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), the mixture is kneaded at 120 ° C. for 1 hour using two rolls, and then cooled by rolling. And then pulverized with a pulverizer to obtain [Masterbatch 4].

~ Preparation of oil phase ~
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular weight polyester 1], 95 parts of Carnauba WAX, and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. Cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Koki Kogyo Co., Ltd.), 3 at 6,200 rpm After mixing for 1 minute, 1200 parts of [Aqueous Phase 1] was added to the container, and mixed with a TK homomixer at 15,000 rpm for 35 minutes to obtain [Emulsion Slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 10 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 1].

~ Cleaning ⇒ Fluoroactive agent treatment ⇒ Drying ⇒ Air sieve ~
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was.
(5): [Filter cake 1] 630 parts and 2928 parts of ion-exchanged water are put in a container, stirred with a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) (rotation speed: 400 rpm for 5 minutes) and heated to 30 ° C. While maintaining the rotation speed and temperature, 11 parts of [Fluoroactive aqueous solution 1] is dropped. After completion of the dropwise addition, the mixture was stirred for 60 minutes and filtered to obtain [filter cake 1 after treatment with a fluorine-based activator].
[Filter cake 1 after treatment with fluorinated activator] was dried at 45 ° C. for 48 hours in a circulating drier.
Then, it was sieved with a mesh of 75 μm to obtain a toner. 1.0 part of silica fine powder (hexamethyldisilazane treatment) having an average particle diameter of 15 nm (primary particle diameter, the same applies hereinafter) and titanium oxide fine powder (isobutyltrimethyl) having an average particle diameter of 15 nm with respect to 100 parts by weight of the toner. [Toner A_Bk] was prepared by mixing 0.5 part of methoxysilane) and 0.6 part of silica fine powder having an average particle size of 90 nm (hexamethyldisilazane treatment) with a Henschel mixer and then sieving.
Similarly, [Toner A_Y] was produced by changing [Masterbatch 1] to [Masterbatch2]. Similarly, [Toner A_C] was prepared by changing [Master batch 1] to [Master batch 3]. Similarly, [Toner A_M] was produced by changing [Master Batch 1] to [Master Batch 4].

(Toner B)
[Toner A_Bk], [Toner A_Y], [Toner A_C], [Toner A_M] [Toner A_Bk], [Toner A_Y], [Toner, except that the steps of ~ emulsification → solvent removal ~ were changed as follows. [Toner B_Bk], [Toner B_Y], [Toner B_C], and [Toner B_M] were produced in the same manner as [A_C] and [Toner A_M].
~ Emulsification⇒Desolvation ~
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Special Machine) for 3 minutes at 6,500 rpm After mixing, 1200 parts of [Aqueous Phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 40 minutes to obtain [Emulsified Slurry 2].
[Emulsion slurry 2] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 10 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 2].

(Toner C)
In [Toner A_Bk], [Toner A_Y], [Toner A_C], and [Toner A_M], [Toner A_Bk] and [Toner A_Y] except that 0.06 part of zinc stearate is mixed with 100 parts by weight of toner. [Toner C_Bk], [Toner C_Y], [Toner C_C], and [Toner C_M] were prepared in the same manner as [Toner A_C] and [Toner A_M].

(Toner D)
In [Toner A_Bk], [Toner A_Y], [Toner A_C], and [Toner A_M], [Toner A_Bk] and [Toner A_Y] except that 0.4 parts of zinc stearate is mixed with 100 parts by weight of toner. [Toner D_Bk], [Toner D_Y], [Toner D_C], and [Toner D_M] were produced in the same manner as [Toner A_C] and [Toner A_M].

