JP2006030263A - Toner, image forming method, and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonmagnetic monocomponent toner which controls the charging property and fluidity of the toner and the bonding force of the toner and silica, suppresses occurrence of problems such as fogging, dropping, filming, fusion and sticking of the toner on a developing roller, etc., and density lowering even in long-term use in a high temperature and high humidity environment, has good property of following a solid image and good suitability to cleaning, and excels in low-temperature fixability. <P>SOLUTION: The nonmagnetic monocomponent toner has toner particles obtained by aggregating and integrating a plurality of polymer fine particles dispersed in an aqueous medium, wherein the toner particles contain at least hydrophobed silica fine powder and an inorganic fine powder which is charged to polarity reverse to that of the hydrophobed silica fine powder when two-component triboelectricity is measured using a ferrite carrier. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a non-magnetic one-component toner used in an electrophotographic method, an electrostatic recording method, a toner jet method or the like, a method for forming an image using an electrophotographic process, and a process cartridge and a developing unit used therefor. Relates to a toner and an image forming method suitable for constituting an electrophotographic process in which non-magnetic one-component toner is contact-developed, and a process cartridge and a developing unit used therefor.

  Conventionally, many methods are known as electrophotographic methods. Generally, a photoconductive substance is used to form an electric latent image on an image carrier (photosensitive member) by various means, and then, The latent image is developed with toner to become a visible image, and if necessary, the toner image is transferred onto a transfer material such as paper, and then the toner image is fixed on the transfer material by heat / pressure to obtain a copy. Is.

  As a method for visualizing an electric latent image, a magnetic two-component developing method comprising a magnetic toner and a carrier, a non-magnetic two-component developing method comprising a non-magnetic toner and a carrier, and a non-magnetic toner using an external additive particle alone are not used. In general, a magnetic one-component development system and a magnetic one-component development system using a magnetic toner are widely used.

  On the other hand, in the electrophotographic industry, the image resolution of printers and the like has been increased to 1200, 2400 dpi. Accordingly, the development method of the printer apparatus is also required to have higher definition. Also, copying machines are becoming more sophisticated and digitized, and as with printers, higher resolution and higher definition are required.

  Further, in recent years, as copiers and printers using electrophotography have been widely used, including in homes, etc., there is an increasing demand for making copy machines or printers inexpensive and small.

  Accordingly, development methods have been improved to meet these requirements, and a non-magnetic one-component contact development method that can be easily achieved for high resolution and high definition among various development methods is preferably used.

  In the one-component development method, if the photosensitive member and the toner carrier have a distance, the electric force lines concentrate on the edge portion of the electrostatic latent image on the photosensitive member, and the toner is developed along the electric force lines. Image quality is likely to deteriorate due to an edge effect in which toner is biased and developed at the edge portion of the image.

  Therefore, the edge effect is prevented by bringing the photosensitive member and the toner carrier very close to each other, but the gap between the photosensitive member and the toner carrier is mechanically set, that is, from the thickness of the toner layer on the toner carrier. However, it is difficult to set the gap small.

  Therefore, the edge effect is prevented by using a one-component contact development method in which the toner carrying member is pressed against the photosensitive member for development. However, if the toner carrier surface moving speed is the same as the photosensitive member surface moving speed, a satisfactory image cannot be obtained when the latent image on the photosensitive member is visualized. Therefore, in the one-component contact development method, by making a difference in the toner carrier surface movement speed with respect to the photoreceptor surface movement speed, a part of the toner on the toner carrier is made to the latent image on the photoreceptor surface. It is developed and some other toner is stripped off, resulting in a developed image without edge effects that is very faithful to the latent image. Furthermore, compared to the two-component development method, this non-magnetic one-component contact development method is considered easier to reduce the size, simplification, and weight of the developing device. There is a great merit for the spread of it.

  In such a contact one-component development method, it is essential to rub the surface of the photosensitive member with toner and a toner carrier. For this reason, toner deterioration occurs due to long-term use, and toner fluidity and charging uniformity are deteriorated. This is undesirable because it causes a decrease in fog and a decrease in transfer efficiency. Further, it is not preferable because the toner is liable to be fused or filmed to the friction charging member, the developing roller, the photosensitive member, etc., and the image quality is lowered. In addition, even if the toner carrying member rubs the surface of the photoconductor, the toner is insufficiently charged. If the toner is charged to some extent, the toner easily adheres to the surface of the photoconductor. This is not preferable.

  Regarding non-magnetic one-component contact development methods, there is a method in which a metal salt compound is externally added (see, for example, Patent Documents 1 and 2). The level.

  High image quality that reproduces minute dots faithfully by having a specific range of the average particle size and shape factor on the toner particles of an external additive possessed by a toner having a specific circularity distribution and a specific weight average particle size. It is described that an image is obtained, the mechanical stress in the developing device is high, and toner deterioration hardly occurs (for example, see Patent Document 3).

  However, the above prior art has a point to be further improved in terms of suppression of fog when performing contact development.

  In addition, an external additive having a volume average particle size of 30 nm to 50 nm is used, and the coverage of the external additive on the toner surface is set to 18% or more and 60% or less, so that the toner on the blade and the developer carrier surface can be obtained. There is a method in which fusion and adhesion can be suppressed (see, for example, Patent Document 4). However, the effect is not sufficient when used in a high-temperature and high-humidity environment, and fog is also insufficient. Further, in non-magnetic one-component contact development, inorganic fine particle external additives, toner fusion, filming, and the like occur on the photoreceptor, but the description thereof is not sufficient.

  Furthermore, in response to the desire to make the copying machine or printer inexpensive and small, sufficient cleaning must be performed not only by the developing method but also by a simple cleaning mechanism. Therefore, a toner having excellent cleaning properties is essential. There is a method in which toner having excellent cleaning properties can be obtained by setting the particle size, particle size distribution, shape factor, BET, and specific gravity of the toner within specific ranges (see, for example, Patent Document 5). However, there is no description about fogging, and the effect was insufficient even by detailed examinations by the present inventors.

  In addition, there is a method in which a toner excellent in developability and cleaning property can be obtained by controlling the arrangement of the release agent layer in toner obtained by aggregating various dispersions such as resin particle dispersion obtained by emulsion polymerization. (For example, refer to Patent Document 6). However, it has been found that developability is insufficient particularly for long-term use in a high temperature and high humidity environment.

  Furthermore, in response to the desire to make copying machines or printers inexpensive and compact, it is necessary to improve not only the development method but also the fixing method. For this reason, the copying machine or printer is designed. Above, it is essential to simplify the fixing method and reduce power consumption.

  As a method for fusing and fixing toner on paper, a fixing method using a heat roll is most commonly used, but means for supplying oil to the heat roll is usually provided for the purpose of preventing offset to the heat roll. In order to prevent wrapping at the time of fixing, means for separating the fixed image from the fixing roller is provided. When simplifying the fixing method, a toner that can obtain a good fixed image without using such means, has excellent fixing strength to a transfer material, and has excellent separation from a fixing roller is required.

  Further, when reducing power consumption, toner for electrophotography used in a copying machine or printer is required to have a low fixing temperature.

  To date, proposals have been made to improve the molecular weight and molecular weight distribution of binder resins in response to the above requirements. For example, a method of using a binder resin that has a low molecular weight and a narrow molecular weight distribution to lower the fixing temperature and further melts sharply during fixing to smooth the image surface has been studied. However, when the molecular weight is lowered, the melting point is lowered, but the internal cohesive force is also lowered. Therefore, there is a problem that it is difficult to peel from the fixing roll at the time of melting.

  In response to the above requirements, a method has been studied in which a release agent is added to the toner so that the toner can be easily peeled off from the fixing roll (see, for example, Patent Document 7). However, in the simplified fixing method, not all toner characteristics are satisfactory. This is because it is difficult to control the distribution and dispersion state of the release agent contained in the toner to an optimum state. In order to satisfy the releasability from the fixing roll, the addition amount of the release agent to the toner is desirably 1 to 20% by mass, and the releasability increases as the addition amount increases. However, particularly when the amount of the release agent added is large, for example, when a toner is prepared by a kneading and pulverizing method, the distribution and dispersion state of the release agent is not controlled to an optimum state, and is generally used as a release agent. If the wax used in general is exposed at a high concentration together with the pigment on the toner surface, the powder fluidity and the thermal cohesiveness are deteriorated. For this reason, when the toner is actually used, problems occur in terms of developability such as blocking, filming, and fusion.

  As a means for overcoming the disadvantages of the toner to which such a wax is added, there is a toner in which a wax is encapsulated in a toner particle by a capsule-type structure (see, for example, Patent Documents 8, 9 and 10). Such a capsule structure toner can reduce the ratio of low molecular weight components such as wax exposed on the surface, and the problems such as blocking and filming described above are relatively small. However, in many cases, such a toner having no surface wax is not always sufficiently releasable from the fixing roll. In order to obtain sufficient separation from the hot roll during fixing, it is necessary to instantly form a release layer such as molten wax between the surface of the hot roll and the molten toner layer. There is a problem that it takes time for the molten wax to diffuse to the interface inside the resin, and the release layer is not instantly formed.

  As a method for overcoming the problems relating to the compatibility of developability and fixability at low energy in the non-magnetic one-component contact development method as described above, there is a method of combining low softening point resin particles and high softening point resin particles ( For example, refer to Patent Document 11), although there is a description of compatibility between fixing at low energy and cleaning properties, but there is no description of fogging, blurring, etc., and the effect is insufficient even by detailed studies by the present inventors. It was something.

Further, there is a method of adding a wax ester containing an oxyacid ester to a toner composition containing a polyester resin having a specified acid value (see, for example, Patent Document 12). Although there is a description about improvement of fusion, there is no description about dropping of a button, cleaning performance, maintenance of transparency at the time of fixing an OHT image, etc., and the effect is insufficient even by detailed examination by the present inventors. It was something.
JP-A-9-127720 JP-A-9-190006 EP 886187A1 JP 2001-166533 A Japanese Patent Laid-Open No. 05-188637 JP 11-327201 A JP 56-87051 A JP-A-60-222868 Japanese Patent Laid-Open No. 61-114247 JP 59-162562 A Japanese Patent Laid-Open No. 06-282099 JP 2000-147827 A

  An object of the present invention is to provide a non-magnetic one-component toner, an image forming method using the toner, a process cartridge, and a developing unit that solve the above problems.

  That is, an object of the present invention is to have excellent fixability at a low temperature, and fogging, blurring, filming, fusion of toner to a developing roller and a toner layer regulating member even in a long-term use in a high temperature and high humidity environment. An object of the present invention is to provide an image forming method, a process cartridge, and a developing unit using a non-magnetic one-component toner that prevents occurrence of problems such as adhesion, fixation, and density reduction, and has good solid followability and cleaning properties.

A toner having toner particles obtained by agglomerating and combining a plurality of polymer fine particles dispersed in an aqueous medium, the toner having a volume average diameter of 4 to 10 μm,
The shape factor SF-1 is 115 to 140,
The average circularity is 0.950-0.990,
The BET specific surface area is 1.50 to 10.0 m ² / g,
The toner particles contain at least a hydrophobized silica fine powder and an inorganic fine powder charged with a polarity opposite to that of the hydrophobized silica fine powder, and the total content of the silica fine powder is 1.0% by mass. A non-magnetic one-component toner having a content of inorganic fine powder of not less than 8.0% by mass and having a polarity opposite to that of the silica fine powder of not less than 0.02% by mass and not more than 5.00% by mass About.

  The toner of the present invention was hydrophobized by controlling the shape factor, average circularity, and BET specific surface area of the toner in a non-magnetic one-component toner, an image forming method using the toner, a process cartridge, and a developing unit. By incorporating silica, and inorganic fine powder charged to the opposite polarity to the silica, particularly the reverse polarity chargeable inorganic fine powder containing a predetermined metal, the chargeability of the toner, the fluidity, and the binding force between the toner and silica can be improved. Control and prevent problems such as fogging, blurring, filming, fusing and fixing of toner to the developing roller and toner layer regulating member, and decrease in density even in long-term use under high temperature and high humidity conditions. Non-magnetic one-component toner having solid followability, cleaning properties, and excellent fixability at low temperature, and an image forming method and a pro It is a scan cartridge.

  As a result of intensive studies by the present inventors, the image forming method by contact development using a non-magnetic one-component toner has excellent fixability at low temperature, and for long-term use in a high temperature and high humidity environment. In order to solve the problem of preventing the occurrence of problems such as fogging, blurring, toner fusing and fixing to the blade and developer carrier surface due to toner deterioration, filming, density reduction, and solid followability And controlling the shape factor, average circularity, specific surface area, and aggregation degree of the toner used in the toner having toner particles obtained by agglomerating and combining a plurality of polymer fine particles dispersed in an aqueous medium, A specified metal that is charged with a polarity opposite to that of the silica fine powder when a two-component tribo is measured using silica and ferrite carrier having a hydrophobized size. Properly contain metal ions, the flowability of the toner by containing the inorganic fine powder, it is possible to control and charging property has been led to completion of the present invention found that it is important. Details will be described below.

  Regarding the particle size of the toner, it is necessary to reduce the particle size in order to obtain an image having high resolution and high definition. Therefore, the weight average diameter of the toner needs to be at least 10 μm or less. However, if the weight average diameter is less than 4 μm, it is not desirable because it is easy to slip through, and it is difficult to regulate by the regulating member.

  Concerning the toner shape factor SF-1, the toner is uniformly charged, the inorganic and organic fine particles added to the toner to improve the chargeability and fluidity of the toner, and the like uniformly adhere to the toner surface; In order to obtain a high-quality image, the toner shape factor SF-1 is desirably 140 or less. However, if the shape factor SF-1 is 115 or less, it is easy to slip through, so that it is difficult to control by the restricting member.

  Further, the shape factor SF-1 is preferably 120 or more and 140 or less, and more preferably 125 or more and 140 or less.

