JP2011158756A - Developer carrier and developing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer carrier configured such that recesses are uniformly formed on the surface of a developer carrier at a low cost, toner held on the surface of the developer carrier is uniformly charged, and stable image quality is obtained even in a large number of copies over a long period of time, and to provide a developing device using the developer carrier. <P>SOLUTION: The developer carrier has a resin layer on the surface of its substrate, the resin layer containing at least binding resin, conductive particles, and bowl-shaped resin particles. The resin layer contains the bowl-shaped resin particles at a ratio of ≥3 pts.mass and ≤40 pts.mass to 100 pts.mass of the binding resin. Recesses are formed on the surface of the resin layer by the shapes of the openings of the bowl-shaped resin particles. In addition, at least the binding resin and the conductive particles are present on the surface of the recesses. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a developer carrying member and a developing device.

  Patent Document 1 discloses a developer carrying member in which the surface of a base is covered with a resin layer, and a hemispherical concave surface is provided on the surface of the resin layer. And according to such a developer carrier, it is described that the performance of the resin layer hardly changes and a high-quality image can be obtained over a long period of time because the change in the surface shape with time is small. .

JP-A-8-305156

The present inventors have studied the developer carrier of Patent Document 1 and have found the following problems. That is, the developer carrier according to Patent Document 1 is manufactured by forming a resin coating layer in which spherical particles are dispersed on a substrate, and then removing the spherical particles in the resin coating layer by polishing or dissolution. However, as for the surface shape of the resin coating layer formed by such a method, a convex part is formed at the edge of the concave surface as shown in FIG. Such protrusions may be scraped by long-term use, changing the surface shape of the developer carrier, and thus changing the charging performance of the developer carrier.
Accordingly, an object of the present invention is to provide a developer carrier in which the surface shape is less likely to change even after long-term use, and as a result, the charging performance to the developer is stable over a long period of time. Another object of the present invention is to provide a developing device having stable developing performance.

  The developer carrier according to the present invention has a resin layer containing at least a binder resin, conductive particles, and bowl-shaped resin particles on the surface of the substrate, and the resin layer contains the bowl-shaped resin particles, A concave portion is formed on the surface of the resin layer due to the shape of the opening of the bowl-shaped resin particles, and at least the binder resin and the conductive particles are present on the surface of the concave portion.

  According to the present invention, it is possible to obtain a developer carrying member and a developing device that can stably charge a toner for a long period of time and contribute to the formation of a high-quality electrophotographic image.

FIG. 3 is an enlarged cross-sectional view of a developer carrier according to the present invention. It is explanatory drawing of a bowl-shaped resin particle. It is sectional drawing which shows the example of the image development apparatus using a magnetic one component developer. It is a figure which shows the example of the image development apparatus which uses a two-component developing agent. It is explanatory drawing of the evaluation method of a sleeve ghost. It is explanatory drawing of the blasting apparatus used for manufacture of a developer carrier.

  The present invention will be described in detail by giving preferred embodiments. FIG. 1 is an enlarged cross-sectional view of the vicinity of the surface of the developer carrying member according to the present invention. The developer carrier has a base 6 and a resin layer 7 covering the peripheral surface thereof. The resin layer 7 contains a binder resin 15, conductive particles 14 dispersed in the binder resin 15, and bowl-shaped resin particles 16. Here, the bowl-shaped resin particles are communicated with the outside by having an opening which is obtained by cutting a part of hollow particles having a void inside as shown in FIG. It is the resin particle which has the shape formed. The detailed structure will be described later. In the resin layer 7, such bowl-shaped resin particles have their openings facing the peripheral surface of the developer carrier, and the surface thereof is covered with a binder resin in which conductive particles are dispersed. ing. As a result, a concave portion 17 derived from the shape of the opening of the bowl-shaped resin particles 16 is formed on the surface of the resin layer 7.

<Substrate>
The base 6 is made of a member such as a cylindrical member, a columnar member, or a belt member. As the substrate 6, a non-magnetic metal or alloy such as aluminum, stainless steel, or brass, which is molded into a cylindrical shape or a columnar shape, polished, ground, or the like is preferably used. Further, in the case of a developer carrying member used in a developing method in direct contact with the photosensitive drum, a cylindrical member in which the base 6 is provided with a rubber layer of urethane, EPDM, silicone rubber or the like on the peripheral surface of a metal cored bar is also provided. Can be used.

<Resin layer>
In the resin layer 7, bowl-shaped resin particles 16 are dispersed so that the opening is directed to the surface side thereof, and the bowl-shaped resin particles 16 are bound to include conductive particles 14 along the inner surface thereof. It is covered with resin. Therefore, a concave portion 17 having a shape having an opening of bowl-shaped resin particles is formed on the surface of the resin layer 7, and the binder resin 15 and the conductive particles 14 exist on the surface of the concave portion 17. The present inventors have studied the shape of the resin particles dispersed and contained in the resin layer. When the resin layer is formed by containing bowl-shaped resin particles, a bowl-shaped opening is formed in the resin layer of the developer carrier. Was found to easily form a uniform recess on the surface of the resin layer reflecting the shape of the inner surface of the opening of the bowl-shaped resin particles. Furthermore, it has been found that a resin layer similar to the resin layer surface portion where no recess is formed is present on the surface of the recess. Further, in order to make the surface of the resin layer into a shape having a more uniform recess, bowl-shaped resin particles in which the average diameters of the openings are made uniform by classification or the like may be included in the conductive resin layer. As a result, the variation in the surface roughness of the developer carrier is further suppressed, and a stable image quality can be obtained.

  The bowl-shaped resin particles 16 are preferably contained in a proportion of 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the binder resin constituting the resin layer. This is because the concave portion for achieving the surface roughness for transporting the developer uniformly and stably by triboelectric charging can be reliably and uniformly formed on the surface of the resin layer 7.

<Bowl-shaped resin particles>
The bowl-shaped resin particles 16 have a ratio between the average diameter of the opening and the average maximum depth from the opening, that is, the average diameter / average maximum depth of the opening is 1.0 or more and 2.0 or less. Is 5.0 μm or more and 20.0 μm or less, and the difference between the outer diameter and the inner diameter around the opening is preferably 0.50 μm or more and 2.0 μm or less. Here, the primary average particle diameter is the average diameter of the openings of the bowl-shaped resin particles. By setting the ratio of the average diameter of the openings to the average maximum depth to be 1.0 or more, the average diameter of the openings becomes larger than the average maximum depth, so that the openings are easily directed to the surface. At the same time, the toner transported in the concave portion comes into contact with the bottom surface of the bowl-shaped particles, and the toner transportability is sufficient. In addition, when the ratio of the average diameter of the openings to the average maximum depth is 2.0 or less, it is difficult to form a relatively shallow concave portion, so that sufficient surface roughness can be obtained and sufficient toner transportability is ensured. it can.
In addition, when the primary average particle size is 5.0 μm or more, the resin layer is difficult to enter until the concave portion is buried in the concave surface, and formation of the concave portion on the surface is not hindered. Further, by setting the primary average particle size to 20.0 μm or less, the opening of the bowl-shaped resin particles can be easily directed to the surface side of the developer carrying member, and uniform concave portions can be easily formed. Further, when the difference between the outer diameter and inner diameter of the edge around the opening is 0.50 μm or more and 2.0 μm or less, the durability of the bowl-shaped resin particles is unlikely to decrease, and the bowl-shaped resin particles when forming the resin layer It becomes easy to form a recess uniformly on the surface of the resin layer due to the damage of the resin.

In the present invention, it is preferable that the surface of the developer carrying member is shaped as follows by using the bowl-shaped resin particles as described above. That is, the total area of the openings of the recesses formed on the surface of the resin layer of the developer carrier is preferably 20% to 70% of the surface area of the resin layer. By setting the area ratio within this range, the concave portions are appropriately formed, so that the developer transportability is sufficient. Further, since the surface roughness does not become excessively large, the frictional charge of the toner is difficult to be non-uniform. The area ratio can be adjusted by increasing or decreasing the content of the bowl-shaped resin particles 14. Further, in the developer carrying member according to the present invention, the inside of the wall of the bowl-shaped resin particles is coated with the binder resin 15 in which the conductive particles 14 are dispersed and is lined. The average diameter of the openings of the recesses formed in this way is preferably 3.0 μm or more and 19 μm or less, and the average maximum depth from the openings of the recesses is preferably 1.5 μm or more and 19.5 μm or less. By setting the numerical value in such a range, the concave portion is not too small or too large with respect to the toner particle diameter, so that the toner transportability is improved and image defects are hardly caused. Further, by setting the maximum depth from the opening within the above numerical range, the toner is reliably conveyed and hardly causes image defects.
Such bowl-shaped resin particles themselves are known as described in Japanese Patent Application Laid-Open No. 10-218950 as “Bowl-shaped polymer particles”. Also, commercially available from Matsumoto Yushi Seiyaku Co., Ltd. as “Matsumoto Microsphere-M-310” (trade name) and “Matsumoto Microsphere M-311” (trade name).

<Binder resin>
A known resin can be used as the binder resin 15. Specific examples include phenolic resin, epoxy resin, polyamide resin, polyester resin, polycarbonate resin, polyolefin resin, silicone resin, fluorine resin, styrene resin, vinyl resin, cellulose resin, melamine resin, urea resin, polyurethane resin, polyimide resin. And acrylic resin. These resins are relatively highly soluble in organic solvents, have excellent dispersibility of conductive particles and bowl-shaped resin particles, and can be easily thinned. In addition, these resins are excellent in adhesion to the substrate and wear resistance, and in particular, when the developer (toner) is negatively charged, an appropriate charge can be imparted to the developer (toner).

