JP2006259312A - Image forming method, process cartridge, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To perform stable and satisfactory image formation with excellent wear resistance, and very little deterioration of photoreceptor while assuring satisfactory clearability. <P>SOLUTION: In the image forming method which has electrostatic charging process, an exposing process, a developing process, a transferring process, and a cleaning process and forms a toner image, the repulsive elasticity at 23°C of the cleaning blade is ≥60 to ≤90%, the abutting pressure on the photoreceptor 40 is ≤0.20 N/cm, the cleaning angle formed by the photoreceptor 40 and the cleaning blade is ≥80°. The toner has a filler layer in the vicinity of the surface of a binder resin. The number average grain size of the primary particles of the external additives of the toner is 20 to 100 nm and the external additives contain the microparticles of grain sizes 10 to 20 nm and large-diameter particles of 200 to 300 nm and the circularity of the toner is specified to ≥0.94. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a cleaning blade, an image forming toner, and a developer used for image formation in an electrostatic copying process such as a copying machine, a facsimile machine, and a printer. Further, the cleaning blade, the toner, and the developer are used. The present invention relates to a process cartridge to be used, an image forming apparatus, and an image forming method.

  An electrophotographic image forming method includes a charging process for applying a charge to the surface of a photoreceptor, which is a latent image carrier, by an electric discharge, an exposure process for forming an electrostatic latent image by exposing the charged photoreceptor surface, A developing process for supplying toner to the electrostatic latent image formed on the surface of the body for development, a transfer process for transferring the toner image on the surface of the photoreceptor to the surface of the transfer body, and fixing the toner image on the surface of the transfer body The image forming apparatus includes a fixing process and a cleaning process for removing toner remaining on the surface of the image carrier after the transfer process.

The cleaning process includes a cleaning device using a cleaning blade, a cleaning device using a fur brush roller made of conductive or insulating fibers, a cleaning device using a cleaning roller having polishing ability, and a lubricant substance to itself. Various types of devices are known, such as a cleaning device using an enclosing cleaning roller, a cleaning device using a magnetic brush roller in which magnetic powder is disposed on the roller surface, and a cleaning device using an aspirator.
The most widely used method is a method using a cleaning blade. It has a simple structure and high toner removability.

In recent years, there has been an increasing demand for higher image quality, and in order to realize particularly high-definition color image formation, toner particles are being reduced in size and spheroidized. The reproducibility of dots can be improved by reducing the particle size, and the developability and transferability can be improved by making the particles spherical. On the other hand, it is difficult to ensure a sufficient cleaning capacity.
Since it is very difficult to produce such a small particle size and spherical toner by the conventional kneading pulverization method, the polymerization produced by suspension polymerization method, emulsion polymerization method, dispersion polymerization method, etc. Toner is being adopted.

However, when the particle size of the toner is reduced to about several μm or less, the non-electrostatic adhesion force such as van der Waals force acting between the toner and the photoconductor increases with respect to its own weight. The moldability deteriorates, affecting the transferability and cleaning properties.
On the other hand, a toner that is spherical and has a shape close to a true sphere has a lower adhesive force to the photoconductor and the like than an indeterminate toner obtained by the kneading and pulverization method, and therefore has high releasability from the photoconductor. Rate is obtained. Further, since the adhesion force between the toner particles is small and is easily affected by the electric force lines, the toner image is faithfully transferred to the latent image along the electric force lines. However, when the transferred object is separated from the photosensitive member, a high electric field is generated between the photosensitive member and the transferred member (burst phenomenon), and the toner on the transferred member and the photosensitive member is disturbed to cause the toner on the transferred member. There is a problem of the generation of dust.
In addition, when polymerized toner with a small particle size is used, it is difficult to clean because the shape is close to a true sphere and the particle size is small compared to the toner produced by the conventional pulverization method. There is a disadvantage that defective cleaning such as a spot occurs.
In particular, when a cleaning blade is used, defective cleaning tends to occur when the edge of the blade is worn or chipped by repeated use. In addition, due to the use, the photoreceptor is worn and fine irregularities are formed, and cleaning defects are likely to occur even when the surface roughness increases.

As described above, when designing a toner with the aim of reducing the particle size and making it spherical, the surface condition of the toner should be adjusted in order to make the adhesion between the toner and the photoreceptor or between the toners appropriate. Control is a new challenge.
In the past, various proposals have been made to control the shape of spherical and small toner particles, particularly for the purpose of improving cleaning properties.
For example, the shape of the toner is represented by using a shape factor SF-1 which is an index representing the degree of roundness of the toner particles and a shape factor SF-2 which is an index representing the degree of unevenness of the toner particles, and SF-1, SF -2 is defined to control the shape of the toner to improve the cleaning property (see, for example, Patent Documents 1 to 6).
However, if the cleaning property is improved only by the surface shape of the toner, it is difficult to achieve both good transferability and image quality. Therefore, the cleaning blade has been improved. In order to prevent the cleaning blade from being worn or chipped, a method of applying or supplying a lubricant to the blade surface is widely used.