  Regarding the circularity of the toner, it is desirable that the average circularity of the toner is 0.950 or more in order to uniformly charge the toner, obtain a fluidity of a certain level or more, and obtain a high-quality image. However, if the average circularity is 0.990 or more, there are few irregularities on the surface, and it is easy to slip through, so it is difficult to control by the restricting member, and also in terms of cleaning, it is easy to slip through the cleaning member and easily cause poor cleaning. Not desirable. More desirably, when the average circularity of the toner is 0.970 or more, a higher quality image can be obtained.

With respect to the specific surface area of the toner calculated by nitrogen adsorption by the BET method, the specific surface area of the toner should be 1.50 m ² / g or more in order to sufficiently charge the toner and to obtain sufficient fluidity. desirable. However, if the specific surface area of the toner is 10.0 m ² / g or more, the fluidity-imparting agent and the charge-imparting agent are easily released from the toner surface. This is undesirable because it causes contamination of the body, latent image carrier, and other charging members, resulting in a problem of deterioration in image quality. More preferably, the specific surface area of the toner is 7.0 or less, more preferably 4.0 or less.

  Regarding the inorganic fine powder contained in the toner, in the toner of the present invention, when the two-component tribo is measured using a hydrophobized silica fine powder and a ferrite carrier, the polarity is opposite to that of the hydrophobized silica fine powder. It is desirable to contain a charged inorganic fine powder, and when the total content of the silica fine powder is 1.0% by mass or more and 8.0% by mass or less and a two-component tribo is measured using a ferrite carrier, the silica The content of the inorganic fine powder charged to a polarity opposite to that of the fine powder is preferably 0.02% by mass or more and 5.00% by mass or less. Further, the silica fine powder preferably has a primary particle size of 30 nm or less and is preferably 1.0% by mass or more, and in particular, the silica fine powder having a primary particle size of 20 nm or less is 1.0% by mass or more. And more desirable. Furthermore, when the two-component tribo is measured using a ferrite carrier, the inorganic fine powder charged with a polarity opposite to that of the silica fine powder has a primary particle size of 100 nm to 400 nm, and further, a predetermined metal or metal ion is added. It is desirable to contain. The total amount of the silica fine powder contained in the toner of the present invention is desirably 1.0% by mass or more and 3.0% by mass or less, and 2.0% by mass or more and 3.0% by mass or less. More desirable. These reasons are shown below.

  An inorganic fine powder that is charged with a polarity opposite to that of the silica fine powder when a two-component tribo is measured using a ferrite carrier on a hydrophobized silica fine powder that plays a role of imparting chargeability and fluidity to the toner. Incorporating the toner together electrostatically increases the binding force between the silica fine powder and the toner, and the silica fine powder is less likely to be detached from the toner even during long-term use, resulting in a decrease in chargeability and fluidity of the toner. In addition, the reversely chargeable inorganic fine powder acts as a microcarrier to improve the charging performance of the silica fine powder, and the toner is sufficiently charged even when used for a long time in a high temperature and high humidity environment. Therefore, it shows excellent performance in fogging and dropping off. In addition, since silica is less likely to be detached from the toner, contamination of the photoreceptor and the like caused by the detached silica fine powder is suppressed, which is desirable. In particular, in the case where the reverse polarity chargeable inorganic fine powder is adhered to the toner surface by a Henschel mixer or the like, it is more desirable because the effect of the microcarrier action is great. In addition, it is desirable to adhere to the toner surface with a Henschel mixer or the like because the adhesion state can be easily adjusted in order to maintain the fluidity and chargeability of the toner for a long period of time in accordance with various materials used at the time of toner preparation. As a result, the amount of the silica fine powder necessary to impart sufficient fluidity and chargeability to the toner is small, and the toner of the present invention has a substantially spherical shape, which is different from the heating unit of the fixing device. The contact is desirable because heat on the toner surface is easily conducted and fixing at a low temperature is possible. In particular, when the content of the silica fine powder is 3.0% by mass or less, the effect of low-temperature fixability is large, and since the content of the silica fine powder is small, the detachment of the silica fine powder is further suppressed. For this reason, the silica fine powder is released from the toner, and the released silica fine powder acts as a reverse microcarrier to inhibit the chargeability of the toner, and other member contamination such as filming occurs. Is also more desirable. However, the silica fine powder shows sufficient fluidity of the toner, the toner is sufficiently charged, does not cause poor supply to the toner carrier, and is uniformly coated on the toner carrier with a regulating member in a thin layer. In order to obtain a high-quality image, it is desirable to contain 1.0% by mass or more, and it is desirable to contain 1.0% by mass or more of those having a primary particle size of 30 nm or less. When the toner is substantially spherical like the toner of the present invention and the silica fine powder is contained in an amount of 1.0% by mass or more, good fluidity can be obtained. It is desirable because stress applied from the developing roller and the regulating member during coating is suppressed, and fusion and fixing to the developing roller and the regulating member are suppressed. Further, when the silica fine powder has a primary particle size of 30 nm or less in an amount of 1% by mass or more, and more desirably, the silica fine powder has a primary particle size of 20 nm or less in an amount of 1% by mass, the toner is easily triboelectrically charged. Therefore, the toner is charged quickly, which is desirable for fogging, blurring and the like.

  Further, it is desirable that the reverse polarity chargeable inorganic fine powder is contained in an amount of 0.02% by mass or more, preferably 0.06% by mass or more, more preferably 0.70% by mass in order to show a sufficient effect. The content of the silica fine powder is desirably 5.00% by mass or less, preferably 3.0% by mass or less, and more preferably 1.0% by mass or less so as not to cancel the charge of the silica fine powder. Further, when the amount of the reverse polarity chargeable inorganic fine powder is more than 5.00% by mass, the amount of the reverse polarity chargeable inorganic fine powder released from the toner surface is large in long-term use, and the influence of the reverse polarity chargeable inorganic fine powder is large. As a result, the toner agglomerates electrostatically, and as a result, the fluidity of the toner is remarkably lowered, resulting in poor supply to the toner carrier, and a uniform coating on the toner carrier with a regulating member. This is not desirable because the image quality deteriorates. When the reverse polarity chargeable inorganic fine powder is 5.00% by mass or less, even if the reverse polarity chargeable inorganic fine powder is liberated from the toner surface in a long-term use, the amount of the reverse polarity chargeable inorganic fine powder is insignificant and inhibits the fluidity of the toner. Rather, it acts as a microcarrier, and as a result, the chargeability of the toner is improved, which is desirable. In the case where the amount of the reverse polarity chargeable inorganic fine powder is 1.00% by mass or less, it is desirable since the effect is further great particularly in terms of the fluidity of the toner. Further, when the silica fine powder is 8.0% by mass or more, even if the reverse polarity chargeable inorganic fine powder is contained, the silica fine powder is easily released from the surface of the toner especially in long-term use. However, it is not desirable because it contaminates the regulating member and the toner carrier, or acts as a reverse microcarrier to inhibit toner charging, resulting in deterioration of fog. In addition, as for the reverse polarity chargeable inorganic fine powder, when using a resin component such as resin particles as the main component as the reverse polarity chargeable fine particles, the environmental dependence is particularly large in a high temperature and high humidity environment. The effect is not sufficient due to softening and a decrease in durability, etc., and the effect is not stable because the chargeability fluctuates significantly in long-term use, and it is often separated from the toner surface. This is undesirable because it contaminates the charging member. Therefore, it is desirable to use inorganic fine powder. Further, the reverse polarity chargeable inorganic fine powder contains a metal belonging to the group IB, IIA, IIB, IIIA, particularly any one of Zn, Mg, Ba, Al or zinc ions, magnesium ions, barium ions, and aluminum ions. In this case, the tendency of hindering the chargeability of the silica fine powder contained in the toner is small, and it is desirable in terms of fogging and the like because the reverse polarity charging performance can be satisfactorily exhibited. In addition, it has been found that since the tendency to electrostatically aggregate with the silica fine powder when contained in the toner is moderate, as a result, it is contained almost uniformly in the toner, so that the effect is remarkably exhibited. Further, it is preferable to use the reverse polarity chargeable inorganic fine powder containing the above-mentioned predetermined metal not only from the viewpoint of electrostatic adhesion but also from the characteristics such as the hardness of the inorganic fine powder. It is desirable. When the silica fine powder and the reverse polarity chargeable inorganic fine powder are contained under the above conditions, the toner has a shape factor SF-1 of 115 to 140 and an average circularity of 0.950 or more. Since the toner is 0.990 or less, the shape of the toner is substantially spherical, and the surface shape of the toner is moderately uneven, so that the fluidity of the toner can be sufficiently secured, and further in a high temperature and high humidity environment. In the long-term use of the toner, since the toner is not in a packing state close to close-packing in the toner container even after being left in a high-temperature and high-humidity environment for a long period of time, there is an appropriate gap, so the toner toner Since the toner is supplied quickly and uniformly at the start of supply to the carrier, there is a problem in the supply of toner to the toner carrier, or the regulation failure due to the regulation member due to being supplied as packed Without fog, for good results in terms such as solid follow-up property can be obtained desirable. At this time, since the reverse polarity chargeable inorganic fine powder exists also in the vicinity of the concave portion of the toner, the silica fine powder is bonded with a strength of a certain level or more and is contained in the vicinity of the concave portion even in long-term use. The reverse-polarity chargeable inorganic fine powder and the silica fine powder are not easily stressed, and the toner of the present invention has stable chargeability and fluidity for a long period of time. This is desirable because of its excellent characteristics. In particular, when the developing method is non-magnetic one-component contact development, the toner of the present invention is desirable because even if the chargeability of the toner is insufficient, the toner tends to adhere to the electrostatic latent image carrier and fog and blurring are likely to occur. In addition, the toner of the present invention is desirable because it maintains stable fluidity for a long period of time with respect to problems such as toner fusing and fixing to the toner regulating member. In addition, in an image forming method using a toner auxiliary charging member, particularly an auxiliary charging roller, the toner charge distribution on the toner carrier is made uniform, and the toner layer on the toner carrier is also uniform, so that a stable and uniform image is obtained. It is more desirable because the concentration can be obtained. The primary particle diameter of the reverse polarity chargeable fine powder can be used if it is 500 nm or less, but if it is 100 nm or more and 400 nm or less, the effect is large and more desirable. At this time, if SF-1 is less than 115 or exceeds 140, the stress applied to the toner is applied almost uniformly over the entire surface, so that almost all of the inorganic fine powder is released or buried, or locally. The toner itself is damaged due to excessive stress, which is not desirable in terms of chargeability and fluidity of the toner.

  In particular, when the reverse polarity chargeable inorganic fine powder is a hydrotalcite and contains magnesium or magnesium ion and zinc or zinc ion, the inorganic fine powder has a higher binding strength with the toner in terms of charging characteristics and hardness. It is further desirable because it becomes suitable.

  In the toner of the present invention, the silica fine powder and the reverse polarity chargeable inorganic fine powder that have been hydrophobized are contained in the toner, and a mixed liquid obtained by mixing various dispersions such as a resin particle dispersion obtained by emulsion polymerization. In the step of forming agglomerated particles using a flocculant or the like, and the subsequent fusing step of fusing by heating or the like, a method of appropriately adding the inorganic fine powder may be used, but the effect of the present invention will be more manifested. As a manufacturing method for this, the following methods can be given. In other words, it is desirable that the inorganic fine powder is externally added to the toner using a Henschel mixer or the like because it is more effective if it is present on the toner surface. Furthermore, the effect is more stable when the inorganic fine powder is uniformly distributed on the toner surface, and the effect itself is greater. Therefore, the toner base particles and the inorganic fine powder are divided into a plurality of parts and charged alternately into a Henschel mixer. It is desirable. Furthermore, due to the mechanism of the effect of the present invention, the inorganic fine powder and the toner base particles are slightly charged by being stirred at a low speed for a short time after being put into a Henschel mixer, so that the opposite polarity inorganic fine powders are weakly charged. The negatively chargeable and positively chargeable materials attract each other, and the toner base particles are also slightly charged, so the toner base particles and each inorganic fine powder attract each other electrostatically, and are allowed to stand for more than a certain time. Two kinds of inorganic fine powders having uniformly opposite charging properties are present on the surface of the toner base particles, and it is desirable that the toner base particles adhere to and adhere easily to the toner base surface when left in that state. At this time, if the negative charge and the positive charge are too charged, silica and the opposite polarity inorganic fine powder are aggregated by electrostatic aggregation, and it is difficult to uniformly adhere to the toner surface by subsequent external addition. Become. Furthermore, even after being left to stand, it is made to flow by releasing the toner base particles in a packing-like state by first stirring at a low speed for a short time, and then externally added with uniform external addition strength in the subsequent external addition. It is desirable to do so. Furthermore, the toner base particles, silica, and the opposite-polarity inorganic fine powder are weakly charged even during the second low-speed agitation, so that the toner base particles and the two inorganic fine powders are uniformly distributed by electrostatic bonding. This is desirable because it is maintained during subsequent external addition at high speed.

  In addition, when the silica fine powder is surface-treated with silicone oil and subjected to a hydrophobic treatment, when the inorganic fine powder is externally added to the toner base particles, the familiarity of the toner base and the reversely chargeable inorganic fine powder is good. Since it tends to be uniformly distributed on the toner surface, a higher quality image can be obtained when used in a high-temperature and high-humidity environment, and contamination of the regulating member and the photoreceptor is suppressed, which is further desirable.

  The weight average particle diameter of the toner can be measured by various methods such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Corp.). In the present invention, Coulter Counter TA-II type (Coulter Corp.) is used. The interface for outputting the number distribution and the volume distribution (manufactured by Nikka) and a personal computer are connected, and 1% NaCl aqueous solution is prepared using first grade sodium chloride as the electrolyte. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample was suspended was dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toners of 2 μm or more were measured using the Coulter Counter TA-II with a 100 μm aperture as an aperture. Volume distribution and number distribution were calculated. Then, a volume-based weight average particle diameter (D4: the median value of each channel is a representative value of the channel) obtained from the volume distribution according to the present invention was obtained.