In the present invention, the resin layer formed on the surface of the developer carrier by the above-described material is a conductive layer in order to prevent poor charge application from the surface of the developer carrier to the developer caused by developer charge-up. Is desirable. In order to make the charging performance to the developer sufficient, the volume resistance value of the resin layer is preferably 10 ⁴ Ω · cm or less, more preferably 10 ³ Ω · cm or less and 10 ⁻² Ω · cm or more.

  The resin layer 7 contains conductive particles in order to adjust the volume resistance value. Specific examples of the conductive particles 14 are given below. Powders of metals (aluminum, copper, nickel, silver, etc.), metal oxides (antimony oxide, indium oxide, tin oxide) and carbon materials (carbon fiber, carbon black, graphite, etc.). Among them, carbon black, particularly conductive amorphous carbon, has high electrical conductivity, and can be given a certain degree of conductivity by simply filling high molecular weight material to impart conductivity and controlling the amount added. It can be suitably used. The amount of conductive particles added is preferably in the range of 8 to 100 parts by mass with respect to 100 parts by mass of the binder resin in order to obtain the volume resistance as described above.

  The conductive particles preferably have a primary average particle size in the resin layer of 15 nm or more and 100 nm or less. When the primary average particle diameter is 15 nm or more and 100 nm or less, the conductive particles are easily dispersed uniformly in the resin layer, so that uniform conductivity is obtained and a uniform concave shape on the surface of the resin layer is easily formed.

  In addition, it is preferable to add a solid lubricant to the resin layer in combination with bowl-shaped resin particles because the surface lubricity is increased and the durability of the resin layer is improved. Examples of such a solid lubricant include crystalline graphite, molybdenum disulfide, boron nitride, mica, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, talc, and fatty acid metal salts such as zinc stearate. Substances. Among these, crystalline graphite is preferable because it does not impair the conductivity of the conductive resin layer, increases surface lubricity, and improves the durability of the resin layer. The volume average particle size of the solid lubricant is preferably 0.2 μm to 5.0 μm, particularly preferably 0.5 μm to 3.0 μm. Moreover, when using a solid lubricant together with a bowl-shaped resin particle, it is preferable that a solid lubricant has a volume average particle diameter smaller than this resin particle.

式中、Ｒ1〜Ｒ4は、それぞれ独立に、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、アルアルキル基を表し、Ｘ-は酸の陰イオンを表す。一般式（1）においてＸ-で表されている酸の陰イオンとしては、有機硫酸イオン、有機スルホン酸イオン、有機リン酸イオン、モリブデン酸イオン、タングステン酸イオン、モリブデン原子或いはタングステン原子を含むヘテロポリ酸イオン等が好ましい。 In the present invention, in order to adjust the chargeability of the developer carrying member, a charge control agent may be contained in the resin layer together with the conductive particles and the bowl-shaped resin particles. Examples of charge control agents that can be used here include modified products of nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate; Onium salts such as phosphonium salts and their lake pigments (the rake agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferricyanide, Russian compounds); metal salts of higher fatty acids; diorganotin oxides such as butyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltinborate, dioctyltinborate, dicyclohexyltinborate Organo tin borate compounds; guanidine; imidazole compounds. Among these charge control agents, when using a negatively chargeable toner having a high degree of spheroidization, a quaternary ammonium salt compound that is positively charged with respect to iron powder is included in the resin layer as the charge control agent. Is preferable in terms of improving the charge imparting property to the toner. At this time, it is more preferable that the resin layer has at least one of an amino group, ═NH group, and NH— bond in the resin structure. By providing a resin layer in which the above quaternary ammonium salt compound and a specific binder resin are combined on the developer carrier, it becomes possible to prevent excessive charging of the negatively charged toner having a high degree of spheroidization. The chargeable toner can be appropriately frictionally charged. This prevents toner charge-up on the developer carrier, prevents toner fusion on the resin layer surface, and maintains high toner charging stability. As a result, environmental stability and long-term stability are improved. It becomes possible to provide the high-definition image which has. As the quaternary ammonium salt compound having the above-mentioned function suitably used in the present invention, any quaternary ammonium salt compound having a positive chargeability with respect to iron powder may be used. For example, the following general formula (1 ).

In the formula, R 1 to R 4 each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group, and X − represents an anion of an acid. Examples of the anion of the acid represented by X- in the general formula (1) include organic sulfate ion, organic sulfonate ion, organic phosphate ion, molybdate ion, tungstate ion, molybdenum atom or tungsten atom. Acid ions and the like are preferable.

  The surface roughness of the resin layer of the developer carrying member is preferably in the range of 0.40 μm to 2.50 μm in terms of arithmetic average roughness (Ra) according to Japanese Industrial Standard (JIS) B0601-2001. As a result, the developer is sufficiently transported, and it is possible to suppress the occurrence of image density reduction due to insufficient developer, scattering and blotch due to excessive charging. Further, the frictional charging of the toner is made uniform, and the occurrence of streaks, reversal fog, and low image density due to insufficient charging can be suppressed. Similarly, the film thickness of the resin layer is preferably in the range of 5.0 μm or more and 50.0 μm or less, although the preferred film thickness varies depending on the development method.

  The resin layer 7 according to the present invention is obtained by dispersing and mixing the binder resin 15, the conductive particles 14, the bowl-shaped resin particles 16, and the like in a solvent to form a paint and coating it on the substrate 6. As a coating method, known methods such as a dipping method, a spray method, and a roll coating method can be applied, but the spray method is particularly preferable in order to uniformly form concave portions derived from bowl-shaped resin particles on the surface. The droplet formed by the spray method is subjected to surface tension (force for maintaining a spherical shape) to reduce the surface area of the droplet itself. Due to this surface tension, the bowl-shaped resin particles present on the surface of the droplets are more spherical than the state in which the convexes protrude from the surface of the droplets, while the concave portions contain other paint components inside the concave portions. , Become more stable. When droplets in such a state are applied to the substrate, the bowl-shaped resin particles present on the surface of the resin layer will exist with the recesses facing the surface of the resin layer, and the recesses will be formed uniformly. can do.

<Developing device>
FIG. 5 is a cross-sectional view of a developing device provided with the developer carrying member of the present invention. An electrostatic latent image carrier (photosensitive drum) 1 for carrying an electrostatic latent image is rotated in the direction of arrow B. A developer carrier 8 facing the photosensitive drum 1 is composed of a metal cylindrical tube (base) 6 and a resin layer 7 formed on the surface thereof. In the hopper 3, a stirring blade 10 for stirring the magnetic one-component toner 4 is provided. The magnetic one-component toner 4 supplied from the hopper 3 to the developer carrier 8 is carried on the developer carrier 8, and the developer carrier 8 rotates in the direction of arrow A as the developer carrier 8 rotates. 8 and the photosensitive drum 1 are conveyed to the developing area D facing each other. In the developer carrier 8, a magnet 5 for magnetically attracting and holding the magnetic one-component toner 4 on the developer carrier 8 is disposed. The magnetic one-component toner 4 is frictionally charged by friction with the developer carrier 8, the developer layer thickness regulating member (elastic blade) 11 and the stirring blade 10, and can develop the electrostatic latent image on the photosensitive drum 1. . In this developing device, the developer layer pressure regulating member 11 is brought into pressure contact with the developer carrier 8 through the developer layer. As a result, a thin layer of magnetic one-component developer is formed on the developer carrier.

  The thin layer of the magnetic one-component toner 4 formed on the developer carrier 8 by the developer layer thickness regulating member 11 is smaller than the minimum gap between the developer carrier 8 and the photosensitive drum 1 in the development region D. Further, it is preferably thin. That is, it is particularly effective for a so-called non-contact type developing apparatus that develops an electrostatic latent image with such a toner thin layer. A developing bias voltage is applied to the developer carrier 8 by a power source 9 in order to cause the magnetic one-component toner 4 carried on the developer carrier 8 to fly. When a DC voltage is used as the developing bias voltage, a voltage having a value between the potential of the image portion of the electrostatic latent image (the region visualized by toner adhesion) and the potential of the background portion is carried by the developer. Application to the body 8 is preferred. On the other hand, in order to increase the density of the developed image or to improve the gradation, an alternating bias voltage is applied to the developer carrier 8 to form an oscillating electric field whose direction is alternately reversed in the developing portion. Also good. In this case, an alternating bias voltage on which a DC voltage component having a value between the above-described image portion potential and background portion potential is superimposed is applied to the developer carrier 8. In the so-called regular development, in which toner is attached to a high potential portion of an electrostatic latent image having a high potential portion and a low potential portion for visualization, toner charged to a polarity opposite to that of the electrostatic latent image is applied. On the other hand, in so-called reversal development, in which toner is attached to a low potential portion of an electrostatic latent image for visualization, toner charged with the same polarity as that of the electrostatic latent image is used. Note that high potential and low potential are expressions based on absolute values. In any case, the magnetic one-component toner 4 is charged to a polarity for developing the electrostatic latent image by friction with the developer carrier 8. The toner image formed on the photosensitive drum 1 moves to a transfer portion (not shown) by the rotation of the photosensitive drum, and electrostatically is transferred onto a transfer material (not shown) supplied in synchronization with the rotation of the photosensitive drum 1 there. Is transcribed. The transfer material onto which the toner image has been transferred is further fixed by a fixing unit to form an image. It is not necessary for the developer layer thickness regulating member 11 to control the layer thickness of the magnetic one-component toner 4 on the developer carrier 8, but using a magnetic blade 2 as shown in FIG. Also good.