For example, a certain amount of toner is consciously supplied to the cleaning blade, and the toner is used as a lubricant (see, for example, Patent Document 7).
However, a toner that often slips through may function as a blade abrasive rather than as a lubricant, and rather promotes wear of the cleaning blade.
In addition, a technique for improving environmental stability by specifying blade physical properties has been proposed (see, for example, Patent Document 8). In the case of a spherical toner having a small particle size, sufficient cleaning properties are not necessarily obtained. The durability was not obtained.

  In addition, a proposal has been made on a technique for ensuring cleaning properties by using a photosensitive member containing a siloxane-based resin and a cleaning blade having specific physical properties (see, for example, Patent Document 9). Reduces the charging characteristics of the photoconductor, and increases the cost by coating the protective layer.

  In addition, although a method has been proposed in which the cleaning aid is retained in the vicinity of the cleaning blade in contact with the photosensitive member (see, for example, Patent Document 10), it is impossible to actually retain the cleaning aid in practice. Usually, the replacement of the cleaning aid and the toner occurs, or the cleaning aid is scraped off and decreases, so that the aid layer cannot be formed stably.

  In the technique described in Patent Document 11 below, since the contact pressure is very high, the photosensitive member and the cleaning blade are easily worn, and the toner is rolled between the photosensitive member and the blade so that the toner is placed on the photosensitive member. This component has a problem that so-called filming is likely to occur.

JP 2000-122347 A JP 2000-267331 A Japanese Patent Laid-Open No. 2001-312191 JP 2002-23408 A JP 2002-31775 A JP-A-9-179411 JP 2002-72713 A Japanese Patent Laid-Open No. 9-50221 JP 2003-98925 A JP 2003-307985 A JP 2003-208035 A

  In view of the above problems, in the present invention, a toner capable of forming a high-definition image that exhibits both good transferability and cleanability, exhibits good fixability, and does not deteriorate image quality even when a large number of sheets are printed. And a cleaning blade that improves the cleaning performance of the toner, and an image forming method, an image forming apparatus, and a process cartridge are provided.

  The invention according to claim 1 is an image forming method for forming a toner image, comprising at least a charging step, an exposure step, a development step, a transfer step, and a cleaning step, wherein the cleaning step includes a cleaning blade. The cleaning blade is in contact with the photosensitive member and removes residual toner on the photosensitive member by a blade cleaning method. The cleaning blade has a rebound resilience at 23 ° C. of 60% to 90%. The contact pressure with respect to the photosensitive member is 0.20 N / cm or less, the cleaning angle formed by the photosensitive member and the cleaning blade is 80 degrees or more, and the toner is a filler at least near the surface of the binder resin. The number average particle size of primary particles of the external additive of the toner is 20 to 100. m and the toner external additive contains fine particles having an average particle diameter of 10 to 20 nm and large particles having an average particle diameter of 200 to 300 nm, and the circularity of the toner is 0.94 or more. An image forming method is provided.

  According to a second aspect of the present invention, there is provided the image forming method according to the first aspect, wherein the cleaning blade has a hardness of 72 degrees or less.

  According to a third aspect of the present invention, there is provided the image forming method according to the first or second aspect, wherein the amount of protrusion of the cleaning blade is 6.0 mm or more.

  According to a fourth aspect of the present invention, in the image formation according to any one of the first to third aspects, the ratio between the thickness of the cleaning blade and the protruding amount is 1: 3 to 1: 5. Provide a method.

  According to a fifth aspect of the present invention, there is provided the image forming method according to any one of the first to fourth aspects, wherein the peak temperature of the loss tangent tan δ in the viscoelasticity measurement is 0 ° C. or lower.

  The invention according to claim 6 provides the image forming method according to any one of claims 1 to 5, wherein a content of the filler in the toner particles is 0.01 to 20% by weight. .

  In a seventh aspect of the present invention, the ratio of the volume average particle diameter of the primary particles of the filler to the volume average particle diameter of the toner is 0.1 or less. The described image forming method is provided.

  In the invention which concerns on Claim 8, the volume average particle diameter of the primary particle of the said filler shall be 0.001-0.5 micrometer, The image forming method as described in any one of Claims 1 thru | or 7 provide.

  In the invention according to claim 9, the filler is a metal oxide, metal hydroxide, metal carbonate, metal sulfate, metal silicate, metal nitride, metal phosphate, metal borate, metal titanium. Inorganic fillers selected from the group consisting of acid salts, metal sulfides, carbons, and / or urethane resins, epoxy resins, vinyl resins, ester resins, melamine resins, benzoguanamine resins, fluororesins, silicone resins, azo pigments, The image forming method according to any one of claims 1 to 8, wherein the image forming method is an organic filler selected from the group consisting of phthalocyanine pigments, condensed polycyclic pigments, dyed lake pigments, and organic waxes.

  In the invention which concerns on Claim 10, the said filler is a filler processed with the surface treating agent chosen from the group which consists of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a tertiary amine compound. The image forming method according to claim 1, wherein the image forming method is used.

  The invention according to claim 11 provides the image forming method according to any one of claims 1 to 10, wherein the filler is selected from the group consisting of silica, alumina, and titania.

  The invention according to claim 12 provides the image forming method according to any one of claims 1 to 11, wherein the filler is an organosol synthesized by a wet method.