  SF-1 indicating the shape factor used in the present invention is a sample of 100 toner images randomly using FE-SEM (S-800) manufactured by Hitachi, Ltd., and the image information is manufactured by Nireco through an interface. Introduced into the image analysis apparatus (Luxex 3) and analyzed, and the value obtained from the following equation was defined as the shape factor SF-1.

Shape factor (SF-1) = {(MXLNG) ² / AREA} × (π / 4) × 100
[In the formula, MXLNG indicates the absolute maximum length, and AREA indicates the projected area of the toner. ]
The toner shape factor SF-1 indicates the degree of sphericity. When the toner shape factor SF-1 is smaller than 115, it gradually indicates a true sphere, and 100 indicates a true sphere. Moreover, when larger than 140, it becomes an indefinite flat particle gradually from a spherical shape.

  The average circularity is measured by the equivalent-circle-diameter-circularity scattergram based on the number of toners measured by the flow type particle image measuring apparatus. In the present invention, “FPIA-1000” (Toa Medical Electronics Co., Ltd.) is used. The measurement was performed using the following formula.

Circularity = circumference with the same particle projected area as the particle image / perimeter of the projected particle image Average circularity = total circularity of each particle / total number of particles Here, "particle projected area" is binarized The area of the toner particle image formed.

  As a specific measurement method, 10 ml of ion-exchanged water from which impure solids and the like are previously removed is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, and then further measurement is performed. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “UH-50 type” (manufactured by SMT Co., Ltd.) equipped with a 5Φ titanium alloy chip as a vibrator is subjected to a dispersion treatment for 5 minutes, and a measurement dispersion liquid and To do. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more.

  To measure the shape of the toner, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 / μl, and 1000 or more toner particles are obtained. measure. After the measurement, the circularity of the toner is obtained using this data.

  This value represents how close the toner is to a sphere, 1.0 is true sphere, and a value smaller than that represents gradually becoming irregular irregular shape.

  The measurement of the BET specific surface area is performed using a known apparatus such as a degassing apparatus Bacuprep 061 (manufactured by Micromesotic), a BET measuring apparatus Gemini 2375 (manufactured by Micromesotic). The BET specific surface area in the present invention is a value of a multipoint BET specific surface area. Specifically, the procedure is as follows.

  After measuring the weight of the empty sample cell, the sample to be measured is filled so as to fall between 0.01 and 0.002 g. Further, the sample cell filled with the sample is set in the degassing apparatus, and degassing is performed at room temperature for 3 hours. After completion of degassing, the mass of the entire sample cell is measured, and the accurate mass of the sample is calculated from the difference from the empty sample cell. Next, empty sample cells are set in the balance port and analysis port of the BET measuring apparatus. Set a dewar with liquid nitrogen in place and measure P0 using the saturated vapor pressure (P0) measurement command. After the P0 measurement is completed, the sample cell prepared for degassing is set in the analysis port, the sample mass and P0 are input, and the measurement is started by the BET measurement command. After that, the BET specific surface area is automatically calculated.

  The primary particle size of the inorganic fine powder is measured as follows.

  The primary particle size is determined by observing the alumina fine powder with a transmission electron microscope, measuring 100 particle sizes of 0.001 μm or more in the visual field to obtain the average particle size, and the dispersed particle size on the toner is measured with a scanning electron microscope. Observe and qualify 100 alumina fine powders in the visual field with XMA, and measure the particle diameter to obtain the average particle diameter.

  Regarding the degree of aggregation, in order to sufficiently charge the toner and to obtain sufficient fluidity, the toner can be used if the degree of aggregation is 70.0 or less, preferably 50.0 or less, more preferably The toner preferably has a toner aggregation degree of 25.0 or less. However, if the toner cohesion is 5.0 or less, it is easy to slip between the developing roller and the toner restricting member, so that the restriction by the restricting member is difficult, and the cleaning member is also easily slipped through in terms of cleaning. It is not desirable because it tends to become.

  The degree of aggregation of the toner in the present invention was measured as follows.

  As a measuring apparatus, a powder tester (manufactured by Hosokawa Micron Co., Ltd.) having a digital vibrometer (manufactured by DEGITAL VIBLATIONMETER MODEL 1332 SHOWA SOKKI CORPORATION) was used.

  As a measurement method, set 390 mesh, 200 mesh, and 100 mesh sieves on the shaking table in the order of narrow opening, ie, 390 mesh, 200 mesh, and 100 mesh sieves so that the 100 mesh sieve is at the top. did.

  An accurately weighed sample of 5 g was added to the set 100 mesh sieve, the displacement value of the digital vibrometer was adjusted to 0.60 mm (peak-to-peak), and vibration was applied for 15 seconds. Thereafter, the mass of the sample remaining on each sieve was measured to obtain the degree of aggregation based on the following formula.

  The measurement samples at that time were each previously left for 24 hours in an environment of 23 ° C. and 60% RH, and the measurement was performed in an environment of 23 ° C. and 60% RH.

Aggregation degree (%) = (residual sample mass on 100 mesh sieve / 5 g) × 100
+ (Residual sample mass on 200 mesh sieve / 5 g) × 60
+ (Residual sample mass on 390 mesh sieve / 5 g) × 20
The toner of the present invention desirably has a melt index (MI) in the range of 0.5 to 40.0, preferably in the range of 3.0 to 30.0.

  This is because the MI of the toner is 0.5 or more, and the toner is not too hard so that the negatively chargeable silica fine powder and the positively chargeable inorganic fine powder can be easily combined with the toner. Further, it is more preferable in that it is advantageous in fixing at a low temperature. Also, by setting it to 40 or less, since the toner is soft, the deterioration rate of the toner at the time of tribocharging during a long-term use is reduced, so that the negatively chargeable silica fine powder and the positively chargeable inorganic fine powder are maintained in the bond with the toner. More preferable in terms.

The melt index here is measured by the manual cutting method under the following measurement conditions using an apparatus described in JIS K7210, a flow test method for thermoplastics of Japanese Industrial Standards. At this time, the measured value is converted into a 10-minute value.
Measurement temperature: 135 ° C
Load: 2.16kg (21.2N)
Sample filling amount: 5-10 g
Furthermore, the toner prepared in particular can be used if the toner has a saturated triboelectric charge amount of −20 mC / kg or more at 23 ° C. and 60% RH, but it is −50 mC / kg or more and −75 mC / kg or less. In some cases, the effect is more prominent, which is further desirable.

  The reason for this is that by setting the saturated triboelectric charge amount to -20 mC / kg or more, particularly -50 mC / kg, the triboelectric charge amount is such that the influence of temperature and humidity can be further reduced, and the image density due to environmental fluctuations decreases. Is more preferable. By setting the saturated triboelectric charge amount to less than -75 μC / g, it is more preferable because generation of blotches and the like caused by the excessive triboelectric charge amount is suppressed and a good image can be obtained.

  The saturated triboelectric charge amount of the toner and the chargeability of the silica fine powder, the reverse polarity chargeable inorganic fine powder, and the other inorganic fine powder used in the present invention were measured by the following methods. FIG. 1 is an explanatory diagram of a triboelectric charge measuring device. F233-1535 (manufactured by Powdertech) was used as a carrier in an environment of 23 ° C. and 60% RH, and a mixture obtained by adding 0.4 g of developer to 19.6 g of carrier was placed in a 50 ml polyethylene bottle and hand-washed 150 times. Shake with. Next, 0.4 to 0.5 g of the mixture is put into a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is formed. The total mass of the measurement container 2 at this time is weighed and is defined as W1g. Next, in the suction machine (at least the insulator is in contact with the measurement container 2), the pressure of the vacuum gauge 5 is set to 250 mmAq by suction from the suction port 7 and adjusting the air volume control valve 6. In this state, suction is performed for 1 minute to remove the developer by suction. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (μF). Moreover, the mass of the whole measuring machine after suction is weighed and is defined as W2 (g). The triboelectric charge amount (μC / g) of this developer is calculated as follows:

Frictional charge (μC / g) = CV / (W1-W2)
Here, when the triboelectric charge amount of the silica fine powder used in the present invention is a negative value, the triboelectric charge amount of the reverse polarity chargeable inorganic fine powder is a positive value, and the triboelectric charge of the silica fine powder is positive. When the amount is a positive value, the triboelectric charge amount of the reverse polarity chargeable inorganic fine powder is a negative value. That is, when the silica fine powder is negatively chargeable, the reverse polarity chargeable inorganic fine powder becomes positively chargeable.

  Next, a toner manufacturing method will be described.

  The toner of the non-magnetic one-component developer of the present invention is added with, for example, a pH adjuster, a flocculant, a stabilizer and the like in an aqueous dispersion containing polymer fine particles, colorant fine particles, and release agent fine particles as follows. A method of aggregating a plurality of the fine particles and thermally fusing the aggregated particles can be suitably used. This is because it is easy to achieve both control of the surface shape of the toner particles and control of the true spherical state of the toner. In addition, since the degree of freedom in selecting the material is large, it is easy to adjust the hardness and charging characteristics of the toner.

  In this toner manufacturing method, in the aggregation step, resin particles, colorant particles, or release agent fine particles that are uniformly dispersed in the mixed solution are aggregated to form aggregated particles. In the thermal fusing step, the resin in the aggregated particles is melted and fused to form toner particles.

  Hereinafter, the method for producing the toner of the present invention will be described in detail.

  The resin particle dispersion is obtained by dispersing at least resin particles in a dispersant. Examples of the resin include thermoplastic binder resins. Specifically, homopolymers or copolymers (styrene-based resins) of styrenes such as styrene, parachlorostyrene, and α-methylstyrene; acrylic Methyl acid, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, methacrylic acid 2 -Homopolymers or copolymers of vinyl group esters such as ethylhexyl (vinyl resins); Homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile (vinyl resins); A single vinyl ether such as ether or vinyl isobutyl ether Polymer or copolymer (vinyl resin); homopolymer or copolymer of vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone (vinyl resin); ethylene, propylene, butadiene, isoprene, etc. Homopolymers or copolymers of olefins (olefin resins); non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, and polyether resins, and these non-vinyl condensation resins And a graft polymer of vinyl monomers. These resins may be used alone or in combination of two or more.

  Among these resins, vinyl resins are particularly preferable. In the case of a vinyl resin, it is advantageous in that a resin particle dispersion can be easily prepared by emulsion polymerization or seed polymerization using an ionic surfactant or the like. Examples of the vinyl monomer include acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, ethylene imine, vinyl pyridine, vinyl amine, and other vinyl polymer acids and vinyl polymer bases. The monomer used as a raw material is mentioned. In the present invention, the resin particles preferably contain the vinyl monomer as a monomer component, and a styrene-acrylic resin with a small change in toner charge amount in a high temperature and high humidity or low temperature and low humidity environment is preferable. In the present invention, among these vinyl monomers, vinyl polymer acids are more preferable from the viewpoint of ease of formation reaction of vinyl resins, and specifically, acrylic acid, methacrylic acid, maleic acid, cinnamon. A dissociable vinyl monomer having a carboxyl group such as an acid or fumaric acid as a dissociating group is particularly preferred from the viewpoint of controlling the degree of polymerization and the glass transition point. Furthermore, at this time, in order to adjust the molecular weight, a chain transfer agent, a crosslinking agent, or the like can be used in combination.

  For example, the chain transfer agent is not particularly limited, and for example, mercaptans such as octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, halogen compounds such as carbon tetrabromide, disulfides and the like are used.

  Further, as the crosslinking agent, those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate can be used. In particular, divinylbenzene is preferably used.

  In the present invention, the radical polymerization initiator can be appropriately used as long as it is water-soluble. For example, persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds [4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis (2-amidinopropane) salts, etc.], Examples thereof include peroxide compounds such as hydrogen oxide and benzoyl peroxide.

  Furthermore, the radical polymerization initiator can be combined with a reducing agent as necessary to form a redox initiator. By using a redox initiator, the polymerization activity is increased, the polymerization temperature can be lowered, and the polymerization time can be further shortened.

  The polymerization temperature may be any temperature as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator. For example, a range of 50 ° C. to 80 ° C. is used. Moreover, it is also possible to superpose | polymerize at room temperature or the temperature close | similar to it by using the polymerization initiator of normal temperature start, for example, the combination of hydrogen peroxide-reducing agent (ascorbic acid etc.).

  Surfactants that can be used for polymerization include sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8- Sodium naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfonate Sulfate ester salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate) , Potassium stearate, calcium oleate), and the like.

  As an average particle diameter of the said resin particle, it is 1 micrometer or less normally, and it is preferable that it is 0.01-1 micrometer. When the average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner is broadened or free particles are generated, which tends to cause a decrease in performance and reliability. On the other hand, when the average particle size is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toners is improved, and the variation in performance and reliability is advantageous.

  The colorant particle dispersion is obtained by dispersing at least colorant particles in a dispersant. Examples of the colorant include phthalocyanine pigments, monoazo pigments, bisazo pigments, magnetic powder, and quinacridone pigments. Specific examples thereof include, for example, carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brillianthamine 3B, brillianthamine. 6B, DuPont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, dioxane Various dyes such as gin, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole, and xanthene; . These colorants may be used alone or in combination of two or more.

  The average particle diameter of the colorant particles is preferably 0.5 μm or less, and more preferably 0.2 μm or less. If the average particle diameter exceeds 0.5 μm, irregular reflection of visible light cannot be prevented, and if coarse particles are present, coloring power, color reproducibility, and OHP permeability are adversely affected, and agglomerated particles described below. In the forming step, the resin particles and the colorant particles do not aggregate, or even if they aggregate, they may be detached at the time of fusion, which is not preferable in that the quality of the obtained toner may deteriorate. On the other hand, when the average particle size is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toner is good, and the variation in performance and reliability is advantageous. .