  When the developer 4 is a non-magnetic one-component toner, the base 6 of the developer carrier 8 may be cylindrical as shown in FIG. The developer carrier 8 is supplied with a new non-magnetic one-component toner to the developer carrier 8 and an elastic roller that scrapes off the non-magnetic one-component toner that returns to the hopper 3 without being used for development. 13 is in contact. The elastic roller 13 has a function of frictionally charging the non-magnetic one-component toner 4 together with the developer carrier 8 and the developer layer thickness regulating member 11.

  The non-magnetic one-component toner carried on the developer carrying member 8 is regulated in layer thickness (carrying amount) by the elastic blade 11 and charged to develop the electrostatic latent image formed on the photosensitive drum 1 Further, the toner is sent to the developing area D facing the photosensitive drum 1 by the rotation of the developer carrier 8. In the development area D, the non-magnetic one-component toner electrostatically flies or contacts the electrostatic latent image from the developer carrying member 8 to develop the electrostatic latent image. During this development, a static voltage is applied from the power source 9 between the photosensitive drum 1 and the developer carrier 8 in order to efficiently transfer the nonmagnetic one-component toner to the electrostatic latent image. At this time, an alternating voltage as described above can be applied in order to increase the contrast of the developed toner image. The developer carrier 8 further rotates and returns to the hopper 3 while carrying the non-magnetic one-component toner that has not been used for development, where the non-magnetic one-component toner is transferred from the surface of the developer carrier 8 to the elastic roller 13. The non-magnetic one-component toner is newly carried on the developing carrier 8 by the elastic roller 13. On the other hand, the toner image formed on the photosensitive drum 1 moves to the transfer region as the photosensitive drum 1 rotates, and is electrostatically transferred to the transfer member supplied in synchronization therewith. The transfer member to which the toner image has been transferred is carried to a fixing region where the toner image is fixed on the transfer member.

<Developer regulating member>
As a developer regulating member, a rough surface having a ten-point average roughness (Rzjis) of 2.0 μm or more and 15.0 μm or less and an unevenness average interval (RSm) of 0.030 mm or more and 0.170 mm or less at a contact portion with the developer carrying member. It is preferable to use an elastic blade having the same. Thereby, toner fusion and toner deterioration on the surface of the developer carrying member can be more effectively suppressed. Such a developer layer thickness regulating member may be any member that can remove the excess of the developer carried thereon from the developer carrying member, return it to the developing container, and charge the developer. For example, as a specific example of the developer layer thickness regulating member, there is a type that is made of an elastic material and is provided in contact with a developer carrier within a developer container. As a material for this type of developer layer thickness regulating member, a material having rubber elasticity is suitable. A resin layer such as a polyamide resin may be provided on the surface of the developer layer thickness regulating member. An elastic plate having metal elasticity is also a good example. The roughened surface of the elastic blade can be formed by physical methods and / or chemical methods.

  The developer carrying member according to the present invention can also be used for development using a two-component developer containing toner and carrier. A two-component developing apparatus in which the developer carrying member of the present invention is incorporated will be described with reference to FIG. In FIG. 4, a non-magnetic developing sleeve (developer carrying member) 221 as a developer carrying member is opposed to the electrostatic latent image holding member 224 rotated in the direction of arrow a in the developing chamber 245 of the developing container 225. Is provided. In the developer carrier 221, a magnetic roller 222 as a magnetic field generating means is fixedly arranged, and the magnetic roller 222 is sequentially S1, N1, S2, N2, N3 from the substantially top position in the rotation direction of the arrow b. Is magnetized. In the developing chamber 245, a two-component developer 241 in which the toner 240 and the magnetic carrier 243 are mixed is accommodated. The developer 241 is sent into the stirring chamber 242 of the developing container 225 through one opening (not shown) of the partition wall 248 open at the upper end at one end of the developing chamber 245. At that time, the toner 240 supplied from the toner chamber 247 into the stirring chamber 242 is replenished and conveyed to the other end of the stirring chamber 242 while being mixed by the first developer stirring / conveying means 250 in the stirring chamber 242. . The developer 241 conveyed to the other end of the stirring chamber 242 is returned to the developing chamber 245 through the other opening (not shown) of the partition wall 248. Therefore, the second developer agitating / conveying means 251 in the developing chamber 245 and the third developer agitating / conveying means 252 that conveys the developer in the direction opposite to the conveying direction by the conveying means 251 in the upper part of the developing chamber 245, It is conveyed to the developer carrying member 221 while being stirred and conveyed. The developer 241 supplied to the developer carrier 221 is magnetically constrained by the magnetic force of the magnet roller 222 described above, and is carried on the developer carrier 221, provided on a substantially top portion of the developer carrier 221. The developer regulating member blade 223 forms a thin layer of the developer 241 on the developing sleeve 221, while the developer carrying member 221 rotates in the direction of arrow B to the developing portion C facing the latent image holding member 224. It is conveyed. Therefore, the electrostatic latent image on the latent image holding member 224 is used for development. The remaining developer 241 that has not been consumed in the development is collected in the developer container 225 by the rotation of the developer carrier 221. In the developer container 225, the remaining developer 241 that is magnetically constrained on the developer carrier 221 by the repulsive magnetic field between N2 and N3 of the same polarity and that has not been consumed in development is stripped off. Yes. In order to prevent toner scattering when the developer 241 rises along the lines of magnetic force due to the magnetic pole N2, the elastic seal member 231 is arranged so that one end thereof is in contact with the developer 241 at the bottom of the developer container 225. Fixed and installed. 3A to 3C schematically illustrate a developing device in which the developer carrier of the present invention can be used. In addition to the layer thickness regulating member described above, the shape of the developing container, the stirring blade There are various forms such as presence / absence of magnetic poles, arrangement of magnetic poles, presence / absence of supply containers, and the like.

<Developer>
The developer (toner) according to the present invention is obtained by blending a binder resin with a colorant, a charge control agent, a release agent, inorganic fine particles and the like, and as a type, a magnetic one-component developer having a magnetic material as an essential component. And non-magnetic one-component developer containing no magnetic material. The type is appropriately selected according to the developing device. In addition, the developer (toner) used in the present invention is preferably in the range of 4 μm or more and 11 μm or less in weight average particle diameter (D4) regardless of the type. If such a developer (toner) is used, a suitable charge amount can be obtained, and good image quality and image density can be achieved. As the binder resin, generally known resins can be used, and examples thereof include vinyl resins, polyester resins, polyurethane resins, epoxy resins, and phenol resins, among which vinyl resins and polyester resins are preferable. The developer (toner) can be used by incorporating a charge control agent into the toner particles (internal addition) or mixing with the toner particles (external addition) for the purpose of improving charging characteristics. This is because the charge control agent enables optimal charge amount control according to the development system. Examples of positive charge control agents include nigrosine, triaminotriphenylmethane-based dyes and modified products of fatty acid metal salts. Examples of the negative charge control agent include acetylacetone metal complexes, monoazo metal complexes, naphthoic acid or salicylic acid-based metal complexes or salts.

  When the developer is a magnetic developer, an iron oxide metal oxide, magnetic metal, or an alloy of magnetic metal with Al, Co, Cu, or the like is blended as the magnetic material. These magnetic materials can also serve as a colorant. Known colorants and dyes can be used as the colorant to be blended in the developer. It is preferable to add a release agent to the developer. As the mold release agent, aliphatic hydrocarbon waxes and waxes mainly composed of fatty acid esters can be suitably used. Further, it is preferable that an inorganic fine powder is externally added to the developer in order to improve environmental stability, charging stability, developability, fluidity, storage stability and cleaning properties, and the developer is present in the vicinity of the developer surface. Examples of the inorganic fine powder include silica, titanium oxide, and alumina, and silica fine powder is particularly preferable. Furthermore, a lubricant such as polyvinylidene fluoride or an abrasive such as cerium oxide may be added as an external additive other than the inorganic fine powder. In order to produce a developer (toner), first, a binder resin, a pigment or dye as a colorant, a release agent, and if necessary, a magnetic material, a charge control agent, and other additives are sufficiently mixed with a mixer. Mix. Next, the obtained mixture is melted using a thermal kneader to make the resins compatible with each other, and the release agent, pigment, dye, and magnetic substance are dispersed or dissolved. The melt is cooled and solidified, and then pulverized and classified to obtain toner particles. Furthermore, a desired additive may be added as necessary and mixed with a mixer to obtain a developer (toner). When such a developer is used after being subjected to a spheroidizing treatment or a surface smoothing treatment by various methods, it is preferable because transferability is good. As such a method, an apparatus having a stirring blade or a blade, and a liner or a casing, for example, smoothes the surface by a mechanical force when the developer passes through a minute gap between the blade and the liner. There are a method in which the toner particles are spheroidized and the developer is spheroidized, a method in which toner particles are suspended in warm water to spheroidize, and a method in which toner is exposed to a hot air stream to spheroidize. In addition, as a method for directly producing a spherical developer, there is a method in which a mixture containing a monomer as a developer binder resin as a main component is suspended in water and polymerized to form toner particles. Generally, the monomer is prepared by uniformly dissolving or dispersing a polymerizable monomer, a colorant, a polymerization initiator, and, if necessary, a crosslinking agent, a magnetic material, a charge control agent, a release agent, and other additives. It is set as a composition. Thereafter, this monomer composition is dispersed in appropriate layers in a continuous layer containing a dispersion stabilizer, such as an aqueous phase, using an appropriate stirrer, and further subjected to a polymerization reaction to develop a developer having a desired particle size. Get the agent.