(Toner E)
[Toner A_Bk], [Toner A_Y], [Toner A_C], [Toner A_M] [Toner A_Bk], [Toner A_Y], [Toner, except that the steps of ~ emulsification → solvent removal ~ were changed as follows. [Toner E_Bk], [Toner E_Y], [Toner E_C], and [Toner E_M] were produced in the same manner as [A_C] and [Toner A_M].
~ Emulsification⇒Desolvation ~
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and TK homomixer (manufactured by Tokushu Kika) for 3 minutes at 6,000 rpm After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at 12,000 rpm for 30 minutes to obtain [Emulsified Slurry 3].
[Emulsion slurry 3] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 10 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 3].

(Toner F)
[Toner A_Bk], [Toner A_Y], [Toner A_C], [Toner A_M] [Toner A_Bk], [Toner A_Y], [Toner, except that the steps of ~ emulsification → solvent removal ~ were changed as follows. [Toner F_Bk], [Toner F_Y], [Toner F_C], and [Toner F_M] were produced in the same manner as [A_C] and [Toner A_M].
~ Emulsification⇒Desolvation ~
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Special Machine) for 3 minutes at 6,500 rpm After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at a rotation speed of 14,500 rpm for 35 minutes to obtain [Emulsified slurry 4].
[Emulsion slurry 2] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 10 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 2].

(Toner G)
In [Toner A_Bk], [Toner A_Y], [Toner A_C], and [Toner A_M], [Toner A_Bk] and [Toner A_Y] except that 0.03 part of zinc stearate is mixed with 100 parts by weight of toner. [Toner G_Bk], [Toner G_Y], [Toner G_C], and [Toner G_M] were produced in the same manner as [Toner A_C] and [Toner A_M].

(Toner H)
In [Toner A_Bk], [Toner A_Y], [Toner A_C], and [Toner A_M], [Toner A_Bk] and [Toner A_Y] except that 0.6 parts of zinc stearate is mixed with 100 parts by weight of toner. [Toner H_Bk], [Toner H_Y], [Toner H_C], and [Toner H_M] were prepared in the same manner as [Toner A_C] and [Toner A_M].

(Toner I)
Toner I binder resin Polyol resin (1/2 outflow start temperature 118 ° C.) 98 parts by weight Release agent Carnauba wax 2.5 parts by weight Colorant Benzimidazolone yellow pigment (CI Pigment Yellow 180) ) 4 parts by weight For magenta toner: quinacridone magenta pigment (CI Pigment Red 122) 6 parts by weight For cyan toner: Copper phthalocyanine blue pigment (CI Pigment Blue 15) 3 parts by weight For black toner: Carbon black 5 weights Partial charge control agent 2.5 parts by weight of salicylic acid derivative zinc salt The above toner constituent materials were sufficiently mixed for each color by a blender, and then melt-kneaded by a biaxial extruder heated to 100 to 110 ° C. The kneaded product was allowed to cool and then coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and each color matrix colored particle I was obtained using an air classifier.
Further, 100 parts by weight of each colored matrix colored particle I, 1.0 part of silica fine powder (hexamethyldisilazane treatment) having an average particle diameter of 15 nm and titanium oxide fine powder (isobutyltrimethoxysilane) having an average particle diameter of 15 nm. Treatment) 0.5 part and 0.6 part of silica fine powder (hexamethyldisilazane treatment) having an average particle diameter of 90 nm were mixed with a Henschel mixer and then subjected to sieving [Toner I_Bk], [Toner I_Y], [Toner Toner I_C] and [Toner I_M] were produced.
Table 3 shows the physical properties of Toners A to I produced as described above.