  The release agent particle dispersion is obtained by dispersing at least release agent particles in a dispersant.

  As the mold release agent, those having a melting point of 150 ° C. or less are used. For example, low molecular weight polyolefins such as polyethylene; silicones having a melting point (softening point) upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide; ester waxes such as stearyl stearate Kinds: Plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, ester Examples thereof include particles such as minerals such as waxes, petroleum-based waxes, and modified products thereof.

  The average particle size of the release agent particles is preferably 2.0 μm or less, and more preferably 1.0 μm or less. When the average particle diameter exceeds 2.0 μm, the wax content tends to occur between the toners, which adversely affects the stability of the image over a long period of time. On the other hand, when the average particle size is within the above range, uneven distribution between toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are reduced.

  There is no restriction | limiting in particular as a combination of the said colorant particle, the said resin particle, and the said mold release agent particle | grains, According to the objective, it can select suitably.

  More preferably used waxes include linear alkyl alcohols having 15 to 100 carbon atoms, linear fatty acids, linear acid amides, linear esters, and montan derivatives. Further, those obtained by removing impurities such as liquid fatty acid from these waxes in advance are also preferred.

  Furthermore, particularly preferably used waxes are ester waxes, and ester waxes belonging to the following formulas (I) to (V) are particularly preferable.

（式中、ａ及びｂは０〜４の整数であり、ａ＋ｂは４である。Ｒ₁及びＲ₂は炭素数が１〜４０の有機基である。ｍ及びｎは０〜４０の整数であり、ｍとｎは同時に０になることはない。）

(In the formula, a and b are integers of 0 to 4 and a + b is 4. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms. M and n are integers of 0 to 40. Yes, m and n are not 0 at the same time.)

（式中、ａ及びｂは０〜３の整数であり、ａ＋ｂは１〜３である。Ｒ₁及びＲ₂は炭素数が１〜４０の有機基である。Ｒ₃は水素原子または炭素数が１以上の有機基である。ｋは１〜３の整数であり、ａ＋ｂ＋ｋ＝４である。ｍ及びｎは０〜４０の整数であり、ｍとｎが同時に０になることはない。）

(In the formula, a and b are integers of 0 to 3, a + b is 1 to _3. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms. R ₃ is a hydrogen atom or a carbon number. Is an organic group of 1 or more, k is an integer of 1 to 3, and a + b + k = 4, m and n are integers of 0 to 40, and m and n are not 0 at the same time.)

（式中、Ｒ₁及びＲ₃は炭素数１〜４０の有機基であり、Ｒ₁とＲ₃は同じものであっても異なっていても良い。Ｒ₂は炭素数１〜４０の有機基を示す。）

(In the formula, R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may be the same or different. R ₂ is an organic group having 1 to 40 carbon atoms. Is shown.)

（式中、Ｒ₁及びＲ₃は炭素数１〜４０の有機基であり、Ｒ₁とＲ₃は同じものであってもなくてもよい。Ｒ₂は炭素数１〜４０の有機基を示す。）

(In the formula, R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may or may not be the same. R ₂ represents an organic group having 1 to 40 carbon atoms. Show.)

（式中、ａは０〜４の整数であり、ｂは１〜４の整数であり、ａ＋ｂは４である。Ｒ₁は炭素数１〜４０の有機基である。ｍ及びｎは０〜４０の整数であり、ｍとｎが同時に０になることはない）
本発明に使用される離型剤は、ＤＳＣ吸熱曲線において、４０〜１２０℃（さらに好ましくは４５〜８５℃）の領域に吸熱メインピークを有することがより好ましい。さらに、吸熱メインピークは、半値幅が１０℃以内（より好ましくは５℃以内）であるシャープメルト性の低軟化点物質が好ましい。

(In the formula, a is an integer of 0 to 4, b is an integer of 1 to 4, and a + b is 4. R ₁ is an organic group having 1 to 40 carbon atoms. (It is an integer of 40, and m and n cannot be 0 at the same time.)
The release agent used in the present invention more preferably has an endothermic main peak in the region of 40 to 120 ° C. (more preferably 45 to 85 ° C.) in the DSC endothermic curve. Further, the endothermic main peak is preferably a sharp-melting low softening point material having a half-value width within 10 ° C. (more preferably within 5 ° C.).

  The amount of the wax added to the toner particles of the present invention is usually 0.1 to 40% by mass, but more preferably 1 to 20% by mass. When the amount is less than 1% by mass, sufficient peelability from the fixing roller cannot be obtained, and when the amount is 20% by mass or more, filming on the photosensitive member or the charge imparting member becomes remarkable.

  In addition to the resin particle dispersion, the colorant particle dispersion, and the release agent dispersion, a particle dispersion obtained by dispersing appropriately selected particles in a dispersant may be further mixed.

  The particles contained in the particle dispersion are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include internal additive particles, charge control agent particles, inorganic particles, and abrasive particles. In the present invention, these particles may be dispersed in the resin particle dispersion or the colorant particle dispersion.

  Examples of the charge control agent particles include particles such as quaternary ammonium salt compounds, nigrosine compounds, compounds composed of complexes of aluminum, iron, chromium, zinc, zirconium, and the like. The charge control agent particles in the present invention are preferably made of materials that are difficult to dissolve in water from the viewpoints of controlling ionic strength that affects the stability during aggregation and fusion and reusing wastewater.

  As an average particle diameter of each above-mentioned particle | grain, it is 1 micrometer or less normally, and it is preferable that it is 0.01-1 micrometer. When the average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner is broadened or free particles are generated, which tends to cause a decrease in performance and reliability. On the other hand, when the average particle size is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toners is improved, and the variation in performance and reliability is advantageous.

  Examples of the dispersant contained in the resin particle dispersion, the colorant particle dispersion, the release agent dispersion, the particle dispersion, and the like include an aqueous medium containing a polar surfactant. Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together. The content of the polar surfactant in the dispersant having the polarity cannot be generally defined and can be appropriately selected according to the purpose.

  Examples of the polar surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type Is mentioned. Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like. Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. These may be used individually by 1 type and may use 2 or more types together.

  In the present invention, these polar surfactants and nonpolar surfactants can be used in combination. Examples of the nonpolar surfactant include nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols.

  As content of the said resin particle in the said resin particle dispersion liquid, it is 5-60 mass% normally, Preferably it is 10-40 mass%. Further, the content of the resin particles in the aggregated particle dispersion when the aggregated particles are formed may be 50% by mass or less, and is preferably about 2 to 40% by mass.

  The content of the colorant particles and the like is about 1 to 10% by mass and preferably about 2 to 6% by mass in the aggregated particle dispersion when the aggregated particles are formed.

  The content of the release agent particles and the like is about 0.5 to 20% by mass in the aggregated particle dispersion when the aggregated particles are formed, and preferably about 1 to 10% by mass. When the content is larger than 5% by mass, the particle size distribution is widened and the characteristics may be deteriorated. In this case, for example, when the resin particles are produced, the above problem can be solved by performing seed polymerization on the release agent.

  The content of each particle such as the additive particles is about 0.01 to 5% by mass and about 0.5 to 2% by mass in the aggregated particle dispersion when the aggregated particles are formed. preferable. If the content is outside the above range, the effect of dispersing the release agent particles or the like may be insufficient, the particle size distribution may be widened, and the characteristics may be deteriorated.

  Furthermore, in order to control the chargeability of the toner obtained, the charge control particles and the resin particles may be added after the aggregated particles are formed.

  The resin particle dispersion is prepared, for example, as follows. That is, the resin in the resin particles is a homopolymer or copolymer (vinyl resin) of a vinyl monomer such as the ester having a vinyl group, the vinyl nitrile, the vinyl ether, or the vinyl ketone. In some cases, a vinyl monomer homopolymer or copolymer (vinyl resin) resin is obtained by emulsion polymerization or seed polymerization of the vinyl monomer in an ionic surfactant. A dispersion is prepared by dispersing particles in an ionic surfactant. When the resin in the resin particles is a resin other than a homopolymer or copolymer of the vinyl monomer, the resin can be dissolved in an oily solvent having a relatively low solubility in water. The resin is dissolved in the oily solvent, and the solution is finely dispersed in water together with an ionic surfactant and a polymer electrolyte using a disperser such as a homogenizer, and then heated or decompressed to remove the oily solvent. By transpiration, a dispersion liquid in which resin particles made of resin other than vinyl resin are dispersed in an ionic surfactant is prepared.

  The dispersion means is not particularly limited, and examples thereof include known dispersion apparatuses such as a rotary shear type homogenizer and a ball mill having a medium, a sand mill, and a dyno mill.

  The colorant particle dispersion liquid, the release agent dispersion liquid, the particle dispersion liquid, and the like are prepared, for example, by adding particles such as the colorant particles to a dispersant and dispersing the particles using the dispersion means. Is done.

(Aggregation process)
In the aggregated particle formation, aggregated particles are formed in the mixed solution to prepare an aggregated particle dispersion. The agglomerated particles can be formed in the mixed solution by adding, for example, a pH adjusting agent, a flocculant, and a stabilizer to the mixed solution and mixing them, and appropriately adding temperature, mechanical power and the like.

  Examples of the pH adjuster include alkalis such as ammonia and sodium hydroxide, and acids such as nitric acid and citric acid. Examples of the flocculant include monovalent metal salts such as sodium and potassium; divalent metal salts such as calcium and magnesium; trivalent metal salts such as iron and aluminum; and alcohols such as methanol, ethanol and propanol. It is done.

  Examples of the stabilizer mainly include the polar surfactant itself or an aqueous medium containing the same. For example, when the polar surfactant contained in the aqueous dispersion is anionic, a cationic one can be selected as the stabilizer.

  The addition / mixing of the flocculant and the like is preferably performed at a temperature below the glass transition point of the resin contained in the mixed solution. When the mixing is performed under this temperature condition, aggregation proceeds in a stable state. The mixing can be performed using, for example, a known mixing device, a homogenizer, a mixer and the like.

  The average particle size of the aggregated particles formed here is not particularly limited, but is usually controlled to be about the same as the average particle size of the toner to be obtained. The control can be easily performed, for example, by appropriately setting and changing the temperature and the stirring and mixing conditions. Through the above-described aggregated particle forming step, aggregated particles having an average particle size substantially the same as the average particle size of the toner are formed, and an aggregated particle dispersion liquid in which the aggregated particles are dispersed is prepared.

(Heat fusion process)
The thermal fusion process is a process in which the aggregated particles are heated and fused. Before entering the fusing step, the pH adjusting agent, the polar surfactant, the nonpolar surfactant, and the like can be appropriately added in order to prevent fusing between toner particles.

  The heating temperature may be from the glass transition temperature of the resin contained in the aggregated particles to the decomposition temperature of the resin. Therefore, the temperature of the heating differs depending on the type of resin of the resin particles and the resin fine particles, and cannot be generally defined. However, in general, the glass of resin contained in the aggregated particles or the adhered particles Transition point temperature to 140 ° C. In addition, the said heating can be performed using a publicly known heating apparatus and instrument.

  As the fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low. That is, the fusion time depends on the temperature of the heating and cannot be defined in general, but is generally 30 minutes to 10 hours.

  In the present invention, the toner obtained after the end of the fusing process can be washed, dried, etc. under appropriate conditions. In addition to the negatively chargeable silica fine powder and the positively chargeable inorganic fine powder used in the present invention, the surface of the obtained toner is generally widely known as an external additive as long as it does not have a substantial adverse effect. It is possible to use organic or inorganic fine particles. These inorganic particles and resin particles may be added by applying a shearing force in a dry state. These inorganic particles and resin particles function as external additives such as fluidity aids and cleaning aids.

  The inorganic fine powder used in the present invention is preferably hydrophobic, and various coupling agents such as a silane coupling agent and a titanium coupling agent can be used, but the degree of hydrophobicity should be increased with silicone oil. Therefore, moisture adsorption of the inorganic fine powder under high humidity is suppressed, and further, contamination of the regulating member and the charging member is suppressed, so that a high-quality image can be obtained, which is more preferable.

  Examples of the silicone oil include dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chloropheny silicone oil, fluorine-modified silicone oil, and the like. Particularly, a functional group containing an aromatic group such as chlorophenyl silicone oil is used. Although what has is preferable, it is not necessarily limited to the above-mentioned thing.

The silicone oil preferably has a viscosity of 50 to 1000 mm ² / s at a temperature of 25 ° C. If it is less than 50 mm ² / s, part of it is exerted by the application of heat, and the charging characteristics tend to deteriorate. When it exceeds 1000 mm ² / s, handling becomes difficult in terms of processing work. A known technique can be used as a method for treating the silicone oil. For example, silicate fine powder and silicone oil are mixed using a mixer. Silicone oil is sprayed into the silicate fine powder using a sprayer. Or the method of mixing a silicic acid fine powder after dissolving silicone oil in a solvent is mentioned. The processing method is not limited to this.

Examples of the reverse polarity chargeable inorganic fine powder used in the present invention include hydrotalcite compounds whose surface may be treated, ZnO, MgO, Al ₂ O ₃ whose surface may be treated, etc. And metal oxides such as Fe ₃ O ₄ and ferrite powder, surface-treated products of compounds having no reverse polarity chargeability, magnesium hydroxide, barium carbonate and the like. Here, the surface treatment refers to modifying the chargeability of the surface of the external additive with a surface treatment agent known as a charge improving agent such as aminosilane, quaternary ammonium compound, higher fatty acid and metal salt thereof. The preferred primary particle diameter of these external additives is usually 500 nm or less, more preferably 400 nm or less. When the reverse polarity chargeable inorganic fine powder is larger than 500 nm, it is difficult to adhere to the toner surface during external addition, and therefore, contamination in the apparatus becomes severe, which is not preferable.