  According to a thirteenth aspect of the present invention, there is provided the image forming method according to any one of the first to twelfth aspects, wherein the inorganic fine particles are silica having a spherical shape.

  According to a fourteenth aspect of the present invention, there is provided the image forming method according to any one of the first to thirteenth aspects, wherein the inorganic fine particles are produced by a sol-gel method.

  In the invention according to claim 15, the shape factor SF-2 of the toner is 120 to 150, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1. The image forming method according to claim 1, which is 01 or more and 1.30 or less.

  In a sixteenth aspect of the present invention, a color image formed on the latent image carrier is sequentially transferred to an intermediate transfer member, and then transferred to a recording medium and fixed to form a full color image. An image forming method according to any one of the above is provided.

  According to a seventeenth aspect of the present invention, there is provided the image forming method according to any one of the first to sixteenth aspects, wherein the toner contains a wax.

  According to an eighteenth aspect of the present invention, there is provided the image forming method according to any one of the first to seventeenth aspects, wherein the binder resin constituting the toner contains a modified polyester.

  In the invention according to claim 19, the binder resin constituting the toner contains an unmodified polyester together with the modified polyester, and the weight A of the modified polyester and the weight B of the unmodified polyester The image forming method according to claim 1, wherein the ratio of A / B is 5/95 to 80/20.

  In the invention according to claim 20, the toner base particles include a toner material liquid in which at least a polyester prepolymer having a functional group containing a nitrogen atom, a polyester, and a filler are dispersed and / or dissolved in an organic solvent. The image forming method according to any one of claims 1 to 19, wherein the image forming method is obtained by dispersing in a water-based medium and crosslinking and / or extending the toner material.

  The invention according to claim 21 is the developer for developing the electrostatic latent image formed on the latent image carrier in the developing step, and the image forming method according to any one of claims 1 to 20 21. An image forming method according to claim 1, wherein a two-component developer comprising a toner applied in step 1 and a magnetic carrier is applied.

  The image formation according to any one of claims 1 to 21, wherein the photoconductor has a protective layer containing inorganic fine particles made of alumina or titanium oxide. Provide a method.

  According to a twenty-third aspect of the invention, there is provided the image forming method according to any one of the first to twenty-second aspects, wherein a coefficient of friction of the surface of the photoconductor is 0.3 or less.

  In the invention according to claim 24, at least a latent image carrier that carries a latent image and a developing unit that supplies toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize the latent image. A process cartridge that is integrally supported and formed detachably on the main body of the image forming apparatus, wherein the process cartridge is applied to the image forming method according to any one of claims 1 to 23. provide.

  In the invention according to claim 25, the latent image carrier that carries the latent image, the charging means that uniformly charges the surface of the latent image carrier, and the surface of the charged latent image carrier based on the image data. Exposure means for exposing and writing an electrostatic latent image, developing means for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier to make it visible, and the surface of the latent image carrier surface An image forming apparatus comprising: a transfer unit that transfers a visible image to a transfer target; a cleaning unit that cleans toner remaining on the photoconductor; and a fixing unit that fixes the visible image on the transfer target. An image forming apparatus for use in the image forming method according to any one of claims 1 to 24 is provided.

According to the present invention, a high-quality image is formed by using a cleaning blade exhibiting a specific rebound resilience under a specific contact condition and using an additive having a specific particle size for a toner having a specific shape. We were able to.
Also, good cleaning characteristics were obtained by specifying the toner shape.
In addition, since the contact condition of the cleaning blade was selected so that the load on the photoconductor was reduced, deterioration of the photoconductor and the cleaning blade was reduced, and durability was improved.
Further, the surface shape of the toner is controlled so that the adhesion force between the toner and the member in each step of the image forming process is in an appropriate range so that the toner contains inorganic fine particles having a volume average particle diameter of 90 to 300 nm. As a result, it was possible to achieve both transferability, fixing property, and cleaning property, and a high-definition image could be formed, and a high-definition and high-definition image was obtained.

  Embodiments of the present invention will be described in detail below, but the present invention is not limited to the examples shown below.

  The image forming method of the present invention forms a toner image through at least a charging step, an exposure step, a development step, a transfer step, and a cleaning step. In the cleaning step, a cleaning blade is used as a photoreceptor. It is assumed that the cleaning is performed by a blade cleaning method that removes transfer residual toner on the photoreceptor, and the rebound resilience at 23 ° C. of the cleaning blade is 60% or more and 90% or less, and the cleaning blade contacts the photoreceptor. The pressure is 0.20 N / cm or less, the cleaning angle formed by the photosensitive member and the cleaning blade is 80 degrees or more, and the toner has a filler layer at least near the surface of the binder resin The number average particle size of primary particles of the toner external additive is 20 to 100 n. The toner external additive contains fine particles having an average particle diameter of 10 to 20 nm and large particles having an average particle diameter of 200 to 300 nm, and the circularity of the toner is 0.94. It shall be above.

  As the hardness of the cleaning blade increases, the cleaning performance decreases. The lower one can improve the filming margin. For this reason, the hardness of the cleaning blade is preferably 72 degrees or less.