In the case of a two-component developer, the carrier preferably has a number average particle diameter (Dv) of 15.0 μm to 70.0 μm, particularly 20.0 μm to 50.0 μm. By setting Dv within this range, the shape of the magnetic carrier can be controlled to be substantially spherical and uniform, so that good charging performance can be maintained. The carrier has a true specific gravity of 3.0 g / cm ³ or more and 5.0 g / cm ³ or less, particularly 3.2 g / cm ³ or more and 4.0 g / cm ³ or less. When the true specific gravity is within this range, the load on the toner is small in the stirring and mixing of the carrier and the toner. Therefore, toner spent on the carrier is suppressed, and separation of the toner from the carrier can be maintained well for a long time. Further, it is preferable because carrier adhesion to the photosensitive drum is suppressed. As the carrier and the magnetic carrier, those having a resin component on at least the surface thereof are preferably used. Examples of such a magnetic carrier include a magnetic metal such as iron, copper, nickel and cobalt, a core material of a magnetic oxide such as magnetite and ferrite, and a resin layer formed thereon, or as described above. A magnetic fine particle dispersed carrier in which magnetic fine particles are dispersed in a resin can be used.

The physical property measurement method according to the present invention will be described below.

(1) Average diameter of bowl-shaped resin particles;
Using an ultra-deep shape measuring microscope (manufactured by KEYENCE, VK-8510; product name), the particle size was confirmed by observation at a magnification of 2000 times. Among these, for the particles with the opening facing upward, the major axis and minor axis of the opening were measured, and the value obtained by dividing the sum of the major axis and the minor axis by 2 was taken as the particle size. The average value of the particle diameters obtained for 100 different particles was defined as the average diameter of the openings (A in FIG. 2). Three-dimensional processing was performed, and the maximum depth from the opening (B in Fig. 2) was measured. The corresponding size was determined by 50% of all samples. For the measurement of the difference between the outer diameter and the inner diameter, randomly select three locations for each particle, measure the difference between the outer diameter and the inner diameter of that part (C in Fig. 2), and average the value for the outer diameter of the particle. And the inner diameter difference.

(2) Evaluation of surface shape of developer carrier;
Using an ultradeep shape measuring microscope (manufactured by KEYENCE, VK-8510; product name), the image is observed at a magnification of 2000 to obtain an image of the surface of the developer carrying member. The major axis and minor axis of the opening of one concave portion confirmed in the image are measured, and the average value is calculated by dividing the sum of the major axis and minor axis by two. Using this average value as the diameter of the opening, the area of the opening of the recess is calculated using this value. The same measurement and calculation are performed for all the concave portions, and the diameter and area ratio of the concave opening on the surface of the developer carrying member are determined. Further, the obtained observation data is subjected to a three-dimensional process, and the maximum depth from the opening of the recess is measured. The same measurement is performed for all the recesses in the image, and the average value is defined as the average maximum depth from the opening. Calculate the area ratio, the diameter of the opening, and the maximum depth from the opening at a total of 6 locations in the axial direction and 3 in the circumferential direction for one developer carrier, and the average value of each area ratio, The average diameter of the opening and the average maximum depth from the opening were used.

The three-dimensional processing method will be described below. An ultra-deep shape measuring microscope VK-8510 (manufactured by KEYENCE; product name) was used to measure the maximum depth of the bowl-shaped resin particles from the opening and the shape of the recesses on the surface of the developer carrier. This device applies the laser emitted from the light source to the object, and measures the shape of the object based on objective lens position information that maximizes the amount of reflected light received by the light receiving element at the confocal position. Is. The measurement conditions were set as follows.
Objective lens magnification: 100x Optical zoom magnification: 1x Digital zoom magnification: 1x
RUN MODE: Color super depth Height lens movement pitch: 0.1μm
Laser gain: 716
Laser offset: -335
Shutter (camera setting): 215

The measurement results were analyzed using image analysis software “VK-H1W (Version 1.07)” (trade name, manufactured by Keyence Corporation) First, tilt correction processing was performed to correct the overall tilt of the measurement results. The processing was performed only for height data, the correction method was in the automatic mode of surface correction, and then smoothing was performed by filter processing to remove the noise component due to the measurement.
Process target: height data,
Processing size: 3 × 3 area smoothing processing,
Number of executions: Once,
File type: Simple average.

  Next, after converting the height data obtained by the measurement into CSV text data, the height from the surface of the resin layer in each recess was set to the maximum depth from the opening of the recess.

(3) Ten-point average roughness (Rzjis) and average roughness (RSm) of the developer layer thickness regulating member;
Before incorporating the developer carrier into the device (new), the ten-point average roughness (Rzjis) and unevenness average spacing (RSm) of the developer layer thickness regulating member are manufactured by Kosaka Laboratory, Inc. according to JIS B0601-2001. The surface roughness measuring instrument “Surf Corder SE-3500” (product name) is used to measure the surface of the roughened surface at five locations in the axial direction, and the average values are calculated as 10-point average roughness (Rzjis) and unevenness average. The interval (RSm) was used. The cut-off was 0.8 mm, the measurement distance was 8.0 m, and the feed rate was 0.5 mm / sec.

(4) Surface roughness (Ra) of developer carrier;
Measure the surface roughness (arithmetic mean roughness) Ra of the developer carrier before incorporating the developer carrier into the device (new) and after durability evaluation according to JIS B0601-2001 by Kosaka Laboratory. The surface roughness Ra was measured with the instrument “Surf Corder SE-3500” (product name) at a total of 9 locations in the circumferential direction for each of the 3 locations in the axial direction. The cut-off was 0.8 mm, the measurement distance was 8.0 m, and the feed rate was 0.5 mm / sec. The developer carrier after the durability evaluation was removed from the developing device, and then air blow was applied to the surface, and the developer adhered to the surface was completely removed, and the measurement was performed.

(5) Toner particle size measurement;
A Coulter Counter TA-II type, Coulter Multisizer II or Coulter Multisizer III (both product names, manufactured by Beckman Coulter, Inc.) were used as measuring devices. Moreover, about 1 mass% NaCl aqueous solution or ISOTON-II (product name, the Beckman Coulter company make) prepared by melt | dissolving sodium chloride (reagent grade 1) was used as electrolyte solution. In 100 to 150 ml of the electrolytic solution, 0.1 ml to 5 ml of a surfactant (alkylbenzene sulfonate solution) was added as a dispersant, and then 2 mg to 20 mg of the sample was added. This was subjected to a dispersion treatment for about 1 minute to 3 minutes with an ultrasonic disperser to prepare a test sample. Using the 30 μm aperture of the measuring device, the volume and number of spherical particles or toner particles in the test sample were measured. The volume distribution and number distribution are calculated from the measurement results, and the weight-based weight average particle diameter (D4) obtained from the volume distribution and the number-based length average particle diameter (D1) obtained from the number distribution (both for each channel). The median value of the channel is the representative value for each channel).

(6) Measurement of the volume average particle size (Dv) of the magnetic carrier;
The particle size of the magnetic carrier particles is measured by a dry method using a particle size distribution measuring device using a method for detecting a light intensity distribution pattern of a particle group such as a laser diffraction particle size distribution measuring device. Any device that can measure the range from submicron to several hundred microns can be used. For example, SALD-3100 (manufactured by Shimadzu Corporation; product name) is used to calculate the volume average particle size (Dv). To do.

(7) Measurement of average circularity C and standard deviation σ of magnetic carrier;
The average circularity C of the carrier is obtained by calculating the average circularity C based on the number distribution using a multi-image analyzer (manufactured by Beckman Coulter). In the measurement, a 50% by volume: 50% by volume mixed solution of a 1% NaCl aqueous solution and glycerin is used as an electrolytic solution. For the preparation of the electrolytic solution, an electrolytic solution prepared using primary sodium chloride or ISOTON-II (trade name, manufactured by Coulter Scientific Japan) can be used. As a dispersant, 0.1 to 1.0 ml of a surfactant (preferably alkylbenzene sulfonate) is added to about 30 ml of an electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. Disperse the electrolyte in which the sample is suspended with an ultrasonic disperser for about 1 minute, and measure with the measuring device using a 200 μm aperture and a 20 × lens. From the measured values, the equivalent circle diameter and the circularity C are calculated. calculate. The conditions for the measurement are as follows.
Average luminance within measurement frame: 220 to 230
Measurement frame setting: 300
SH (threshold): 50
Binarization level: 180

The outline of the measurement is as follows. Put the electrolyte in a glass measuring container, put the measurement sample in it to a concentration of 5 to 10%, and stir at the maximum stirring speed. Set the sample suction pressure to 10 kPa. Since the carrier has a large specific gravity and tends to settle, the measurement time should be 15 to 30 minutes. In addition, the measurement is interrupted every 5 to 10 minutes to replenish the sample solution and the electrolytic solution-glycerin mixed solution. Resume measurement after refilling. The number of measurements shall be 2000. After the measurement is finished, the main body software removes a defocused image, aggregated particles (multiple simultaneous measurements), etc. on the particle image screen. The measurement principle of this device is to ignite a strobe with a current pulse generated when particles in Coulter Multisizer II pass through the aperture as a trigger, record the projected image with a CCD, and perform image analysis processing. Since the plot on the obtained graph and the particle image photograph correspond to 1: 1, it is possible to remove defocused or aggregated particles as described above.
The circularity and equivalent circle diameter of the carrier are calculated by the following formulas (1) and (2).
Circularity = (4 × Area) / (MaxLength ² × π) (1)
Equivalent circle diameter = 2 × (Area / π) ^1/2 ... Formula (2)
Here, “Area” is the projected area of the binarized carrier particle image, and “MaxLength” is the maximum diameter of the projected carrier particle image. The equivalent circle diameter is represented by the diameter of a perfect circle when “Area” is the area of the perfect circle. The equivalent circle diameter is 4 to 100 μm divided into 256, and is used logarithmically based on the number distribution standard. Calculate (average circularity C-2σ) from the average circularity C and standard deviation σ obtained by the main software, find the number of particles below (average circularity C-2σ) on the graph, Divide to find the presence rate. These series of measurements and calculations are performed by the software attached to the multi-image analyzer.