  Among the above external additives, hydrotalcite compounds are particularly preferable as the reverse polarity chargeable inorganic fine powder according to the present invention. Among these, it is most preferable to contain a powder of a compound represented by the following general formula (II) (compound (2)).

Mg ²⁺ _y1 · M2 ²⁺ _y2 ... Mj ²⁺ _yj · Al ³⁺ _x1 · L2 ³⁺ _x2 ... Lk ³⁺ _xk · (OH) ₂ · (X / n) A ⁿ⁻ · mH ₂ O (II)
(Where 0 <[X = (x1 + x2 +... + Xk)] ≦ 0.5, Y = (y1 + y2 +... + Yj) = 1−X, j and k are integers greater than or equal to 2, M2, M3,. Are different metals selected from the group consisting of Zn, Ca, Ba, Ni, Sr, Cu and Fe, L2, L3... And Lk are different metals selected from the group consisting of B, Ga, Fe, Co and In, A ⁿ⁻ is an n-valent anion, m ≧ 0.)
At this time, it is particularly desirable that y1 ≧ 0.6, and it is more desirable that Zn is contained in the hydrotalcite.

The specific surface area of the hydrotalcite used in the present invention is preferably 3.0~150m ² / g, more preferably 7.0~120m ² / g. An effect of 3.0 m ² / g or more is more effective, and an effect of 150 m ² / g or less is more preferable in terms of uniformity of image density because of good toner fluidity.

  In accordance with the BET method, the specific surface area was determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device Auto Soap 1 (manufactured by Yuasa Ionics) and calculating the specific surface area using the BET multipoint method.

Furthermore, the volume resistance value of the hydrotalcite used in the present invention is preferably 5.0 × 10 ^{6 to} 8.0 × 10 ¹⁵ Ω · cm. If it is 5.0 × 10 ⁶ Ω · cm or more, it is preferable because it has a high ability to retain electric charges in a high humidity environment. Further, it is preferably 8.0 × 10 ¹⁵ Ω · cm or less because the chargeability of the toner can be easily controlled.

  The Mohs hardness of the hydrotalcite used in the present invention is preferably 2.0 to 2.5. When the Mohs hardness is 2.0 or more, it is preferable in terms of stress resistance against the toner regulating member and the like. A Mohs hardness of 2.5 or less is preferable because adhesion to the toner surface is easy.

  The hydrotalcite used in the present invention is preferably hydrophobized with a surface treating agent in order to stabilize the environment. As the surface treatment agent, higher fatty acids, coupling agents, and esters can be used, and higher fatty acids are particularly preferable. Specific examples include palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and lauric acid. Of these, linoleic acid and linolenic acid are particularly preferred.

  The surface treatment of the compound (II) with the surface treatment agent is carried out, for example, when the surface treatment agent is in a liquid state or when dissolved in water, alcohols or the like to form a liquid, the liquid surface treatment agent and the compound ( The powder of II) or an aqueous suspension thereof can be carried out by mechanical mixing under heated or non-heated conditions. For example, when the surface treatment agent is dissolved under heating conditions, it can be carried out by mechanically mixing with the compound (II) under heating dissolution conditions. After sufficient mixing treatment, a surface treated product can be obtained by appropriately selecting and carrying out means such as washing with water, dehydration, drying, pulverization, and classification as required. The content of the surface treatment agent in the surface treatment product of the compound (II) obtainable as described above can be appropriately selected and changed, but is about 0.1 to about 10 weight based on the weight of the compound (II). An amount such as% can be exemplified.

  Compound (II) can be produced by a conventionally known method. For example, the production methods described in Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 47-32198, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 48-29477, Japanese Patent Publication No. 51-29129, etc. It can be manufactured by a similar manufacturing method. Further, the compound (II) obtained by the conventional method is heat-treated, for example, in an autoclave or in an aqueous medium, for example, at a temperature of about 120 to about 250 ° C. and under a condition of about 5 to about 40 hours, and filtered and dried. Etc., compound (II) having a desired BET specific surface area and average secondary particle size can be obtained. The heat treatment may be performed by hydrothermal treatment under pressure until the BET specific surface area and the average secondary particle size condition are satisfied, and the high temperature side is more preferable.

  In the one-component developer of the present invention, other additives such as Teflon (registered trademark) powder, lubricant powder such as polyvinylidene fluoride powder, cerium oxide powder, silicon carbide, and the like within a range that does not substantially adversely affect the developer. Abrasives such as powder and strontium titanate powder; fluidity-imparting agents such as titanium oxide powder; anti-caking agents or conductivity-imparting agents such as carbon black powder and tin oxide powder are used in small amounts as developability improvers. You can also.

In the present invention, as a material that can be used as a developing roller, an elastic roller having a structure in which an elastic layer and preferably a relatively high resistance layer is provided on a conductive substrate is used. As the roller elastic layer, rubber or sponge such as chloroprene rubber, isoprene rubber, EPDM rubber, polyurethane rubber, epoxy rubber, butyl rubber, silicone rubber, styrene-butadiene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester thermoplastic elastomer The conductive layer has a volume resistivity of 10 ⁹ Ωcm or less, and preferably 10 ³ Ωcm or more, for example, a thermoplastic elastomer such as ethylene-vinyl acetate thermoplastic elastomer.

  Examples of means for controlling the conductivity include a method of dispersing conductive particles such as carbon, aluminum, nickel, and titanium oxide, and a method of using ionic conductivity by containing a quaternary ammonium salt, lithium perchlorate, or the like. .

  As a relatively high resistance layer, for example, a fluororesin such as tetrafluoroethylene perfluoroalkyl vinyl ether copolymer, polyvinylidene fluoride, a silicone resin such as methyl silicone, methyl phenyl silicone, and silicone acrylic, nylon-6, Polyamide resins such as nylon-12, nylon-46 and aramids, polyester resins such as PET, polyolefin resins such as PE and PP, epoxy resins, vinyl chloride resins, polyurethane resins, polycarbonate resins, melamine Acrylic resins such as styrene-based resins, styrene-based resins, and polymethacrylates, polyacetal-based resins, vinyl acetate-based resins, phenol-based resins, and the like can be used after appropriately adjusting the resistance.

  The developing roller used in the present invention has an Asker C hardness of 30 ° or more and 60 ° or less, and a developing roller having a surface roughness Rz (JIS) of 3 μm or more and 10 μm or less is not significantly stressed on the toner. In addition, it is desirable because a sufficient image density can be obtained without causing poor regulation.

  Further, a bias may be applied to the charged toner that is regulated by the developing roller and the toner layer regulating member and further in contact with the toner carrying member. This not only increases the charging of the toner but also makes it uniform, which is desirable because it improves the image quality including fogging and blurring.

As the auxiliary charging roller, a rubber or sponge material appropriately adjusted in resistance, such as chloroprene rubber, isoprene rubber, EPDM rubber, polyurethane rubber, epoxy rubber, butyl rubber, and silicone rubber, is preferably used. The rate is 10 ⁹ Ωcm or less, preferably 10 ⁴ Ωcm or more.

  The photosensitive layer of the electrophotographic photoreceptor used in the present invention has a single layer or a laminated structure. In the case of a single layer structure, the photosensitive layer contains both a charge generating material that generates carriers and a charge transport material that transports carriers. In the case of a laminated structure, a charge generation layer containing a charge generation material that generates carriers and a charge transport layer containing a charge transport material that transports carriers are stacked to form a photosensitive layer. The surface layer may be formed by either a charge generation layer or a charge transport layer.

  The single-layer photosensitive layer preferably has a thickness of 5 to 100 μm, particularly preferably 10 to 60 μm. Moreover, it is preferable to contain 20-80 mass% of charge generation materials and charge transport materials with respect to the total mass of a layer, and it is preferable that it is 30-70 mass% especially. The single-layer photosensitive layer contains a binder resin in addition to the charge generation material and the charge transport material, and may contain an ultraviolet absorber, an antioxidant, other additives and the like as necessary.

  In the laminated photosensitive layer, the thickness of the charge generation layer is preferably 0.001 to 6 μm, and particularly preferably 0.01 to 2 μm. The content of the charge generating material is preferably 10 to 100% by mass, particularly 40 to 100% by mass, based on the total mass of the layer. The charge generation layer may be composed of only a charge generation material. In other cases, the charge generation layer may contain the binder resin or the like. The thickness of the charge transport layer is preferably 5 to 100 μm, and particularly preferably 5 to 19 μm. The content of the charge transport material is preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass. The charge transport layer contains a binder resin in addition to the charge transport material, and may contain other optional components similar to those described above.

  Examples of charge generating materials used in the present invention include phthalocyanine pigments, polycyclic quinone pigments, azo pigments, perylene pigments, indigo pigments, quinacridone pigments, azulenium salt dyes, squarylium dyes, cyanine dyes, pyrylium dyes, thiopyrylium dyes, xanthene dyes. Quinoneimine dye, triphenylmethane dye, styryl dye, selenium, selenium-tellurium, amorphous silicon, and hardened cadmium.

  Examples of charge transport materials used in the present invention include pyrene compounds, carbazole compounds, hydrazone compounds, N, N-dialkylaniline compounds, diphenylamine compounds, triphenylamine compounds, triphenylmethane compounds, pyrazoline compounds, styryl compounds, and stilbene compounds. Is mentioned.

  As binder resin used for the photosensitive layer, polyester, polyurethane, polyarylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamideimide, polysulfone, polyallyl ether, polyacetal, phenol resin, acrylic resin, silicone resin, Examples thereof include epoxy resins, urea resins, allyl resins, alkyd resins, and butyral resins. Furthermore, reactive epoxy, (meth) acrylic monomers and oligomers can also be used after being mixed and cured.

  In the electrophotographic photoreceptor used in the present invention, a protective layer may be laminated on the photosensitive layer as described above. The thickness of the protective layer is preferably from 0.01 to 20 μm, particularly preferably from 0.1 to 10 μm. The protective layer usually has a structure in which a charge generating material or a charge transporting material, a metal and its oxide, nitride, salt, alloy, and a conductive material such as carbon are dispersed in a binder resin. Examples of the binder resin, charge generating material, and charge transporting material used for the protective layer include the same materials as those used for the photosensitive layer.

  The conductive support used for the electrophotographic photoreceptor used in the present invention is a metal or alloy such as iron, copper, nickel, aluminum, titanium, tin, antimony, indium, lead, zinc, gold and silver, or their Oxides, carbon, conductive resins, etc. can be used. There are cylindrical, belt-like and sheet-like shapes. Moreover, although the said electroconductive material may be shape-processed, you may apply | coat as a coating material or may vapor-deposit. In addition, the electroconductive support body used for this example is a cylindrical thing about 30 mm in diameter as above-mentioned.

  Further, as described above, an undercoat layer may be provided between the conductive support and the photosensitive layer. The undercoat layer is mainly composed of a binder resin, but may contain the conductive material or an acceptor compound. The binder resin that forms the undercoat layer is polyester, polyurethane, polyarylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamideimide, polysulfone, polyallyl ether, polyacetal, phenol resin, acrylic resin, silicone Examples thereof include resins, epoxy resins, urea resins, allyl resins, alkyd resins, and butyral resins.

  Further, as described above, a conductive layer may be provided between the conductive support and the photosensitive layer. When the photoreceptor has both the undercoat layer and the conductive layer, the conductive support, the conductive layer, the undercoat layer, and the photosensitive layer are usually laminated in this order. The conductive layer generally has a configuration in which the conductive material is dispersed in a binder resin similar to that used in the undercoat layer.

  As a method for producing the electrophotographic photosensitive member used in the present invention, a method of laminating an undercoat layer, a photosensitive layer, a protective layer and the like on a conductive support by vapor deposition or coating is usually used. For coating, a bar coater, knife coater, roll coater, attritor, spray, dip coating, electrostatic coating, powder coating and the like are used. In addition, in order to form the undercoat layer, the photosensitive layer, the protective layer, and the like by a coating method, a solution in which each component is dissolved and dispersed in an organic solvent, a dispersion, or the like is applied by the above method. After that, the solvent may be removed by drying or the like. Alternatively, when a reaction-curable binder resin is used, a solution, a dispersion, or the like in which the constituent components of each layer are dissolved and dispersed in the resin raw material component and an appropriate organic solvent that is added as necessary is used as described above. After the coating, for example, the resin raw material may be reacted and cured by heat or light, and the solvent may be removed by drying or the like as necessary.

  It is desirable to have at least a charge generation layer on the conductive substrate of the photoreceptor and a charge transport layer on the charge generation layer, and a layer of 19 μm or less on the charge generation layer. This is because if the layer thickness formed on the charge generation layer is larger than 19 μm, the sensitivity is lowered and the formed film is difficult to be uniform. Moreover, the problem that the residual amount of the solvent used on manufacture tends to increase also arises.