  If the protruding amount of the cleaning blade is short, the cleaning performance is deteriorated. When the length is longer, the cleaning property is improved, and in particular, the environmental stability is improved. For this reason, the protrusion amount of the cleaning blade is preferably 6.0 mm or more.

Further, when the cleaning blade is thick, the cleaning performance is deteriorated. When the length is longer, the cleaning property is improved, and particularly the environmental stability is improved. In view of this point, it has been found that a good cleaning property can be obtained when the ratio of the thickness of the cleaning blade to the protruding amount is 1: 3 to 1: 5.
When the ratio is small, the cleaning stability is lowered, and abnormal sounds such as chatter are likely to occur. Further, when the ratio is increased, blade turning tends to occur.

  Further, the lower the peak temperature of the loss tangent tan δ in the viscoelasticity measurement, the better the environmental stability. The rate of change of this temperature characteristic increases as it approaches the peak temperature. If there is a gap between the operating temperature range and the peak temperature, the rate of change of tan δ becomes small. In view of this point, it is desirable that the peak temperature be 0 ° C. or lower.

Also, the cleaning property improves as the cleaning blade rebound resilience increases. Specifically, it was confirmed that the resilience is preferably 60% or more, and more preferably 65 to 85%.
The contact pressure of the cleaning blade with respect to the photosensitive member is preferably 0.20 N / cm or less. When the contact pressure is lowered, the cleaning property is improved, and an abnormal image such as a decrease in durability due to photosensitive wear resistance and filming is improved. A more preferable range is 0.050 to 0.150 N / cm.
The cleaning blade has high rebound resilience, and the cleaning performance improves when the contact pressure is low, so the cleaning blade edge vibrates in small increments, so-called stick-slip vibration is quickened, and blade edge position fluctuations are reduced. Cleaning performance is improved because there is no change in the cleaning conditions and the toner is repelled by the vibration of the blade edge.

Next, the toner will be described.
As for the particle size of the inorganic fine particles of the external additive applied to the toner, it is preferable that the number average particle size of the primary particles is 20 to 100 nm and the particles have particle sizes of 10 to 20 nm and 200 to 300 nm. It has also been found that the toner is preferably an image forming toner containing at least a resin particle for toner containing a binder resin and a filler, and inorganic fine particles.
When the primary particle diameter of the inorganic fine particles has the particle size distribution as described above, transferability is improved and cleaning properties are also improved.

In addition, it is assumed that a filler layer is formed on the toner, which makes the surface of the toner particles uneven, thereby improving the cleaning property.
By setting the toner circularity to 0.94 or more, a high transfer rate can be obtained, and since there is little change in the amount of toner colliding with the cleaning blade, a stable cleaning operation can be performed, and good cleaning properties and durability can be obtained. In addition, the transferred visible image can also be obtained as an image having no halftone unevenness.

  The volume average particle diameter of the toner is preferably 5.5 μm or less. As a result, an image having high resolution and high character sharpness was obtained.

The surface friction resistance of the photoreceptor is preferably 0.25 or less.
The blade edge is deformed by dragging the blade by the photoconductor, but the deformation is prevented if the photoconductor has a sufficiently low frictional resistance.

  Regarding the toner applied to the method of the present invention, since the filler layer is formed in the vicinity of the surface of the resin particle for toner, the toner surface can be formed with an appropriate uneven shape, and the average of the primary particles is in the surface state. By containing inorganic fine particles having a particle size of 90 to 300 nm and a toner having a circularity of 0.94 or more, the adhesion state between the resin particles for toner and the inorganic fine particles is determined in each step of the image forming process. It has been confirmed that the toner can be in an appropriate range and the toner can be appropriately contacted with each member to improve transferability, form a high-quality image, and maintain good cleaning properties.

As described above, the resin particles for toner have a filler layer near the surface.
Although this filler layer can be observed with a transmission electron microscope (TEM), the filler resin is not covered with the filler layer on the outermost surface of the resin particles for toner, and the filler layer is formed along the surface shape. It is preferable that
The inclusion is a state in which the filler is present inside the outermost surface of the toner resin particles, and the filler is exposed to the outside of the toner resin particles or adsorbed on the surface of the toner resin particles. When the toner is completely covered, the filler characteristics are dominant as the surface and bulk characteristics of the toner resin particles, and the characteristics of the toner resin particle binder resin are hardly exhibited.
On the contrary, when the filler is included, the characteristics of the binder resin are easily expressed. As a result, the low-temperature fixability is improved, and when the wax is contained, the wax is likely to ooze out during the heat fixing, so that the hot offset resistance is improved.

  The filler layer is preferably formed along the surface shape (unevenness) of the resin particles for toner, but it is not necessary to use the entire vicinity of the surface of the resin particles for toner as the filler layer.