<Career>
Next, a specific production example of the carrier used for evaluation is shown.
Acrylic resin solution (solid content 50 wt%) 21.0 parts guanamine solution (solid content 70 wt%) 6.4 parts alumina particles [0.3 μm, specific resistance 10 ¹⁴ (Ω · cm)] 7.6 parts silicone resin solution 65 0.0 part [solid content: 23 wt% (SR2410: manufactured by Toray Dow Corning Silicone)]
Aminosilane 1.0 part [100 wt% solid content (SH6020: manufactured by Toray Dow Corning Silicone)]
60 parts of toluene 60 parts of butyl cellosolve was dispersed with a homomixer for 10 minutes to obtain a blend coating film forming solution of acrylic resin and silicone resin containing alumina particles. A fired ferrite powder [(MgO) 1.8 (MnO) 49.5 (Fe ₂ O ₃ ) 48.0: average particle size: 35 μm] was used as the core material, and the above coating film forming solution was formed on the surface of the core material. It was applied with a Spira coater (manufactured by Okada Seiko Co., Ltd.) to a thickness of 0.15 μm and dried. The obtained carrier was baked by standing in an electric furnace at 150 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain a carrier. The measurement of the binder resin film thickness was performed by observing the cross section of the carrier with a transmission electron microscope so that the coating film covering the carrier surface could be observed. Thus, a carrier having a weight average particle diameter of 35 μm was obtained.
Table 4 shows the results of evaluating the produced photoreceptor and toner.

(About Fig. 1 and Fig. 2)
21 conductive support 24 subbing layer 25 charge generation layer 26 charge transport layer 28 surface layer (about FIGS. 6 to 8)
10, 10Y, 10M, 10C, 10K Photoconductor 11, 11Y, 11M, 11C, 11K Charging member 12, 12Y, 12M, 12C, 13K Image exposure member 13, 13Y, 13M, 13C, 13K Developing member 14 Transport roller 15 Transfer Paper 16, 16Y, 16M, 16C, 16K Transfer member 17, 17Y, 17M, 17C, 17K Cleaning member 18 Static eliminating member 20Y, 20M, 20C, 20K Image forming element 21 Paper feed roller 22 Registration roller 23 Transfer member (secondary transfer) Element)
24 Fixing member

Japanese Patent No. 2520270 Japanese Patent No. 3585197 JP 2001-166521 A Japanese Patent Publication No. 6-82221 JP 2002-196523 A JP 2001-66814 A JP 2007-233356 A Japanese Patent No. 3963473 JP 2007-233359 A JP 2009-31499 A Japanese Patent No. 3640918 JP-A-6-250439

Claims (6)

In the image forming apparatus having the electrophotographic photosensitive member having at least a conductive photosensitive layer and a surface layer on a support, the surface of the surface layer of the electrophotographic photosensitive member, enclose take many projections and respective protrusions And an electrophotographic photosensitive member having concave portions connected in a mesh lattice, wherein the constituent material of the convex portions is different from the constituent material of the surface layer, and the longest diameter of the convex portions is 10 to 500 μm, and The height of the convex portions is 0.5 to 5 μm, the number of the convex portions is 2 to 5000 per 1 mm square of the surface layer of the electrophotographic photosensitive member, and the toner used in the image forming apparatus is A toner material solution in which at least a polymer having a site capable of reacting with a compound having an active hydrogen group, polyester, colorant, and release agent is dissolved or dispersed in an organic solvent is subjected to a crosslinking reaction or in an aqueous medium. At least one reaction of the extension reaction Obtained by the response, average circularity of spherical toner der of 0.96 to 0.99 in weight average particle diameter of 2-6 [mu] m, the lubricant relative to 100 parts by weight of the toner as external additives 0 An image forming apparatus comprising 0.05 to 0.5 parts by weight . The image forming apparatus according to claim 1 , wherein the lubricant is a metal soap. Comprising a plurality of electrophotographic photosensitive member, the toner image formed on the electrophotographic photosensitive member, an image forming apparatus according to claim 1 or 2, characterized in that it is sequentially transferred to the transfer medium. Charging means, an image forming apparatus according to any one of claims 1 to 3, wherein applying a direct current voltage superimposed with alternating voltage. Image forming method characterized by forming an image using an image forming apparatus according to any one of claims 1 to 4. It is detachably mountable to an image forming apparatus according to any one of claims 1 to 5, for an image forming apparatus characterized by comprising integrated detachably and a developing device and at least a latent electrostatic image bearing member Process cartridge.

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