As the photosensitive member contact charging member, in the case of a roller or a blade, a metal such as iron, copper or stainless steel, a carbon dispersion resin, a metal or a metal oxide dispersion resin, or the like is used as a conductive substrate. A plate shape or the like can be used. For example, the elastic roller is composed of a conductive substrate provided with an elastic layer, a conductive layer, and a resistance layer. The roller elastic layer includes chloroprene rubber, isoprene rubber, EPDM rubber, polyurethane rubber, epoxy rubber. , Rubber or sponge such as butyl rubber, styrene-butadiene thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, ethylene-vinyl acetate thermoplastic elastomer, etc. The volume resistivity is 10 ⁷ Ω · cm or less, preferably 10 ⁶ Ω · cm or less. For example, metal vapor deposition film, conductive particle dispersion resin, conductive resin, etc. are used. Specific examples include vapor deposition films of aluminum, indium, nickel, copper, iron, etc., and examples of conductive particle dispersion resin include carbon. In addition, conductive particles such as aluminum, nickel, and titanium oxide are dispersed in a resin such as urethane, polyester, vinyl acetate-vinyl chloride copolymer, and polymethyl methacrylate. Examples of the conductive resin include quaternary ammonium salt-containing polymethyl methacrylate, polyvinyl aniline, polyvinyl pyrrole, polydiacetylene, and polyethyleneimine. The resistance layer is, for example, a layer having a volume resistivity of 10 ⁶ to 10 ¹² Ω · cm, and a semiconductive resin, a conductive particle-dispersed insulating resin, or the like can be used. As the semiconductive resin, resins such as ethyl cellulose, nitrocellulose, methoxymethylated nylon, ethoxymethylated nylon, copolymerized nylon, polyvinyl hydrin, and casein are used. Examples of conductive particle-dispersed resins include small amounts of conductive particles such as carbon, aluminum, indium oxide, and titanium oxide in insulating resins such as urethane, polyester, vinyl acetate-vinyl chloride copolymer, and polymethyl methacrylate. Examples include dispersed ones.

As the charging member, a brush whose resistance is adjusted by dispersing a conductive material in commonly used fibers is used. As the fiber, generally known fiber can be used, and examples thereof include nylon, acrylic, rayon, polycarbonate, polyester and the like. As the conductive material, generally known conductive materials can also be used, and metals such as copper, nickel, iron, aluminum, gold and silver, or iron oxide, zinc oxide, tin oxide, antimony oxide and titanium oxide. Metal oxides such as carbon black, and conductive powder such as carbon black. These conductive powders may be subjected to surface treatment for the purpose of hydrophobization and resistance adjustment as necessary. In use, it is selected in consideration of dispersibility with fibers and productivity. As the shape of the brush, the fiber thickness is 1 to 20 denier (fiber diameter of about 10 to 500 μm), the brush fiber length is 1 to 15 mm, and the brush density is 10,000 to 300,000 per square inch (1 Those of about 1.5 × 10 ^{7 to} 4.5 × 10 ⁸ per square meter are preferably used.

  In the image forming method of the present invention, it is desirable that the photosensitive member contact charging member is a roller because of excellent charging uniformity.

  Next, the developing method and process cartridge of the present invention will be described.

  FIG. 2 shows a specific example of a developing device applied to the present invention. In FIG. 2, a developing device 13 is located in a developer container 23 containing a non-magnetic toner 17 as a one-component developer, and an opening extending in the longitudinal direction in the developer container 23. A drum) 10 and a toner carrier 14 disposed opposite to each other, and an electrostatic latent image on the latent image carrier 10 is developed and visualized. The photoreceptor contact charging member 11 is in contact with the latent image carrier 10. The bias of the photoreceptor contact charging member 11 is applied by a power supply 12.

  The toner carrier 14 is horizontally provided with the substantially right half-peripheral surface shown in the drawing through the opening into the developer container 23 and the left substantially half-periphery surface exposed to the outside of the developer container 23. The surface exposed to the outside of the developing container 23 is in contact with the latent image carrier 10 located on the left side of the developing device 13 as shown in FIG.

The toner carrier 14 is rotationally driven in the direction of the arrow B, and the surface thereof has moderate unevenness for increasing the probability of rubbing with the toner 17 and for carrying the toner 17 well. When the toner carrier 14 is used by contacting the latent image carrier 10 with the toner carrier 14 as shown in FIG. 2, as an example, the NBR base layer is coated with ether urethane as a surface layer, having a diameter of 16 mm and a surface roughness. An elastic roller having an Rz of ³ to 10 μm and a resistance of 10 ⁴ to 10 ⁸ Ω can be used. The peripheral speed of the latent image carrier 10 is 50 to 170 mm / s, and the peripheral speed of the toner carrier 14 is rotated at a peripheral speed of 1 to 2 times the peripheral speed of the latent image carrier 10.

  At the upper position of the toner carrier 14, a metal plate such as SUS, a rubber material such as urethane or silicone, or a metal thin plate made of SUS or phosphor bronze having spring elasticity is used as a base, and the contact surface to the toner carrier 14. A regulating member 16 made of a rubber material bonded to the side is supported by the blade support metal plate 24 and is provided so that the vicinity of the free end side is in contact with the outer peripheral surface of the toner carrier 14 by surface contact. The contact direction is a so-called counter direction in which the tip side with respect to the contact portion is located upstream of the rotation direction of the toner carrier 14. As an example of the toner regulating member, a plate-like urethane rubber having a thickness of 1.0 mm is bonded to the blade support metal plate 24, and the contact pressure against the toner carrier 14 is appropriately set. The linear pressure was converted from a value obtained by inserting three metal thin plates having a known friction coefficient into the abutting portion and pulling out the central one with only a spring. The regulating member 14 having a rubber material or the like adhered to the abutting surface side is desirable because it has an adhesive property to the toner, and can suppress the fusion and fixing of the toner to the regulating member during long-term use. Further, the restricting member 14 may be in contact with the toner carrying member 14 by edge contact in which the tip is contacted. In the case of edge contact, it is more desirable in terms of toner layer regulation to set the contact angle of the regulating member with respect to the tangent of the toner carrying body at the contact with the toner carrying body to be 40 degrees or less.

  The elastic roller 15 is in contact with the contact portion of the toner regulating member 16 with the surface of the toner carrier 14 on the upstream side in the rotation direction of the toner carrier 14 and is rotatably supported. Examples of this structure include a foamed skeleton-like sponge structure and a fur brush structure in which fibers such as rayon and nylon are planted on a cored bar in terms of supplying the toner 17 to the toner carrier 14 and stripping off the undeveloped toner. As an example of the elastic roller, an elastic roller 15 having a diameter of 12 mm in which a polyurethane foam is provided on the core metal 15a is used. The contact width of the elastic roller 15 with respect to the toner carrier 14 is preferably 1 to 8 mm, and it is preferable that the toner carrier 14 has a relative speed at the contact portion.

  The toner charging roller 29 is an elastic body such as NBR or silicone rubber, and is attached to the suppression member 30. The contact load of the toner charging roller 29 on the toner carrier 14 by the suppressing member 30 was set to 0.49 to 4.9N. By the contact of the toner charging roller 29, the toner layer on the toner carrier 14 is finely packed and uniformly coated. The longitudinal positional relationship between the elastic blade 16 and the toner charging roller 29 is preferably arranged so that the toner charging roller 29 can reliably cover the entire contact area of the elastic blade 16 on the toner carrier 14.

  In addition, for driving the toner charging roller 29, it is essential to follow or have the same peripheral speed with the toner carrier 14, and if a peripheral speed difference occurs between the toner charging roller 29 and the toner carrier 14, the toner coat is not uniform. And unevenness occurs on the image, which is not preferable.

  The bias of the toner charging roller 29 is applied by a power source 27 between the toner carrier 14 and the latent image carrier 10 in a direct current (27 in FIG. 2), and the toner 17 on the toner carrier 14 is a toner charging roller. From 29, charge is applied by discharge.

  The bias of the toner charging roller 29 is a bias equal to or higher than the discharge start voltage having the same polarity as the toner, and is set so that a potential difference of 1000 to 2000 V occurs with respect to the toner carrier 14.

  After being charged by the toner charging roller 29, the toner layer formed as a thin layer on the toner carrier 14 is uniformly conveyed to a developing unit that is a portion facing the latent image carrier 10.

  In this developing portion, the toner layer formed on the toner carrier 14 is formed by a DC bias applied between the toner carrier 14 and the latent image carrier 10 by the power source 27 as shown in FIG. The electrostatic latent image on the latent image carrier 10 is developed as a toner image.

  Although the above description has been given of the development method and the case where the present invention is applied to a process cartridge comprising a developing device detachable from the image forming apparatus main body, the developing apparatus is configured to be fixed in the image forming apparatus main body and replenish only toner. You may apply to. In addition, the photosensitive drum, cleaning blade, waste toner container, and charging device can be provided with at least the above-described developing device, or can be applied to a process cartridge that can be attached to and detached from the image forming apparatus main body. May be.

  Further, when there is a step of cleaning the toner remaining on the photoconductor without being transferred by placing a blade-like cleaning member in pressure contact with the photoconductor, etc., in order to facilitate cleaning in the previous stage of the cleaning step. It is desirable to add a static eliminating step for neutralizing the surface of the photoreceptor.

  Next, the fixing method and fixing device of the present invention will be described.

  The toner of the present invention is heat-fixed to a transfer material such as plain paper or an overhead projector (OHP) transparent sheet by contact heat fixing means.

  As the contact heating fixing means, a heating and pressing roll fixing device, or a heating body fixedly supported, and a pressure that is in pressure-contact with the heating body and in close contact with the heating material through a thin film Examples thereof include a surf fixing unit that heats and fixes the toner depending on the member.

  Therefore, in order to shorten the standby time and reduce the power consumption, a surf fixing method using a film having a small heat capacity is desirable. As shown in FIG. 3, the heating or fixing device using the surf fixing method includes a pressure roller 36. The pressure roller 36 is provided with a cored bar. The pressure roller 36 is rotatable.

For the measurement of fog, a commercially available LBP-2710 (manufactured by Canon Inc.) is used as an image forming apparatus, the product toner is extracted from the commercially available magenta cartridge, the interior is cleaned by air blow, and 300 g of the toner of the present invention is then removed. For other cyan, yellow, and black cartridges, the product toner is removed and inserted into each station, and a durability test is performed at a printing rate of 2% in a high temperature and high humidity environment (30 ° C., 80% RH). The fog amount of the 5000-th image sample from the beginning was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. and calculated from the following formula. The smaller the value, the less fog. A fogging amount of 2% or less was regarded as no practical problem. As a transfer material used for the durability test, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.

Fog amount (%) = (Whiteness before printout) − (Whiteness of non-image forming portion (white background portion) of recording material after printing)
Solid follow-up performance uses a commercially available LBP-2710 (manufactured by Canon Inc.) in a hot and humid environment (30 ° C., 80% RH), removes the product toner from the commercially available magenta cartridge, and cleans the inside by air blow. After that, 300 g of the toner of the present invention was filled, and for other cyan, yellow, and black cartridges, the product toner was removed and inserted into each station, and image evaluation was performed. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.

A full-surface solid chart of the image formation test chart is used. The results of measurement of the paper were evaluated as follows: A: The toner was uniformly transferred and colored on the entire surface. B: A portion with a low density partially existed after 70 mm from the image leading edge. C: 70 mm from the image leading edge. After that, there is a place where the toner is not transferred to the paper and the background of the paper is exposed. The drop-off is a commercially available LBP-2710 (manufactured by Canon Inc.) in a high temperature and high humidity environment (30 ° C., 80% RH). ) To remove the product toner from the commercially available magenta cartridge, clean the inside with air blow, fill with 300 g of the toner of the present invention, and remove the product toner for the other cyan, yellow and black cartridges. Insert into each station, perform a durability test at a printing rate of 2%, and visually evaluate the 5000th image sample from the beginning. It was. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Not generated at all B: One present on the image C: Two to three present on the image but no practical problem D: Generated and practically problematic There is toner on the developing roller and the toner layer regulating member For fusing and fixing, use a commercially available LBP-2710 (manufactured by Canon Inc.) in a hot and humid environment (30 ° C., 80% RH), remove the product toner from the commercially available magenta cartridge, and air blow to the inside. After cleaning, 300 g of the toner of the present invention is filled. For other cyan, yellow, and black cartridges, the product toner is removed and inserted into each station, and a durability test is performed at a printing rate of 2%. The 5000th image sample was visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Not generated at all B: Slightly generated, but no problem in practical use C: Generated, there is a problem in practical use Cleaning performance is LBP-2710 (Canon) available in a hot and humid environment (30 ° C., 80% RH) The product toner is extracted from the commercially available magenta cartridge, the interior is cleaned by air blow, and 300 g of the toner of the present invention is filled. For other cyan, yellow, and black cartridges, the product toner is used. Was inserted into each station, and 10,000 sheets were continuously printed out at a printing rate of 2%, and the cleaning property and image quality were visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. (A with good cleaning, A with poor quality, that is, with the blade's elasticity decreasing, and the toner slipping through, a slight amount of black horizontal streaks appear in the image, but B with no problems in practice occurs. Those having practical problems are indicated by C.)
To reduce the image density, use a commercially available LBP-2710 (manufactured by Canon Inc.) in a hot and humid environment (30 ° C., 80% RH), remove the product toner from the commercially available magenta cartridge, and clean the inside with air blow. After that, 300 g of the toner of the present invention is filled, and for other cyan, yellow, and black cartridges, the product toner is removed and inserted into each station, and a durability test is performed at a printing rate of 2%. For comparison, the density of the image sample of the 5000th endurance from the beginning was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd., and the density difference was evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: No decrease in density B: A decrease in density of 0.01
C: Concentration decrease is 0.02
D: Density decrease is 0.03 or more Fixing property is obtained by using a commercially available LBP-2710 (manufactured by Canon Inc.) in a normal temperature and humidity environment (23.5 ° C. 60%), and removing the product toner from the commercially available magenta cartridge. After extracting and cleaning the inside with air blow, the toner of the present invention is filled with 300 g, and the other toners of cyan, yellow, and black are removed from the product and inserted into each station, and the machine and toner are filled. From the state that the cartridge is familiar with the environment (after being left in the environment for 24 hours), the power is turned on and immediately after waiting for the weight up, a 200 μm width horizontal line pattern (width 200 μ, interval 200 μm) is printed out and the first printed image is fixed. Used for sex evaluation. The fixing property was evaluated by rubbing the image with Sylbon paper at a load of 100 g for 5 reciprocations, and peeling of the image was evaluated by the average of the reduction rate (%) of the reflection density.

  For the evaluation, bond paper having a surface smoothness of 10 [sec] or less was used. The evaluation criteria are shown below.