The film thickness of the filler layer formed in the vicinity of the surface of the resin particles for toner can be measured by analyzing the image of the cross section of the resin particles with a transmission electron microscope (TEM).
That is, resin particles are dispersed in a sucrose saturated solution (67% by mass solution) (hereinafter,% means mass% unless otherwise specified), frozen at −100 ° C., and then cryocooled. After slicing to a thickness of about 1000 angstroms and staining the filler with ruthenium tetroxide, the resin particle cross section was photographed with a transmission electron microscope at a magnification of 10000 times, and an image analysis apparatus (for example, Nexus NEW CUBE ver. 2.5 ( NEXUS, etc.), etc.), the area where the filler occupies 50% or more in the area where the thickness is a certain distance from the surface of the resin particle in the vertical direction inside the particle in the cross section where the cross-sectional area is maximum. Let the distance be the thickness of the filler layer.
In addition, let the said measured value be the average value which computed each value about ten resin particles chosen at random.

The film thickness of the filler layer is 0.005 μm to 0.5 μm, preferably 0.01 μm to 0.2 μm, and more preferably 0.02 μm to 0.1 μm.
In order to form the filler layer, at least a binder resin and a toner material liquid in which a filler is dispersed in an organic solvent are used as particles in an aqueous medium, and toner resin particles are produced by a process such as solvent removal and drying. Therefore, it can form preferably.
The uneven shape on the surface of the toner resin particles is a step of removing the solvent, and when the volume of the resin particles for toner shrinks, the surface area reduction rate is significantly slower than the volume shrinkage rate because the filler layer is formed. It is considered that the resin particle surface is formed to have an appropriate elasticity and to increase the viscosity of the resin particle surface from the inside of the resin particle.
If the thickness of the outer shell layer of the filler is within the above range, the difference in viscosity between the resin particle surface and the resin particle inside becomes large, and irregularities are easily developed on the particle surface.

The method for dispersing the filler is not particularly limited, and a known method can be applied.
For example, the following methods (1) to (5) and a combination thereof can be applied.
(1) Resin (a) and filler (b) are melt-kneaded by a kneader in the presence of a solvent (u) and / or a dispersant as required, and a master batch in which (b) is dispersed in (a) A method of obtaining (mb1).
(2) After the filler (b) is dissolved or suspended in the solvent (u) together with the resin (a) or the precursor (a0) of the resin (a) as necessary, cooling crystallization, solvent crystallization, etc. The method of precipitating in the liquid.
(3) The filler (b) is dissolved or suspended in the solvent (u) together with the resin (a) or the precursor (a0) of the resin (a) as necessary, and precipitated in the gas phase by spray drying or the like. And then mixing and dispersing in the solvent (u).
(4) The filler (b) is dissolved or suspended in the solvent (u) together with the resin (a) or the precursor (a0) of the resin (a) as necessary, and then mechanically wet pulverized by a disperser. Or the method of crushing.
(5) A method of adding and mixing (b) synthesized in the solvent (u).

From the viewpoint of dispersion stability, for example, the following method is preferred.
A method in which a filler (b) dispersed in water is wet-treated by adding a treating agent (d), and then a solvent-substituted organosol is added and mixed.
Metal oxide hydrogel synthesized by hydrothermal synthesis method, sol-gel method or the like, or dispersion of organic fine particles obtained by emulsion polymerization, seed polymerization, suspension polymerization or the like is used as the surface treatment agent (d). And a method of replacing the water with a solvent (u) (preferably methyl ethyl ketone, ethyl acetate, etc.).
Commercially available organosols obtained by the above method (for example, organosilica sol manufactured by Nissan Chemical Industries, etc.) can also be used.

Next, the filler will be described in detail.
The volume average particle diameter of the primary particles of the filler is preferably 0.001 to 0.5 μm, more preferably 0.001 to 0.1 μm, and particularly preferably 0.002 to 0.05 μm.
When the volume average particle size of the filler is 0.1 μm or more, it is preferably measured using a laser particle size distribution measuring device, and when it is 0.1 μm or less, it is preferably calculated from the BET specific surface area and the true specific gravity.
The BET specific surface area can be measured using an apparatus based on a normal nitrogen adsorption method (for example, trade name: QUANTTASORB (manufactured by QUANTACHROME)). The primary particle diameter of (b1) can be measured by dividing the reciprocal of the BET specific surface area of (b1) by the true specific gravity of (b1).

The content of (b) in (a) is preferably 0.01 to 50%, more preferably 0.05 to 45%, and particularly preferably 0.1 to 40%.
The content of (b1) in (a) is preferably 0.01 to 20%, more preferably 0.05 to 18%, and particularly preferably 0.1 to 15%.
The proportion of (b1) in (b) is preferably 10% or more, more preferably 20% or more.

  The higher the aspect ratio of the filler (b1), the higher the effect of forming irregularities on the surface of the resin particle (A). Therefore, as the aspect ratio of (b1) is higher, the unevenness can be formed on the surface of the resin particle with a lower addition amount.

  The filler (b) [including the filler (b1)] is not particularly limited as long as it is an inorganic or organic particulate substance that does not dissolve in the solvent (u). (B) may be used alone or in combination of two or more depending on the purpose. In (b), colorants, waxes, charge control agents and the like generally used for toner resin particles are included. Moreover, these can also be made into (b1) by the following filler surface treatment.