(8) Volume resistance of the resin layer;
As a sample, a PET sheet having a thickness of 7 μm or more and 20 μm or less formed on a 100 μm thick PET sheet was used. The volume resistance value was measured using a 4-terminal probe with a resistivity meter Loresta AP or Hiresta IP (both product names, manufactured by Mitsubishi Yuka Co., Ltd. (currently Mitsubishi Chemical Corporation)) as a measuring device. The volume resistance was measured under the measurement environment of 20 ° C. to 25 ° C. and 50% RH to 60% RH.

(9) Measurement of primary average particle diameter of conductive particles of 1 μm or less;
Using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation; product name), conductive particles were photographed at a photographing magnification of 60,000 or 300,000 times. The axis is measured and the average value is taken as the particle size of the particle. This was measured for 100 samples, and the 50% value was taken as the primary particle size. When it was difficult to photograph the particles at a predetermined magnification, the photograph was enlarged and printed so that the predetermined magnification was obtained after photographing at a low magnification.

(10) Measurement of primary average particle diameter of conductive particles exceeding 1 μm;
Measurement was performed using “Laser Diffraction Scattering Particle Size Analyzer LS-230 Model” (product name) manufactured by Beckman Coulter Inc. That is, 1 to 25 mg of a measurement sample was added to 50 ml of IPA, and dispersion treatment was performed for 1 to 3 minutes with an ultrasonic disperser to obtain a sample solution. On the other hand, using a small amount of module, the measurement solvent was isopropyl alcohol (IPA). First, the measurement system of the apparatus was washed with IPA for about 5 minutes, and then the background function was executed. After that, gradually add the sample solution into the measurement system and adjust the sample concentration in the measurement system so that the PIDS (Polarization Intensity Differential Scattering) signal on the screen of the device is 45% to 55%. It was. The volume average particle diameter was determined from the volume distribution created from the measurement results, and was used as the primary average particle diameter.

(11) Average circularity of toner particles;
Measurement was performed in an environment of 23 ° C./60% RH using a flow type particle image analyzer FPIA-2100 (product name) manufactured by Sysmex Corporation. For toner particles having an equivalent circle diameter in the range of 0.60 μm or more and 400 μm or less, the area of the projected image and the perimeter were measured, and the equivalent circle diameter was determined from the area of the projected image of the toner particles measured there. The circularity of toner particles having an equivalent circle diameter in the range of 0.60 μm or more and 400 μm or less was determined by the following equation. Further, for toner particles having an equivalent circle diameter of 3 μm or more and 400 μm or less, the total circularity and the total number of particles were determined. The value obtained by dividing the total sum of the obtained circularity by the total number of particles was defined as the average circularity.
Circularity a = L ₀ / L
(In the formula, L ₀ represents the perimeter of a circle having the same area as that of the projected image of the toner particles, and L represents the image processing resolution when the image processing resolution is 512 × 512 (0.3 μm × 0.3 μm pixel). Indicates the perimeter of the projected image of toner particles.)

  The circularity is an index of the degree of unevenness of the toner particles, and indicates 1.00 when the toner particles are completely spherical. The more complicated the surface shape, the smaller the circularity. As a specific measurement method, 0.1 to 0.5 ml of alkylbenzene sulfonate is added as a dispersant in 200 to 300 ml of water from which impurities have been removed in advance, and 0.1 to 0.5 g of a measurement sample is further added. The suspension in which the sample is dispersed is dispersed with an ultrasonic transmitter for 2 minutes to prepare a test sample solution having a toner particle concentration of 20,000 / μl or more and 10,000,000 / μl or less. Measure the degree distribution. As an ultrasonic transmitter, the following apparatus is used and the following dispersion conditions are used. Equipment: UH-150 (product name, manufactured by SMT Co., Ltd.), OUTPUT level: 5, constant mode.

The outline of measurement of circularity is as follows.
The test sample solution is passed through a flat and flat flow cell (thickness: about 200 μm) flow path (expanded along the flow direction). A strobe and a CCD camera are mounted on opposite sides of the flow cell so as to form an optical path that passes across the thickness of the flow cell. While the test sample liquid is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, and each particle is a two-dimensional projection having a certain range parallel to the flow cell. Taken as an image. From the area of the projected image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter. Further, the equivalent circle diameter of each particle is determined from the area of the projected image of each particle having a circle equivalent diameter of 0.60 μm or more and 400 μm or less and the perimeter of the projected image using the above circularity calculation formula. Further, based on the obtained result, an average circularity (may be referred to as an average circularity) of toner particles having an equivalent circle diameter of 3 μm or more and 400 μm or less is calculated.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% in the following mixing | blending are a mass part and the mass%, respectively.

  The bowl-shaped resin particles used in the present invention are “Matsumoto Microsphere M-310” and “Matsumoto Microsphere M-311” (both trade names, Matsumoto Yushi Seiyaku Co., Ltd.). By classifying these particles, bowl-shaped resin particles (B-1 to B-10) as shown in Table 1 were obtained.

<Conductive particles C-1 to C-6>
The conductive particles C-1 to C-5 used in the present invention are commercially available products. C-6 was prepared as follows. Β-resin was extracted from coal tar pitch by solvent fractionation. This β-resin was subjected to hydrogenation and heavy treatment, and then the solvent-soluble component was removed with toluene to obtain mesophase pitch powder. This was finely pulverized, oxidized in air at about 300 ° C., further treated at 2800 ° C. in a nitrogen atmosphere, and then classified to give a volume average particle size of 2100 nm and a graphitization degree p (002) of 0.00. No. 39, graphitized particles C-6 were obtained. Table 2 shows the particle diameters of the C-1 to 6 conductive particles.

<Preparation of Toner Z-1>
<< Preparation of Binder Resin A >>
The following raw materials are put in a 5-liter four-necked flask at the following molar ratio, a reflux condenser, a water separator, an N ₂ gas introduction pipe, a thermometer and a stirring device are attached, and further, N ₂ gas is introduced into the flask. The polycondensation reaction was performed at 180 ° C. After completion of the reaction, the resin was filtered, washed with water, dehydrated and dried to obtain a binder resin A.
・ Propylene oxide addition bisphenol A 66mol ratio ・ Ethylene oxide addition bisphenol A 35mol ratio ・ Terephthalic acid 30mol ratio ・ Trimellitic acid 30mol ratio ・ Adipic acid 38mol ratio

Next, the following mixture was premixed with a Henschel mixer, then melt-kneaded with a biaxial extruder heated to 115 ° C., and then cooled and solidified.
Binder resin A 100 parts Magnetic material (average particle size: 0.25 μm) 95 parts Monoazo iron complex “T-77” (trade name, manufactured by Hodogaya Chemical Co., Ltd.) 2.5 parts Polypropylene (melting point: 145 ° C. ) 3.0 parts This solidified kneaded product was coarsely pulverized with a hammer mill to obtain a coarsely pulverized toner. This was finely pulverized using a mechanical pulverizer (trade name: Turbo Mill; manufactured by Turbo Industry Co., Ltd.). The finely pulverized product obtained was classified and removed at the same time using a multi-division classifier (trade name: Elbow Jet Classifier; manufactured by Nittetsu Mining Co., Ltd.) to obtain a raw material toner. The obtained raw material toner particles had a weight average particle diameter (D4) measured by Coulter counter method of 6.4 μm and an average circularity of 0.957. 100 parts of the raw material toner particles were treated with hexamethyldisilazane and mixed with 1.2 parts of hydrophobic silica fine powder treated with dimethyl silicone oil with a Henschel mixer to obtain negatively charged toner Z-1.