Fixability A: Density reduction rate of less than 10% B: Density reduction rate of 10% or more and less than 20% C: Density reduction rate of 20% or more, but the evaluation image before rubbing with sylbon paper has no fixing defect D: Sylbon paper Fixation failure has occurred in the evaluation image before rubbing with filming Filming was performed using a commercially available LBP-2710 (manufactured by Canon Inc.) in a high temperature and high humidity environment (30 ° C., 80% RH), and the commercially available magenta. Remove the product toner from the cartridge, clean the inside with air blow, fill with 300g of the toner of the present invention, and for other cyan, yellow, and black cartridges, remove the product toner and insert it into each station for printing An endurance test was conducted at a rate of 2%, and an image sample of the 5000th endurance from the beginning was visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Not generated at all B: Slightly generated but practically no problem C: Slightly generated but practically no problem D: Occurred and practically problematic Hereinafter, the present invention will be described in detail with reference to examples. However, this does not limit the present invention in any way.

  The present invention will be specifically described below with reference to examples and comparative examples. In addition, “parts” in the following examples and the like are “parts by mass”.

--Preparation of resin particle dispersion 1--
-70 parts by mass of styrene-27 parts by mass of n-butyl acrylate-3 parts by mass of acrylic acid-1.5 parts by mass of dodecyl mercaptan A mixture of the above and dissolved is a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) 1.5 parts by mass and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.8 parts by mass dissolved in ion-exchanged water 120 parts by mass were dispersed in a flask. Emulsified, slowly mixed for 10 minutes, charged with 10 parts by mass of ion-exchanged water in which 1.2 parts by mass of ammonium persulfate was dissolved, replaced with nitrogen, and then stirred while stirring the contents of the flask. Was heated in an oil bath until the temperature reached 70 ° C., and emulsion polymerization was continued for 4 hours. Thus, a resin particle dispersion 1 in which resin particles having an average particle diameter of 0.12 μm were dispersed was prepared.

--Preparation of resin particle dispersion 2--
-74 parts by mass of styrene-24 parts by mass of n-butyl acrylate-1.5 parts by mass of divinylbenzene-2 parts by mass of acrylic acid A mixture of the above and dissolved is used as a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) 1.5 parts by mass and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.0 parts by mass were dissolved in 130 parts by mass of ion-exchanged water and dispersed in a flask. The mixture was emulsified and slowly mixed for 10 minutes, and then 10 parts by mass of ion-exchanged water in which 0.7 parts by mass of ammonium persulfate was dissolved was added. After nitrogen substitution, the contents in the flask were stirred. Was heated in an oil bath until the temperature reached 70 ° C., and emulsion polymerization was continued for 4 hours to prepare a resin particle dispersion 2 in which resin particles having an average particle size of 0.24 μm were dispersed.

--Preparation of resin particle dispersion 3--
-73 parts by mass of styrene-24 parts by mass of n-butyl acrylate-2 parts by mass of divinylbenzene-2 parts by mass of acrylic acid A mixture of the above and dissolved is used as a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Nonipol 400) ) 1.5 parts by weight and 3.6 parts by weight of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) dissolved in 120 parts by weight of ion-exchanged water were dispersed in a flask and emulsified. Then, while slowly mixing for 10 minutes, 10 parts by mass of ion-exchanged water in which 1.0 part by mass of ammonium persulfate was dissolved was added thereto, and after replacing with nitrogen, the contents were 70 with stirring in the flask. The mixture was heated in an oil bath until the temperature reached 0 ° C., and emulsion polymerization was continued for 4 hours to prepare resin particle dispersion 3 in which resin particles having an average particle size of 0.09 μm were dispersed.

--Preparation of resin particle dispersion 4--
-73 parts by mass of styrene-24 parts by mass of n-butyl acrylate-1 part by mass of divinylbenzene-2 parts by mass of acrylic acid A mixture of the above and dissolved is a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Nonipol 400) ) 1.5 parts by mass and 2.0 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) dissolved in 120 parts by mass of ion-exchanged water were dispersed in a flask and emulsified. Then, while slowly mixing for 10 minutes, 10 parts by mass of ion-exchanged water in which 1.0 part by mass of ammonium persulfate was dissolved was added thereto, and after replacing with nitrogen, the contents were 70 with stirring in the flask. The mixture was heated in an oil bath until the temperature reached 0 ° C., and emulsion polymerization was continued as it was for 4 hours to prepare a resin particle dispersion 4 in which resin particles having an average particle diameter of 0.28 μm were dispersed.

--Preparation of resin particle dispersion 5--
-73 parts by mass of styrene-24 parts by mass of n-butyl acrylate-1 part by mass of divinylbenzene-2 parts by mass of acrylic acid A mixture of the above and dissolved is a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Nonipol 400) ) 1.5 parts by mass and 2.7 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) dissolved in 120 parts by mass of ion-exchanged water were dispersed in a flask and emulsified. Then, while slowly mixing for 10 minutes, 10 parts by mass of ion-exchanged water in which 1.0 part by mass of ammonium persulfate was dissolved was added thereto, and after replacing with nitrogen, the contents were 70 with stirring in the flask. The mixture was heated in an oil bath until the temperature reached 0 ° C., and emulsion polymerization was continued for 4 hours to prepare a resin particle dispersion 5 in which resin particles having an average particle diameter of 0.14 μm were dispersed.

--Preparation of resin particle dispersion 6--
-73 parts by mass of styrene-25 parts by mass of n-butyl acrylate-0.25 parts by mass of divinylbenzene-2 parts by mass of acrylic acid A mixture of the above and dissolved is a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) 1.5 parts by mass and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.2 parts by mass were dissolved in 120 parts by mass of ion-exchanged water and dispersed in a flask. The mixture was emulsified and slowly mixed for 10 minutes, and then 10 parts by mass of ion-exchanged water in which 0.7 parts by mass of ammonium persulfate was dissolved was added. After nitrogen substitution, the contents in the flask were stirred. Was heated in an oil bath until the temperature reached 70 ° C., and emulsion polymerization was continued as it was for 4 hours to prepare a resin particle dispersion 6 in which resin particles having an average particle diameter of 0.31 μm were dispersed.

-Preparation of resin particle dispersion 7-
-Styrene 75 parts by mass-n-Butyl acrylate 25 parts by mass-Acrylic acid 2 parts by mass Mixing and dissolving 1.5 parts by mass of a nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) And an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.2 parts by mass dissolved in 120 parts by mass of ion-exchanged water, dispersed in a flask, emulsified, and slowly for 10 minutes. While mixing, 10 parts by mass of ion-exchanged water in which 1.0 part by mass of ammonium persulfate was dissolved was added, and after nitrogen substitution, an oil bath was used until the contents reached 70 ° C. while stirring the flask. Then, emulsion polymerization was continued for 4 hours to prepare a resin particle dispersion 7 in which resin particles having an average particle diameter of 0.29 μm were dispersed.

-Preparation of resin particle dispersion 8-
-Styrene 75 parts by mass-n-Butyl acrylate 25 parts by mass-Acrylic acid 2 parts by mass Mixing and dissolving 1.5 parts by mass of a nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) And anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 3.2 parts by mass dissolved in 120 parts by mass of ion-exchanged water, dispersed in a flask, emulsified, and slowly for 10 minutes. While mixing, 10 parts by mass of ion-exchanged water in which 1.0 part by mass of ammonium persulfate was dissolved was added, and after nitrogen substitution, an oil bath was used until the contents reached 70 ° C. while stirring the flask. And the emulsion polymerization was continued for 4 hours to prepare a resin particle dispersion 8 in which resin particles having an average particle diameter of 0.15 μm were dispersed.

--- Preparation of release agent particle dispersion--
-50 parts by mass of an ester compound mainly composed of behenyl behenate (Unistar M-2222SL, manufactured by NOF Corporation)
-6 parts by weight of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
・ Ion-exchanged water 200 parts by mass The above was heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then dispersed with a pressure discharge homogenizer, and the average particle size was 0.5 μm. A release agent particle dispersion was prepared by dispersing the release agent.

-Preparation of colorant particle dispersion 1-
・ C. I. Pigment Red 122 20 parts by mass, anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 mass parts The above was mixed and it disperse | distributed using the sand grinder mill. When the particle size distribution in the colorant particle dispersion 1 was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the contained colorant particles was 0.2 μm and 1 μm. No coarse particles exceeding were observed.

-Preparation of colorant particle dispersion 2-
C. I. Pigment Red 122 is C.I. I. A colorant particle dispersion 2 was prepared in the same manner as the colorant particle dispersion 1, except that the pigment blue was changed to 15: 3.

-Preparation of colorant particle dispersion 3-
C. I. Pigment Red 122 is C.I. I. A colorant particle dispersion 3 was prepared in the same manner as the colorant particle dispersion 1 except that the pigment yellow 17 was used.

-Preparation of colorant particle dispersion 4-
C. I. Colorant particle dispersion 4 was prepared in the same manner as colorant particle dispersion 1, except that Pigment Red 122 was changed to carbon black.

--Preparation of charge control particle dispersion--
-5 parts by mass of a metal compound of di-alkyl-salicylic acid (charge control agent, Bontron E-84, manufactured by Orient Chemical Industries)
・ Anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 mass parts The above was mixed and it disperse | distributed using the sand grinder mill. When the particle size distribution in the charge control particle dispersion 1 was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the charge control particles contained was 0.2 μm and 1 μm. No coarse particles exceeding were observed.

<Preparation of liquid mixture>
-Resin particle dispersion 1 380 parts by weight-Colorant dispersion 1 40 parts by weight-Release agent dispersion 70 parts by weight The above is put into a 1 liter separable flask equipped with a stirrer, condenser, and thermometer. Stir. The mixture was adjusted to pH = 5.2 using 1N potassium hydroxide.

<Agglomerated particle formation>
As a flocculant, 150 parts by mass of a 10% sodium chloride aqueous solution was dropped into this mixed solution, and the mixture was heated to 57 ° C. while stirring the inside of the flask in a heating oil bath. At this temperature, 3 parts by mass of the resin particle dispersion 1 and 10 parts by mass of the charge control agent particle dispersion were added. After maintaining at 52 ° C. for 2 hours, observation with an optical microscope confirmed that aggregated particles having an average particle diameter of about 7.1 μm were formed.

<Fusion process>
Then, after adding 3 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC), the mixture was heated to 95 ° C. while continuing stirring using a magnetic seal in a stainless steel flask. For 4.5 hours. And after cooling, the reaction product is filtered, washed thoroughly with ion-exchanged water, then fluidized-bed dried at 45 ° C, and the shape is adjusted by dispersing it in a gas phase of 200-300 ° C with a spray dryer. As a result, a magenta toner base 1 was obtained. 1 kg of the toner base, 1.1 parts by mass of hydrophobic silica hydrophobized with chlorophenyl silicone oil having a primary particle size of 34 nm (hydrophobic degree 95%, negative chargeability), and zinc oxide having a primary particle size of 480 nm (positive charging) Property) 0.04 parts by mass are equally divided into four parts, and the toner base, hydrophobic silica and zinc oxide are alternately put into the Henschel mixer FM10B. At this time, the inside of the Henschel mixer was made to be in a nitrogen atmosphere, and when the hydrophobic silica and zinc oxide were charged, they were charged while sieving with a mesh having an opening of 500 μm. Then, after stirring for 60 seconds at 300 rpm, it is left as it is for 24 hours. After that, it is stirred for 60 seconds at 300 rpm, then stirred for 180 seconds at 4000 rpm, and further left for 24 hours, and then sieved with a mesh having a mesh size of 43 μm. Got. The physical properties of Toner 1 are shown in Table 1.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 5, the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 3, and the hydrophobic silica at the fusing step is changed. The addition amount was changed from 1.1 parts by mass to 7.9 parts by mass, zinc oxide was surface-treated with linolenic acid, and the addition amount of the zinc oxide was further changed from 0.04 parts by mass to 3.2 parts by mass. In the same manner, Toner 2 was obtained. The physical properties of Toner 2 are shown in Table 1.

  Addition of hydrophobic silica during the fusing step, using the resin particle dispersion 1 at the time of preparing the mixed liquid of toner production example 1 as the resin particle dispersion 2 and the resin particle dispersion 1 at the time of forming the aggregated particles as the resin particle dispersion 2. Toner 3 was obtained in the same manner except that the amount was changed from 1.1 parts by weight to 5.5 parts by weight, and the amount of zinc oxide added was changed from 0.04 parts by weight to 4.8 parts by weight. The physical properties of Toner 3 are shown in Table 1.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 2, the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 4, and the hydrophobic silica in the fusing process is changed. The primary particle size is 27 nm, the addition amount is 1.1 parts by mass to 5.0 parts by mass, the zinc oxide is surface-treated with linolenic acid, and the addition amount of the zinc oxide is 0.04 parts by mass to 3.0 parts by mass. Toner 4 was obtained in the same manner except that the amount of The physical properties of Toner 4 are shown in Table 1. At this time, the zinc oxide surface-treated with linolenic acid was positively charged.

  The primary particle size of hydrophobic silica during the fusing step of Toner Production Example 1 was 27 nm, the addition amount was changed from 1.1 parts by weight to 1.3 parts by weight, and zinc oxide was surface-treated with linolenic acid. Toner 5 was obtained in the same manner except that the amount of was changed from 0.04 parts by mass to 0.06 parts by mass. The physical properties of Toner 5 are shown in Table 1.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 2, the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 4, and the hydrophobic silica in the fusing process is changed. The primary particle size is 27 nm, the addition amount is 1.1 to 5.0 parts by mass, the zinc oxide is surface-treated with linolenic acid, the primary particle size is 380 nm, and the addition amount is 0.04 parts by mass. Toner 6 was obtained in the same manner except that the amount was 3.0 parts by mass. The physical properties of Toner 6 are shown in Table 1. At this time, the zinc oxide surface-treated with linolenic acid was positively charged.