Examples of organic fillers include vinyl resins, urethane resins, epoxy resins, ester resins, polyamides, polyimides, silicone resins, fluorine resins, phenol resins, melamine resins, benzoguanamine resins, urea resins, and aniline resins. Resin beads such as ionomer resin, polycarbonate, cellulose, and a mixture thereof.
Also, ester wax (carnauba wax, montan wax, rice wax, etc.), polyolefin wax (polyethylene, polypropylene, etc.), paraffin wax, ketone wax, ether wax, long chain (C30 or higher) aliphatic alcohol, long chain (C30 or more) Fatty acids and organic waxes such as a mixture thereof can be used. In addition, various organic dyes or organic pigments such as azo, phthalocyanine, condensed polycyclic, dye lake and the like, which are generally used as colorants, and derivatives thereof can be used. Among these, various organic dyes or organic pigments such as azo, phthalocyanine, condensed polycyclic, and dye lake, and derivatives thereof are preferably applicable.

Examples of the inorganic filler include silica, diatomaceous earth, alumina, zinc oxide, titania, zirconia, calcium oxide, magnesium oxide, iron oxide, copper oxide, tin oxide, chromium oxide, antimony oxide, yttrium oxide, cerium oxide, samarium oxide, Metal oxides such as lanthanum oxide, tantalum oxide, terbium oxide, europium oxide, neodymium oxide, ferrites, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, heavy calcium carbonate , Metal carbonates such as light calcium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, metal sulfates such as calcium sulfate, barium sulfate, gypsum fiber, calcium silicate (wollastonite, zonotlite), kaolin, clay, tar , Mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fibers, glass beads, glass flakes and other metal silicates, aluminum nitride, boron nitride, silicon nitride and other metal nitrides, potassium titanate, titanium Metal titanates such as calcium oxide, magnesium titanate, barium titanate, lead zirconate titanate aluminum borate, metal borates such as zinc borate and aluminum borate, metal phosphates such as tricalcium phosphate, Examples thereof include metal sulfides such as molybdenum sulfide, metal carbides such as silicon carbide, carbons such as carbon black, graphite, and carbon fiber, and other fillers.
Among these, a metal oxide is preferable as (b1), and silica, alumina, and titania are more preferable.

As the inorganic fine particles, inorganic oxides can be applied. For example, oxides of silica, alumina, titania, and the like using metals such as silicon, aluminum, titanium, zirconium, cerium, iron, and magnesium can be applied. Particularly preferred are silica, titania and alumina.
When the average particle size of the inorganic oxide is less than 90 nm, the inorganic oxide is buried in the toner by use over time in which the toner receives an impact force by stirring and mixing with the carrier or the toners in the developing device. .
When the average particle diameter exceeds 300 nm, the inorganic oxide easily desorbs from the toner surface, and is desorbed from the toner surface by mixing / stirring in the developing device 5 to change the toner characteristics. Will occur.
Therefore, the average particle size of the inorganic oxide is desirably 90 to 150 nm.

The inorganic oxide is preferably contained in an amount of 0.4 wt% or more based on the toner.
Since the inorganic oxide has a large particle size, the number per unit weight is small, and when it is less than 0.4 wt%, the number of inorganic oxides on the toner surface is small and the effect of improving the transfer rate is reduced. However, it is necessary not to exceed 5 wt%. If it exceeds 5 wt%, the amount present on the toner surface increases, and the toner surface is covered and easily detached from the toner surface, causing an abnormal image.

Examples of inorganic oxides include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, iron oxide, magnesium oxide, calcium oxide, manganese oxide, zinc oxide, strontium oxide, strontium titanate, acid value barium, and acid value cesium. Or other inorganic oxides. Interoxide compounds such as strontium titanate and barium titanate can also be used. Of these oxides, silicon oxide is particularly preferable.
In the case of silicon oxide, the color is white and it can be used for a color toner, and is highly safe. As manufacturing methods, two types of manufacturing methods have been established, and amorphous and spherical shapes can be easily produced.
In the case of the amorphous form, there is a combustion type silica in which silicon tetrachloride is burned in the gas phase, and in the case of the spherical form, there is a method for producing silicon oxide by a sol-gel method in which silicon oxide is precipitated in the aqueous phase. In the sol-gel method, alkoxysilane is hydrolyzed and condensed in an aqueous solution to deposit silicon oxide. Examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetraisoproxysilane, and tetrabutoxysilane. Examples of the hydrolysis catalyst include ammonia, urea, monoamine and the like.
By making the inorganic oxide spherical, the fluidity of the toner can be increased. Also, the transfer rate can be improved.
Furthermore, it is effective to perform surface modification treatment with a hydrophobizing agent or the like. Typical examples of the hydrophobizing agent include the following. Dimethyldichlorosilane (DDS), trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyl Examples include trichlorosilane, chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, hexamethyldisilazane (HMDS), hexaphenyldisilazane, hexatolyldisilazane, and the like. The inorganic oxide is preferably used in the range of 0.1 to 2 wt% with respect to the toner. If it is less than 0.1 wt%, the effect of improving toner aggregation is poor, and if it exceeds 2 wt%, problems such as toner scattering between fine lines, contamination in the machine, scratches and abrasion of the photoreceptor tend to occur.

Furthermore, in addition to the inorganic oxide described above, inorganic fine particles are added to the toner as an external additive.
The external additive is added to control the flow characteristics and charging characteristics of the toner. Examples of inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, oxidation Examples thereof include chromium, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
In addition, polymer fine particles such as polystyrene, methacrylic ester and acrylate copolymer obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine and nylon, thermosetting Polymer particles made of resin may be used.