<Preparation of Toner Z-2>
<< Preparation of Binder Resin B >>
The following mixture is added dropwise to 200 parts of cumene refluxing (temperature: 146 ° C. to 156 ° C.) over 4 hours to complete solution polymerization under reflux of cumene, and the cumene is heated to 200 ° C. under reduced pressure. Removal of styrene-acrylic copolymer was obtained.
・ Styrene 69 parts ・ Butyl acrylate 15 parts ・ Monobutyl malate 7 parts ・ Di-tert-butyl peroxide 0.5 part

30 parts of the obtained styrene-acrylic copolymer was dissolved in the following mixture.
・ Styrene 50 parts ・ Butyl acrylate 20 parts ・ Monobutyl malate 2 parts ・ Divinylbenzene 0.4 parts ・ Benzoyl peroxide 0.8 parts ・ Tert-butylperoxy-2-ethylhexanoate 0.6 parts

  To the obtained mixed solution, 170 parts of water in which 0.15 part of polyvinyl alcohol partially saponified product was dissolved was added and stirred to obtain a suspension dispersion. Further, 100 parts of water was added, and the inside atmosphere was placed in a reactor substituted with nitrogen, and polymerization was carried out at 80 ° C. for 8 hours. After completion of the polymerization, the resin B was separated by filtration, washed with water, dehydrated and dried to obtain a binder resin B. Binder resin B had a Tg of 61.7 ° C. and a weight average molecular weight of 13,000.

Next, the following mixture was premixed with a Henschel mixer, then melt-kneaded with a biaxial extruder heated to 115 ° C., and then cooled and solidified.
・ Binding resin B 100 parts ・ Magnetic material (average particle size: 0.22 μm) 95 parts ・ Monoazo iron complex “T-77” (product name) 1.5 parts ・ Paraffin (melting point: 76 ° C.) 5 parts Solidified kneaded product A raw material toner was obtained by the same treatment as in the toner Z-1. The weight average particle diameter (D4) measured by the Coulter Counter method of this raw material toner was 6.6 μm, and the average circularity was 0.942. A negatively charged toner Z-2 is obtained by mixing 100 parts by mass of the toner particles with hexamethyldisilazane and 1.2 parts by mass of hydrophobic silica fine powder treated with dimethylsilicone oil using a Henschel mixer. It was.

<Adjustment of Toner Z-3>
<Production of Polymerized Toner Base Particles for Toner Z-3>
To 900 parts of ion-exchanged water heated to 60 ° C., 3 parts of tricalcium phosphate was added and stirred at 10000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare an aqueous medium. On the other hand, the following raw materials were put into a homogenizer (manufactured by Nippon Seiki Co., Ltd.), heated to 60 ° C., dispersed by stirring at 8000 rpm with a TK homomixer, and then a polymerization initiator 2,2′-azobis. 5 parts of (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.
Styrene 135 parts N-butyl acrylate 55 parts C.I. I. Pigment Blue 15: 3 17 parts Aluminum salicylate compound 3 parts Polyester resin 15 parts Stearate stearate wax (DSC main peak 60 ° C) 40 parts Divinylbenzene 0.5 parts Note) Aluminum salicylate compound is manufactured by Orient Chemical Co., Ltd. "Bontron E-88" (product name). The polyester resin is a polycondensate of propylene oxide-modified bisphenol A and isophthalic acid, Tg = 65 ° C., Mw = 10000, Mn = 6000.

  The polymerizable monomer composition was put into the aqueous medium, and granulated by stirring at 8000 rpm using a TK homomixer at 60 ° C. in a nitrogen atmosphere. Thereafter, the mixture was transferred to a reaction vessel equipped with a propeller type stirring device and stirred, and the temperature was raised to 70 ° C. over 2 hours. After another 4 hours, the temperature was raised to 80 ° C. at a heating rate of 40 ° C./Hr. The reaction was carried out at 5 ° C. for 5 hours to produce polymer particles. After the completion of the polymerization reaction, the slurry containing the polymer particles is cooled, washed with 10 times the amount of water as the slurry, filtered and dried, and the particle size is adjusted by classification to obtain cyan toner base particles (weight average particle size) 6.1 μm and an average circularity of 0.969) were obtained.

  To 100 parts of the toner base particles, 1.0 part of hydrophobic silica fine powder surface treated with hexamethylene disilazane (average primary particle diameter 7 nm), 0.15 part of rutile titanium oxide fine powder (primary average particle diameter 45 nm) and rutile Type titanium oxide fine powder 0.5 part (average primary particle size 200 nm) was dry mixed with a Henschel mixer for 5 minutes to obtain toner Z-3 as a non-magnetic one-component developer having an average circularity of 0.969.

<Adjustment of Toner Z-4>
<< Preparation of Binder Resin C >>
10 parts of styrene as a vinyl copolymer material, 5 parts of 2-ethylhexyl acrylate, 2 parts of fumaric acid, 5 parts of a dimer of α-methylstyrene, and 5 parts of dicumyl peroxide are placed in a dropping funnel. It was. Moreover, the following material was put into the glass 4 liter four neck flask as a material of the polyester unit.
Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 27 parts Polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 13 parts Terephthalic acid 10 parts Trimellitic anhydride 5 parts Fumaric acid 24 parts 2-Ethylhexanoic acid 0.4 part A thermometer, stir bar, condenser and nitrogen inlet tube were attached to this four-necked flask, and this four-necked flask was placed in a mantle heater. installed. Next, after the inside of the four-necked flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and while stirring at a temperature of 125 ° C., the monomer and the polymerization of the vinyl copolymer from the previous dropping funnel The initiator was added dropwise over about 5.5 hours. Next, the temperature was raised to 200 ° C. and reacted for about 5 hours to obtain a binder resin C having a weight average molecular weight of 79000 and a number average molecular weight of 4000.

Next, the following materials were mixed with a Henschel mixer, and then kneaded with a twin-screw kneader “PCM-30 type” (product name, manufactured by Ikekai Tekko Co., Ltd.) set at a temperature of 130 ° C.
Binder resin C 100 parts Purified normal paraffin (Maximum endothermic peak temperature by DSC = 80 ° C., weight average molecular weight 800) 5 parts
0.5 parts of 3,5-di-t-butylsalicylic acid aluminum compound
C. I. Pigment Blue 15: 3 5 parts The obtained kneaded product was cooled and solidified, and coarsely pulverized to 1 mm or less with a hammer mill. The obtained coarsely pulverized toner was finely pulverized using a collision-type airflow pulverizer using high-pressure gas. The obtained toner fine powder was classified by a multi-division classifier using the Coanda effect to obtain cyan particles having a weight average particle diameter of 7.2 μm and an average circularity of 0.930. Further, this cyan particle was surface-modified with a hybridizer (manufactured by Nara Machinery Co., Ltd.) at a rotation speed of 6800 rpm, a processing time of 3 minutes, and a processing frequency of 2 times, and a cyan toner having a weight average particle diameter of 6.0 μm and an average circularity of 0.944. Z-4 was obtained.

<Preparation of magnetic carrier Y-1>
<< Manufacture of carrier core >>
A silane coupling agent of 4.0% by mass for magnetite powder with a number average particle size of 250 nm and specific resistance of 5.1 × 10 ⁵ Ω · cm, hematite powder with a number average particle size of 260 nm and specific resistance of 4.9 × 10 ⁷ Ω · cm (3 -(2-Aminoethylaminopropyl) trimethoxysilane) was added, and surface treatment was performed by mixing and stirring at 110 ° C. in a container at high speed.
Phenol 10 parts by weight Formaldehyde solution (formaldehyde 37% by weight aqueous solution) 6 parts by weight Treated magnetite 1 76 parts by weight Treated hematite 1 8 parts by weight

キャリアコア1の表面はキャリアコアに対して0.12質量％のγ-アミノプロピルトリメトキシシランで処理され、下記の基が存在していることが確認できた。

The above materials were placed in a flask and mixed well at 40 ° C. to obtain a reaction medium. The amount of dissolved oxygen in the reaction medium at this time was 7.3 g / m ³ . Next, nitrogen gas was introduced into the reaction medium at a flow rate of 1.5 × 10 ⁻² m ³ / h for 20 minutes, and the internal atmosphere was replaced with nitrogen. At this time, the amount of dissolved oxygen in the reaction medium was 1.0 g / m ³ . Next, 5 parts by weight of 28% ammonia water and 10 parts by weight of water were added. After that, the amount of nitrogen introduced was suppressed to 0.3 × 10 ^-2 m ³ / h, and the room temperature increased from room temperature to 85 ° C at an average rate of 3.0 ° C / min. The mixture was heated and allowed to cure by stirring at this temperature for 3 hours. The stirring blade peripheral speed at this time was 1.8 m / sec. Thereafter, the mixture was cooled to 30 ° C., water was added to remove the supernatant, and the precipitate was washed with water and then air-dried. Subsequently, this was dried under reduced pressure (5 hPa or less) at a temperature of 60 ° C. to obtain a spherical magnetic carrier core 1 in which a magnetic material was dispersed. While continuously applying a shear stress to the surface of the carrier core 1 obtained above, a 3% by mass methanol solution of γ-aminopropyltrimethoxysilane represented by the following formula was applied to volatilize the methanol. .

The surface of the carrier core 1 was treated with 0.12% by mass of γ-aminopropyltrimethoxysilane with respect to the carrier core, and it was confirmed that the following groups were present.