  The primary particle size of hydrophobic silica during the fusing process of Toner Production Example 1 was 27 nm, the addition amount was changed from 1.1 parts by weight to 3.0 parts by weight, and zinc oxide was surface-treated with linolenic acid. The toner 7 was obtained in the same manner except that the toner was added to 120 nm and the addition amount was changed from 0.04 parts by mass to 0.06 parts by mass. The physical properties of Toner 7 are shown in Table 1. At this time, the zinc oxide surface-treated with linolenic acid was positively charged.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 2, the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 4, and the hydrophobic silica in the fusing process is changed. The primary particle size is 27 nm, the addition amount is 1.1 to 5.0 parts by mass, and zinc oxide is hydrotalcite A (surface treatment with linolenic acid, positive chargeability) having a primary particle size of 350 nm. Toner 8 was obtained in the same manner except that the addition amount was changed from 0.04 parts by mass to 3.0 parts by mass. The physical properties of Toner 8 are shown in Table 1. Hydrotalcite A is shown in Table 3.

  Hydrotalcite A having a primary particle size of hydrophobic silica of 27 nm, an addition amount of 1.1 to 2.7 parts by mass, and zinc oxide having a primary particle size of 150 nm in the fusing step of Toner Production Example 1 Toner 9 was obtained in the same manner except that the amount added was changed from 0.04 parts by mass to 0.06 parts by mass (surface treatment with linoleic acid, positive chargeability). The physical properties of Toner 9 are shown in Table 1. Hydrotalcite A is shown in Table 3.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 4 and the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 5, so that the hydrophobic silica in the fusing step is changed. The primary particle size is 22 nm, the amount added is 1.1 to 2.8 parts by mass, and zinc oxide is hydrotalcite A (surface treatment with linoleic acid, positive chargeability) having a primary particle size of 350 nm, Toner 10 was obtained in the same manner except that the addition amount was changed from 0.04 parts by mass to 1.3 parts by mass. The physical properties of the toner 10 are shown in Table 1. Hydrotalcite A is shown in Table 3.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 7, and the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 8. The primary particle size is 27 nm, the amount added is 1.1 to 3.8 parts by mass, and zinc oxide is hydrotalcite A (surface treatment with linoleic acid, positive chargeability) having a primary particle size of 350 nm, Toner 11 was obtained in the same manner except that the amount added was changed from 0.04 parts by mass to 2.3 parts by mass. The physical properties of the toner 11 are shown in Table 1. Hydrotalcite A is shown in Table 3.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 6 and the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 6. The primary particle size is 22 nm, the amount added is 1.1 to 2.2 parts by mass, and zinc oxide is hydrotalcite B (surface treatment with linoleic acid, positive chargeability) having a primary particle size of 350 nm, Toner 12 was obtained in the same manner except that the addition amount was changed from 0.04 parts by mass to 0.7 parts by mass. The physical properties of the toner 12 are shown in Table 1. Hydrotalcite B is shown in Table 3.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 6 and the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 6. The primary particle size is 17 nm, the amount added is 1.1 to 2.7 parts by mass, and zinc oxide is hydrotalcite A (surface treatment with linoleic acid, positive chargeability) having a primary particle size of 350 nm, Toner 13 was obtained in the same manner except that the addition amount was changed from 0.04 parts by mass to 1.5 parts by mass. The physical properties of the toner 13 are shown in Table 1. Hydrotalcite A is shown in Table 3.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 6 and the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 6. The primary particle size is 17 nm, the addition amount is 1.1 to 2.7 parts by mass, and zinc oxide is hydrotalcite A (surface treatment with linoleic acid, positive chargeability) having a primary particle size of 350 nm, Toner 14 was obtained in the same manner except that the addition amount was changed from 0.04 parts by mass to 0.8 parts by mass. The physical properties of the toner 14 are shown in Table 1. Hydrotalcite A is shown in Table 3.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 6 and the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 6. The primary particle size is 12 nm, the amount added is 1.1 to 2.5 parts by mass, and zinc oxide is hydrotalcite A (surface treatment with linoleic acid, positive chargeability) having a primary particle size of 350 nm, Toner 15 was obtained in the same manner except that the addition amount was changed from 0.04 parts by mass to 0.7 parts by mass. The physical properties of the toner 15 are shown in Table 1. Hydrotalcite A is shown in Table 3.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 6 and the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 6. The primary particle size is 7 nm, the addition amount is 1.1 parts by mass to 2.0 parts by mass, and zinc oxide is hydrotalcite A (surface treatment with linoleic acid, positive chargeability) having a primary particle size of 350 nm, Toner 16 was obtained in the same manner except that the addition amount was changed from 0.04 parts by mass to 0.7 parts by mass. The physical properties of the toner 16 are shown in Table 1. Hydrotalcite A is shown in Table 3.

  In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 6 and the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 6. The primary particle size is 7 nm, the addition amount is 1.1 parts by mass to 2.0 parts by mass, and zinc oxide is hydrotalcite A (surface treatment with linoleic acid, positive chargeability) having a primary particle size of 350 nm, Toner 17 was obtained in the same manner except that the amount added was changed from 0.04 parts by mass to 1.0 part by mass. The physical properties of the toner 17 are shown in Table 1. Hydrotalcite A is shown in Table 3.

(Comparative Example 1)
In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 7, and the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 6. The primary particle size is 34 nm, the amount added is 1.2 to 0.8 parts by mass, and zinc oxide is hydrotalcite C (surface treatment with palmitic acid, positive chargeability) having a primary particle size of 350 nm, Toner 18 was obtained in the same manner except that the amount added was changed from 0.04 parts by mass to 0.5 parts by mass. The physical properties of the toner 18 are shown in Table 1. Hydrotalcite C is shown in Table 3.

(Comparative Example 2)
In the toner production example 1, the resin particle dispersion 1 at the time of preparing the mixed solution is changed to the resin particle dispersion 6 and the resin particle dispersion 1 at the time of forming the aggregated particles is changed to the resin particle dispersion 6. Toner 19 was obtained in the same manner except that the addition amount was changed from 1.2 parts by weight to 3.5 parts by weight and no zinc oxide was contained. The physical properties of the toner 19 are shown in Table 1.

It is explanatory drawing of the apparatus used for the measurement of the charge amount of an inorganic fine particle or a toner. It is the schematic of the image development apparatus which performs nonmagnetic one-component contact development. Schematic of the fixing device.

Explanation of symbols

1 Suction machine 2 Measuring container 3 Conductive screen (500 mesh)
4 Lid 5 Vacuum gauge 6 Air flow control valve 7 Suction port 8 Condenser 9 Electrometer 10 Latent image carrier (photosensitive drum)
11 Photoconductor contact charging member (elastic roller)
DESCRIPTION OF SYMBOLS 12 Power supply 13 Developing apparatus 14 Toner carrier 15 Elastic roller 16 Elastic blade (regulation member)
17 Toner 24 Blade support sheet metal 25 Stirrer 26 Toner leakage prevention member 27 Power supply 29 Toner charging roller (pressure contact elastic member)
30 Suppression Member 31 Heater Base 32 Heating Element 33 Temperature Detection Element 34 Holder 35 Film 36 Pressure Roll 37 Film Drive Roll 38 Tension Roll 39 Toner P Transfer Paper

Claims (21)

A toner having toner particles obtained by agglomerating and combining a plurality of polymer fine particles dispersed in an aqueous medium, the toner having a volume average diameter of 4 to 10 μm,
The shape factor SF-1 is 115 to 140,
The average circularity is 0.950-0.990,
The BET specific surface area is 1.50 to 10.0 m ² / g,
The toner particles contain at least a hydrophobized silica fine powder and an inorganic fine powder that is charged with a polarity opposite to that of the hydrophobized silica fine powder when a two-component tribo is measured using a ferrite carrier. In addition, the total content of the silica fine powder is 1.0% by mass or more and 8.0% by mass or less, and the content of the inorganic fine powder charged to a polarity opposite to that of the silica fine powder is 0.02% by mass or more and 5.00%. A non-magnetic one-component toner having a mass% or less. 2. The toner according to claim 1, wherein the toner has a BET specific surface area of 1.50 to 7.0 m ² / g, and contains 1.0% by mass or more of the silica fine powder having a primary particle size of 30 nm or less. The toner described.   3. The toner according to claim 1, wherein a primary particle diameter of the reverse polarity chargeable inorganic fine powder is 100 nm or more and 400 nm or less.   The toner according to any one of claims 1 to 3, wherein the reverse polarity chargeable inorganic fine powder is hydrotalcite and contains magnesium or magnesium ions.   The toner according to claim 1, wherein the toner has an MI of 3.0 or more and 30.0 or less.   6. The toner according to claim 1, wherein the silica fine powder having a primary particle diameter of 20 nm or less is contained in an amount of 1.0% by mass or more.   The toner according to claim 1, wherein the toner has a saturated triboelectric charge amount of −50 mC / kg or more and −75 mC / kg or less in an environment of 23 ° C. and 60% RH. An image forming method for forming an image using a non-magnetic one-component toner, the image forming method comprising:
A toner layer forming step of regulating a toner layer on the toner carrier by bringing a toner regulating member into contact with the surface of the toner carrier;
An auxiliary charging step of controlling charging of the toner particles regulated by the toner regulating member by an auxiliary charging member in contact with the toner carrier;
A developing step of developing the electrostatic latent image by bringing the toner layer carried on the surface of the toner carrier into contact with the surface of the electrostatic latent image carrier to form a toner image on the electrostatic latent image carrier;
Having at least
The toner is a toner having toner particles obtained by aggregating and coalescing a plurality of polymer fine particles dispersed in an aqueous medium,
The volume average diameter is 4 to 10 μm,
The shape factor SF-1 is 115 to 140,
The average circularity is 0.950-0.990,
The specific surface area is 1.50 to 10.0 m ² / g,
The toner particles contain at least a hydrophobized silica fine powder and an inorganic fine powder that is charged with a polarity opposite to that of the hydrophobized silica fine powder when a two-component tribo is measured using a ferrite carrier. In addition, the total content of the silica fine powder is 1.0% by mass or more and 8.0% by mass or less, and the content of the inorganic fine powder charged to a polarity opposite to that of the silica fine powder is 0.02% by mass or more and 5.00%. An image forming method, wherein the image forming method is at most mass%. The BET specific surface area of the toner is 1.50 to 7.0 m ² / g, and the silica fine powder having a primary particle size of 30 nm or less is contained in an amount of 1.0% by mass or more. The image forming method described.   10. The image forming method according to claim 8, wherein a primary particle diameter of the reverse polarity chargeable inorganic fine powder is 100 nm or more and 400 nm or less.   11. The image forming method according to claim 8, wherein the reverse polarity chargeable inorganic fine powder is hydrotalcite and contains magnesium or magnesium ions.   12. The image forming method according to claim 8, wherein the MI of the toner is 3.0 or more and 30.0 or less.   13. The image forming method according to claim 8, wherein the silica fine powder having a primary particle size of 20 nm or less is contained in an amount of 1.0% by mass or more.   14. The image forming method according to claim 8, wherein the toner has a saturated triboelectric charge amount of −50 mC / kg or more and −75 mC / kg or less in an environment of 23 ° C. and 60% RH. A process cartridge for forming an image using non-magnetic one-component toner,
A photosensitive member, a charging member in contact with the photosensitive member, a developing container for containing toner, a developing roller provided in an opening of the developing container, and a nip formed with the developing roller and carried on the developing roller A toner regulating member for regulating the toner layer thickness and triboelectrically charging the toner, and an auxiliary member in contact with the toner carrier for controlling the charging of the toner particles regulated by the toner regulating member A charging member, and a toner supply member for supplying toner to the developing roller; the photosensitive member is negatively charged by the charging member in contact with the photosensitive member; an electrostatic latent image is formed by digital exposure; Toner is supplied to the developing roller by the toner supply member, and the toner layer is formed by the regulating member for forming a thin layer on the developing roller. The auxiliary charging member in contact with the carrier to control the charging of the toner in the process cartridge to obtain a toner image by developing the toner on the photosensitive member by a developing roller for developing in contact with the photosensitive member,
The toner is a toner having toner particles obtained by aggregating and coalescing a plurality of polymer fine particles dispersed in an aqueous medium,
The volume average diameter is 4 to 10 μm,
The shape factor SF-1 is 115 to 140,
The average circularity is 0.950-0.990,
The specific surface area is 1.50 to 10.0 m ² / g,
The toner particles contain at least a hydrophobized silica fine powder and an inorganic fine powder that is charged with a polarity opposite to that of the hydrophobized silica fine powder when a two-component tribo is measured using a ferrite carrier. In addition, the total content of the silica fine powder is 1.0% by mass or more and 8.0% by mass or less, and the content of the inorganic fine powder charged to a polarity opposite to that of the silica fine powder is 0.02% by mass or more and 5.00%. A process cartridge having a mass% or less. 16. The toner according to claim 15, wherein the toner has a BET specific surface area of 1.50 to 7.0 m ² / g and contains 1.0% by mass or more of the silica fine powder having a primary particle size of 30 nm or less. The described process cartridge.   The process cartridge according to claim 15 or 16, wherein a primary particle size of the reverse-polarity chargeable inorganic fine powder is 100 nm or more and 400 nm or less.   18. The process cartridge according to claim 15, wherein the reverse polarity chargeable inorganic fine powder is hydrotalcite and contains magnesium or magnesium ions.   19. The process cartridge according to claim 15, wherein the MI of the toner is 3.0 or more and 30 or less.   20. The process cartridge according to any one of claims 15 to 19, wherein the silica fine powder having a primary particle size of 20 nm or less is contained in an amount of 1.0% by mass or more.   21. The process cartridge according to claim 15, wherein a saturated triboelectric charge amount of the toner in an environment of 23 ° C. and 60% RH is −50 mC / kg or more and −75 mC / kg or less.

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