In the same manner as the inorganic oxide, such an external additive for inorganic fine particles can be subjected to surface treatment to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity.
For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. It is done. In particular, it is preferable to use hydrophobic silica and hydrophobic titanium oxide obtained by subjecting silica and titanium oxide to the above surface treatment. The primary particle diameter of the inorganic fine particles is preferably 8 to 50 nm, and particularly preferably 8 to 40 nm.
The use ratio of the inorganic fine particles is preferably 0.01 to 5 wt% of the toner, and particularly preferably 0.1 to 2.0 wt%.

As a method of containing the inorganic oxide having an average particle diameter of 90 to 300 nm and the inorganic fine particles of the external additive as described above, there is usually a method in which these inorganic oxide and the toner base particles are put in a mixer and stirred. Can be mentioned.
As another method, there is a method in which the toner is externally added in an aqueous and / or alcohol solvent. In this method, an inorganic oxide is added to a toner dispersed in an aqueous solvent, and adhered to the toner surface.
When this inorganic oxide is hydrophobized, it may be dispersed after a small amount of alcohol or the like is used in combination to lower the interfacial tension to facilitate wetting. Thereafter, the solvent can be removed by heating to fix it, and desorption can be prevented. Thereby, the inorganic oxide can be uniformly dispersed on the toner surface.
Further, when the toner and the additive are dispersed in the aqueous solvent, the additive can be dispersed more uniformly on the toner surface by adding the surfactant.
Further, it is preferable to use an inorganic oxide or a surfactant having a polarity opposite to that of the toner.

Next, the average circularity of the toner will be described.
The average circularity of the toner is a value obtained by optically detecting particles and dividing by the perimeter of an equivalent circle having the same projected area.
Specifically, it can be measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation).
In a predetermined container, 100 to 150 mL of water from which impure solids have been previously removed is added, 0.1 to 0.5 mL of a surfactant is added as a dispersant, and about 0.1 to 9.5 g of a measurement sample is further added. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the concentration and dispersion of the dispersion are set to 3,000 to 10,000 / μL, and the shape and distribution of the toner are measured.
In the method of the present invention, the toner is assumed to have an average circularity of 0.94 or more and a projected shape that is close to a circle, so that the dot reproducibility is excellent and a high transfer rate can be obtained.
When the average circularity is less than 0.94, the toner is separated from the spherical shape, the dot reproducibility is deteriorated, and the number of contact points with the photosensitive member as the latent image carrier increases, so that the releasability. Deteriorates and the transfer rate decreases.
Furthermore, the toner of the present invention has moderate irregularities on the surface.
As described above, the spherical toner having a low adhesion between the toner and the latent image carrier or the toner can obtain a high transfer rate, but has problems due to generation of transfer dust and a decrease in cleaning properties. Therefore, the surface of the toner is not smooth, and it is preferable that the surface of the toner has irregularities and is in proper contact with the latent image carrier.

Next, the shape factor of the toner will be described.
The toner applied in the method of the present invention preferably has a shape factor SF-2 of 120 or more and 150 or less.
The shape factor SF-2 indicates the degree of unevenness of the shape of the toner, and a photograph of the toner is taken with a scanning electron microscope (S-800: manufactured by Hitachi, Ltd.), and this is taken as an image analysis device (LUSEX3: Nireko). Analysis and calculation).

Specifically, as shown in the following equation (1), the square of the perimeter PERI of the figure formed by projecting the toner onto the two-dimensional plane is divided by the figure area AREA and multiplied by 100π / 4. is there.
SF-2 = {(PERI) 2 / AREA} × (100π / 4) (1)
If the value of SF-2 is less than 120, the toner surface has few irregularities and a sufficient contact area with the latent image carrier cannot be obtained. In addition, as the value of SF-2 increases, the unevenness of the toner shape becomes more prominent. However, when the value exceeds 150, the surface unevenness prevents the toner from being faithfully transferred to the latent image during transfer. It is not preferable because it leads to a decrease.

Further, the toner of the present invention has a volume average particle diameter (Dv) of 2 μm or more and 8 μm or less, and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.00. It is preferable that it is 1.30 or more.
By using a toner having such a particle size and particle size distribution, it is excellent in heat-resistant storage stability, low-temperature fixability, and hot offset resistance, and particularly when used in a full-color copying machine, etc. It was confirmed that sex was obtained.
In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. In addition, when the volume average particle size is smaller than the range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the magnetic carrier during a long period of stirring in the developing device, and the charging ability of the magnetic carrier is reduced. When used as a developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.
On the contrary, when the volume average particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed. In many cases, the variation in toner particle size becomes large.
The particle size of the toner is further preferably 2.5 to 7 μm.
On the other hand, if Dv / Dn exceeds 1.30, the charge amount distribution becomes wide and the resolving power decreases, which is not preferable.
The average particle size and particle size distribution of the toner can be measured using a Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter).
Specifically, it can be measured by using a Coulter Counter TA-II type connected to an interface (manufactured by Nikka Giken) and a personal computer (PC9801: manufactured by NEC) that outputs number distribution and volume distribution.