  While stirring the carrier core 1 treated with the above silane coupling agent at 50 ° C., silicone resin SE2410 (Toray Dow Corning Co., Ltd.) diluted with toluene so that the silicone resin solid content is 20% is stirred in the carrier core. )) Was added under reduced pressure, and a 1.0 mass% resin coat (referred to as coat 1) was applied to the carrier core. Thereafter, the mixture was stirred for 2 hours in a nitrogen gas atmosphere to volatilize toluene, and then heat treated at 140 ° C. for 2 hours in a nitrogen atmosphere to loosen the agglomerates, and then coarse particles were sieved with a sieve having an opening of 76 μm. The magnetic carrier Y-1 having a volume average particle diameter of 34.09 μm, an average circularity C of 0.923, a standard deviation σ of 0.028, and an average circularity C-2σ of 0.867 or less and a particle abundance ratio of 2.9% by number is obtained. Obtained. Most of the obtained magnetic carriers were spherical or elliptical, and there were very few amorphous particles.

<Example 1>
Resol type phenolic resin solution J-325 containing 40% methanol (Dainippon Ink & Chemicals, Inc .; product name) 167 parts (100 parts solids), 65 parts of conductive particles C-1 and 70 parts of methanol In addition, it was dispersed for 2 hours in a horizontal sand mill (using glass beads with a diameter of 1 mm as media particles). Add 302 parts of bowl-shaped resin particles B-1 and 30 parts of methanol to 302 parts of the resulting dispersion, and disperse for 30 minutes in a vertical sand mill (using 1 mm diameter glass beads as media particles). Used to separate the glass beads. Methanol was added to the obtained dispersion so that the solid concentration was 34% to obtain a coating solution.
The upper and lower ends of an aluminum cylindrical tube having an outer diameter of 14 mm, a wall thickness of 2 mm, and a surface Ra of 0.3 μm were masked. While holding and rotating the cylindrical tube along the vertical direction, the coating liquid was applied while lowering the spray gun at a constant speed, and then heated at 150 ° C. for 30 minutes in a hot air drying furnace. Thus, a resin layer was formed to obtain developer carrier S-1. Attach a magnet roller to developer carrier S-1, attach flanges to both ends, and attach it as a developer carrier to a toner cartridge of Laser Jet 4300 (product name) manufactured by Hewlett-Packard. Using. The outline of this developing apparatus is as shown in FIG. A Laser Jet 4300 equipped with this developing device was subjected to a durability test of 20,000 sheets in an intermittent mode of 1 sheet / 7 seconds using toner Z-2. The developer layer thickness regulating member attached to the toner cartridge was removed, and a new elastic blade having a roughened surface was attached. In the initial evaluation, the durability test was interrupted at the 10th sheet, and the durability evaluation was performed after the end of the durability test. A section of about 5 mm × 5 mm square is cut out from the obtained developer carrying member. The concave part of the resin layer surface of this section was photographed using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation). Images were taken at a magnification of 60,000 times, and it was confirmed that conductive particles were present in the resin layer on the surface of the recess. Image evaluation was conducted at normal temperature and humidity (23 ° C, 50% RH; N / N), low temperature and low humidity (15 ° C, 10% RH; L / L), and high temperature and high humidity (32 ° C, 85% RH; H / H).

  Evaluation items, measurement methods and evaluation criteria are as follows.

(A) Image density;
The reflection density of a solid black circle image included in a test chart with an image ratio of 5.5% is measured at 10 locations using a reflection densitometer (trade name: RD918, manufactured by Macbeth), and the average value of the measured values is taken. Concentration.

(I) fog;
The reflectance of the solid white area in the image and the reflectance of the unused transfer paper were measured at 10 random locations with a reflectometer TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.). Value—average reflectance of unused transfer paper), and this is defined as the fog density. Based on this value, the following criteria were evaluated.
A: 1.0% or less (fogging is not visually recognized).
B: More than 1.0% and 2.0% or less (fogging is not allowed unless attention is paid).
C: More than 2.0% and 3.0% or less (although fog is present, there is no practical problem).
D: Over 3.0% (fogging is noticeable).

(C) Sleeve ghost;
As shown in FIG. 5, it consists of a solid white portion 51 and a solid black portion 52, which are alternately present at a width of 4.5 cm from the tip, and a halftone portion 53 adjacent to the initial (20th sheet) and at the end of the durability evaluation. A4 standard chart was printed. The difference in density appearing on the obtained halftone image was visually observed and evaluated according to the following criteria.
A: No difference in shading is observed.
B: A slight shading difference is observed.
C: Practical level with slight difference in shading.
D: Conspicuous shade difference is within 4.5cm E: Conspicuous shade difference is over 4.5cm

(D) Arithmetic mean roughness (Ra) of the developer carrier surface;
Ra of the developer carrier after the initial stage and durability was measured by the method described in (4) above.

(5) Resistant resistance of the resin coating layer;
The surface of the developer carrier after the durability evaluation was observed at 200 times using an ultra-deep shape measuring microscope (manufactured by Keyence Corporation; product name: VK-8510), and the degree of toner contamination was evaluated according to the following criteria. .
A: Only minor contamination is observed.
B: Some contamination is observed.
C: Contamination is partially observed.
D: Significant contamination is observed.

  Tables 3 and 4 show the configuration of developer carrier S-1 and the shape of the recesses on the surface of developer carrier. Tables 5, 6 and 7 show the results of the above evaluations under each environment.

<Examples 2-3 and Comparative Examples 1-2>
A developer carrier was prepared and evaluated in the same manner as in Example 1 except that the addition amount of the bowl-shaped resin particles B-1 was changed as shown in Table 3 below.

<Comparative Example 3>
Resol type phenol resin solution J-325 containing 40% methanol (Dainippon Ink Chemical Co., Ltd .; product name) 167 parts (100 parts solids), conductive particles C-1 65 parts methanol 100 parts In addition, this was dispersed for 2 hours in a horizontal sand mill (using glass beads having a diameter of 1 mm as media particles), and then methanol was added so that the solid concentration was 34% to obtain a coating solution.

An aluminum cylindrical tube having an outer diameter of 14 mm, a wall thickness of 2 mm, and a surface Ra of 0.3 μm was attached to the sand blasting apparatus shown in FIG. 6, and blasting was performed using # 100 spherical glass beads as the abrasive grains 106. “Pneumatic blaster” (trade name, manufactured by Fuji Seisakusho) was used as a blasting apparatus, and the air pressure was 2 kg / cm ² . The treatment time was 40 seconds and the rotational speed of the cylindrical tube was 60 rpm. The arithmetic mean roughness (Ra) of the cylindrical tube surface after the treatment was 1.00. The upper and lower end portions of the blasted cylindrical tube were masked, and the shaft was held so that the axis was along the vertical direction. The coating liquid was applied while rotating the cylindrical tube while lowering the spray gun at a constant speed, and then heated at 150 ° C. for 30 minutes in a hot air drying furnace to form a resin layer. Thus, developer carrier S-18 was produced.

<Comparative example 4>
A developer carrier S-19 was produced and evaluated in the same manner as in Example 1 except that the coating liquid of Comparative Example 3 was used.

<Comparative Example 5>
A developer carrier S-20 was prepared in the same manner as in Example 1 except that 20 parts of the spherical resin particles “Opto Beads 6500M” (trade name, manufactured by Nissan Chemical Industries, Ltd.) were used as the bowl-shaped resin particles B-1. ,evaluated.

<Examples 4 to 12>
Each developer carrier was prepared and evaluated in the same manner as in Example 1 except that the bowl-shaped resin particles B-1 in Example 1 were changed as shown in Table 3 below.

<Examples 13 to 15>
Each developer carrier was prepared and evaluated in the same manner as in Example 1 except that the conductive particles C-1 in Example 1 were changed as shown in Table 3 below.
The coating liquid was dispersed in the same manner as in Example 2 except that the conductive particles C-4 were used, but the viscosity was high and the produced developer carrier was wrinkled on the surface. There wasn't. The developer carrier had a dispersion average particle size of 11 μm.
A section of about 5 mm × 5 mm square was cut out from each developer carrier (S-1 to S-15) obtained. The concave portion of the surface of the resin layer of this section was photographed using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation; product name). Images were taken at a magnification of 60,000 times, and it was confirmed that conductive particles were present in the resin layer on the surface of the recesses for all developer carriers. Tables 3 to 4 show the configurations of the developer carriers of Examples 1 to 15 and the shape of the recesses on the surface of the developer carriers. The evaluation results are shown in Tables 5-7.

<Examples 16 to 19>
A developer carrier was prepared and evaluated in the same manner as in Example 1 except that the elastic blade in Example 1 was replaced with an elastic blade having the surface roughness (Rzjis) and Rsm having the values shown in Table 3.

  The surface roughness (Ra) described in Table 4 is a value for the developer carrier used when the evaluation was performed in an N / N environment.

この塗工液を、外径16mm、肉厚2mm、表面のRaが0.3μmのアルミニウム製円筒管に実施例１と同様にして塗布、硬化させて樹脂層を形成し、現像剤担持体S-21を作製した。この現像剤担持体S-21を、市販のレーザービームプリンタ「レーザーショットLBP5000」（キヤノン株式会社製；製品名）のシアン用カートリッジの現像装置に組み込んだ。この現像装置の概略は図4に示すとおりである。また、当該カートリッジにトナーとしてトナーZ-3を充填した。当該シアン用カートリッジを前記レーザービームプリンタに装填し、1枚/10秒の間欠モードで3000枚の耐久テストを行った。初期評価は10枚目の時に耐久テストを中断して、そして耐久評価は耐久テスト終了後に、実施例１と同様に行った。現像剤担持体S-21の構成と現像剤担持体表面の凹部形状を表8、9に、評価結果を表10に示す。 <Example 20>
Resol type phenolic resin solution J-325 containing 40% methanol (Dainippon Ink Chemical Co., Ltd .; product name) 167 parts (100 parts as solid content), 65 parts of conductive particles C-1, 10 parts of the charge control agent represented by A) and 70 parts of methanol were added and dispersed in a horizontal sand mill (using glass beads with a diameter of 1 mm as media particles) for 2 hours. To 312 parts of the resulting dispersion, 25 parts of bowl-shaped resin particles B-2 and 30 parts of methanol were added, and this was dispersed for 30 minutes with a vertical sand mill (using glass beads with a diameter of 1 mm as media particles). After separating the glass beads using a sieve, methanol was added so that the solid concentration was 34% to obtain a coating solution.

This coating solution was applied and cured in the same manner as in Example 1 on an aluminum cylindrical tube having an outer diameter of 16 mm, a wall thickness of 2 mm, and a surface Ra of 0.3 μm to form a resin layer. 21 was produced. This developer carrier S-21 was incorporated into a developing device for a cyan cartridge of a commercially available laser beam printer “Laser Shot LBP5000” (manufactured by Canon Inc .; product name). The outline of this developing apparatus is as shown in FIG. The cartridge was filled with toner Z-3 as toner. The cyan cartridge was loaded into the laser beam printer, and a durability test of 3000 sheets was performed in an intermittent mode of 1 sheet / 10 seconds. In the initial evaluation, the durability test was interrupted at the 10th sheet, and the durability evaluation was performed in the same manner as in Example 1 after the end of the durability test. Tables 8 and 9 show the configuration of the developer carrier S-21 and the shape of the recesses on the surface of the developer carrier, and Table 10 shows the evaluation results.

<Examples 21 to 22>
A developer carrier was prepared in the same manner as in Example 20 except that the addition amount of the bowl-shaped resin particles B-2 in Example 20 was changed as shown in Table 8, and evaluated in the same manner as in Example 1. . Further, a section of about 5 mm × 5 mm square was cut out from each developer carrier (S-21 to S-23). The concave part of the resin layer surface of this section was photographed using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation). Images were taken at a magnification of 60,000 times, and it was confirmed that conductive particles were present in the resin layer on the surface of the recesses for all developer carriers.

<Comparative Example 6>
In Example 20, the bowl-shaped resin particles B-2 were changed to spherical resin particles (trade name: Optobead 6500M, manufactured by Nissan Chemical Industries, Ltd.), and the addition amount was changed to 30 parts. Otherwise, a developer carrier was prepared in the same manner as in Example 20, and evaluated in the same manner as in Example 1. Tables 8 to 9 show the details of the recessed portions of the developer carrying members of Examples 20 to 22 and Comparative Example 6, and Table 10 shows the evaluation results.

<Example 23>
Resol type phenolic resin solution J-325 containing 40% methanol (Dainippon Ink Chemical Co., Ltd .; product name) 167 parts (100 parts as solid content), 65 parts of conductive particles C-1 10 parts and 70 parts of methanol were added and dispersed for 2 hours in a horizontal sand mill (using glass beads with a diameter of 1 mm as media particles). To 312 parts of the resulting dispersion, 30 parts of bowl-shaped resin particles B-2 and 30 parts of methanol are added, and this is dispersed with a vertical sand mill (using glass beads with a diameter of 1 mm as media particles) for 30 minutes. The glass beads were separated using a sieve. Thereafter, methanol was added so that the solid content concentration was 34% to obtain a coating solution.

  This coating solution is applied and cured in the same manner as in Example 1 to an aluminum cylindrical tube having an outer diameter of 24.5 mm, a wall thickness of 2 mm, and a surface Ra of 0.2 μm to form a surface layer. -25 was produced.

  A digital roller iR6570 (manufactured by Canon Inc .; product name) in which a magnetic roller is inserted into the developer carrier S-25 and flanges are attached to both ends, and the electrostatic latent image carrier is an amorphous silicon drum photoreceptor. It was incorporated in the developing device. The outline of this developing apparatus is as shown in FIG. In order to strengthen the magnetic binding force, the magnet roller was an all-pole magnetic up magnet roll in which the magnetic force was all increased by 10% compared to the magnet roller used in the developing device. Further, the toner coat forming means (magnetic blade) formed of ferromagnetic iron was disposed so that the tip thereof was opposed to the magnetic pole of the magnet. The toner coat forming means is inclined so that the thickness of the portion supported by the toner container is 1.8 mm and the thickness of the tip of the portion facing the developer carrier is 0.6 mm. Yes. A durability test of 1 million sheets was performed in continuous mode using toner Z-1. In the initial evaluation, the durability test was interrupted at the 10th sheet, and the durability evaluation was performed in the same manner as in Example 1 after the end of the durability test. Tables 11 and 12 show the configuration of developer carrier S-25 and the shape of the recesses on the surface of the developer carrier, and Table 13 shows the evaluation results.

<Examples 24 to 25>
A developer carrier was prepared in the same manner as in Example 23 except that the amount of the bowl-shaped resin particles B-2 in Example 23 was changed as shown in Table 11, and evaluated in the same manner as in Example 1. A section of about 5 mm × 5 mm square was cut out from each developer carrier thus obtained. The concave portion of the surface of the resin layer of this section was photographed using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation; product name). Images were taken at a magnification of 60,000 times, and it was confirmed that conductive particles were present in the resin layer on the surface of the recesses for all developer carriers.

<Comparative Example 7>
The bowl-shaped resin particles B-2 in Example 23 were changed to the spherical resin particles used in Comparative Example 6, and the addition amount was changed to 30 parts. Otherwise, a developer carrier was prepared in the same manner as in Example 23 and evaluated in the same manner as in Example 1. Tables 11 to 12 show the details of the recess shapes of the developer carriers of Examples 23 to 25 and Comparative Example 7, and Table 13 shows the evaluation results.

<Example 26>
Resol type phenolic resin solution containing 40% methanol (trade name: J-325; manufactured by Dainippon Ink & Chemicals, Inc.) 167 parts (100 parts as solid content), 24 parts of conductive particle carbon black C-1 and 6 parts of graphitized particles C-6 and 70 parts of methanol were added, and dispersed for 2 hours in a horizontal sand mill (using glass beads having a diameter of 1 mm as media particles). To 267 parts of the obtained dispersion, 30 parts of bowl-shaped resin particles B-3 and 30 parts of methanol are added, and this is dispersed for 30 minutes with a vertical sand mill (using glass beads with a diameter of 1 mm as media particles). The glass beads were separated using a sieve. Thereafter, methanol was added so that the solid content concentration was 34% to obtain a coating solution. This coating solution was applied and cured in the same manner as in Example 1 on an aluminum cylindrical tube having an outer diameter of 16 mm, a wall thickness of 2 mm, and a surface Ra of 2.0 μm to form a surface layer. 29 was produced. A magnet roller was assembled to developer carrier S-29 and incorporated in the developing device of a copying machine “iRC3200N” (manufactured by Canon Inc .; product name). The outline of this developing device is as shown in FIG. In the copying machine “iRC3200N” equipped with this developing device, a durability test of 30,000 sheets was performed in an intermittent mode of 1 sheet / 10 seconds using toner Z-4 and carrier Y-1. In the initial evaluation, the durability test was interrupted at the 10th sheet, and the durability evaluation was performed in the same manner as in Example 1 after the end of the durability test. Tables 14 and 15 show the configuration of the developer carrier S-29 and the shape of the recesses of the developer carrier, and Table 16 shows the evaluation results.

<Examples 27 to 28>
A developer carrier was prepared in the same manner as in Example 26 except that the addition amount of the bowl-shaped resin particles B-3 in Example 26 was changed as shown in Table 14, and evaluated in the same manner as in Example 1. . A section of about 5 mm × 5 mm square was cut out from each developer carrier thus obtained, and the concave portion of the resin layer surface of the section was photographed using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation). Images were taken at a magnification of 60,000 times, and it was confirmed that conductive particles were present in the resin layer on the surface of the recesses for all developer carriers.

<Comparative Example 8>
A developer carrier was prepared in the same manner as in Example 26 except that the bowl-shaped resin particles B-3 in Example 26 were replaced with the spherical resin particles used in Comparative Example 6, and evaluated in the same manner as in Example 1. . Details of the surface shapes of the developer carrying members of Examples 26 to 28 and Comparative Example 8 are shown in Tables 14 to 15, and the evaluation results are shown in Table 16.

5 Multipolar magnet (Magnet roller)
6 Base (Metal cylindrical tube)
7 Conductive resin layer 8 Developer carrier (Developer carrier)
14 conductive particles 15 binder resin 16 bowl-shaped resin particles

Claims (2)

  The substrate surface has a resin layer containing at least a binder resin, conductive particles, and bowl-shaped resin particles, the resin layer contains the bowl-shaped resin particles, and the openings of the bowl-shaped resin particles are A developer-carrying member, wherein a recess is formed on the surface of the resin layer depending on the shape of the developer, and at least the binder resin and the conductive particles are present on the surface of the recess.   A developer, a developer container that contains the developer, a developer carrier that carries the developer contained in the developer container and transports the developer to the development region, and the developer provided in contact with the developer carrier A developing device comprising a developer layer thickness regulating member for regulating a layer thickness of a developer on the carrier, wherein the developer carrier is the developer carrier according to claim 1.

Images