Next, a method for manufacturing the cleaning blade will be described.
The cleaning blade can be produced by a conventionally known composition and construction method.
In general, urethane rubber or the like that can easily obtain high elasticity can be applied.
For polyurethane elastomers, polyethylene adipate ester or polycaprolactone ester is usually used as the polyol component, and a prepolymer is prepared using 4,4′-diphenylmethane diisocyanate as the polyisocyanate component. It is manufactured by adding a catalyst, crosslinking in a predetermined mold, post-crosslinking in a furnace, and then aging at room temperature.

As the high molecular weight polyol, for example, a polyester polyol which is a condensate of an alkylene glycol and an aliphatic dibasic acid, for example, ethylene adipate ester polyol, butylene adipate ester polyol, hexylene adipate ester polyol, ethylene propylene adipate ester polyol, ethylene Polyester polyols such as butylene adipate ester polyol, polyester polyols of alkylene glycol and adipic acid such as ethylene neopentylene adipate polyol, polycaprolactone polyols such as polycaprolactone ester polyol obtained by ring-opening polymerization of caprolactone, poly Polyesters such as (oxytetramethylene) glycol and poly (oxypropylene) glycol Ether-based polyols and the like can be applied.
Other low molecular weight polyols include, for example, 1,4-butanediol, ethylene glycol, neopentyl glycol, hydroquinone-bis (2-hydroxyethyl) ether, 3,3′-dichloro-4,4′-diaminodiphenyl. Dihydric alcohols such as methane, 4,4'-diaminodiphenylmethane, 1,1,1-trimethylolpropane, glycerin, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylol Trivalent and higher polyhydric alcohols such as ethane, 1,1,1-tris (hydroxyethoxymethyl) propane, diglycerin, pentaerythritol and the like can be mentioned.
Specific examples of the curing catalyst include 2-methylimidazole and 1,2-dimethylimidazole. In particular, 1,2-dimethylimidazole is preferably used. Such a catalyst is usually used in an amount of 0.01 to 0.5 parts by weight, preferably 0.05 to 0.3 parts by weight, based on 100 parts by weight of the main agent.

Next, a toner manufacturing method will be described.
For example, the toner can be made of the following constituent materials.
(Modified polyester)
The toner contains a modified polyester as a binder resin.
The modified polyester refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or resin components having different configurations are bonded to the polyester resin by a covalent bond, an ionic bond, or the like.
Specifically, the polyester terminal is modified by introducing a functional group such as a carboxylic acid group or an isocyanate group that reacts with a hydroxyl group into the polyester terminal and further reacting with an active hydrogen-containing compound.

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

The urea-modified polyester is produced as follows.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable.
Examples of the dihydric alcohol (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.), alkylene ether glycol (diethylene glycol). , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.), alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols, bisphenol Alkylene oxide Lumpur acids (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts.
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is combined use with.
The trihydric or higher polyhydric alcohol (TO) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.), and trihydric or higher phenols. (Trisphenol PA, phenol novolak, cresol novolak, etc.), and alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC), (DIC) alone, (DIC) and a small amount of (TC) Is preferred.
Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.), alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.), aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) , Naphthalenedicarboxylic acid, etc.).
Among these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polyvalent carboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.), alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) ), Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.), araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.), isocyanates, the above polyisocyanates as phenol derivatives, oximes, Those blocked with caprolactam or the like, and combinations of two or more of these may be mentioned.

The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1.
When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates.
When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. .
If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

Next, as an amine filler to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4), Examples include amino acid (B5), and amino acid block of B1 to B5 (B6).
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.) and alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.) and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like. Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amine fillers, preferred are B1 and a mixture of B1 and a small amount of B2.

The ratio of the amine filler is usually 1 as an equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the polyester prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine filler. / 2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2.
When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The above-mentioned modified polyester applied to the method of the present invention is produced by a one-shot method or a prepolymer method.
The weight average molecular weight of the modified polyester is usually 10,000 or more, preferably 21 million, and more preferably 30,000 to 1,000,000.
The peak molecular weight at this time is preferably 1000 to 10000. When the molecular weight is less than 1000, the elongation reaction hardly occurs, the elasticity of the toner is small, and as a result, the resistance to hot offset deteriorates. On the other hand, when it exceeds 10,000, the problem in production becomes high in the deterioration of fixability, particle formation and pulverization.
The number average molecular weight of the modified polyester is not particularly limited when the unmodified polyester described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. In the case of the modified polyester alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.
In the crosslinking and / or elongation reaction between the polyester prepolymer (A) and the amine filler for obtaining the modified polyester, a reaction terminator can be used as necessary to adjust the molecular weight of the resulting urea-modified polyester. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).
In addition, the molecular weight of the produced | generated polymer can be measured using THF as a solvent using gel permeation chromatography (GPC).

(Unmodified polyester)
In the method of the present invention, not only the modified polyester is used alone, but also an unmodified polyester may be contained as a binder resin component together with the modified polyester.
By using the unmodified polyester in combination, the low-temperature fixability and the gloss when used in a full-color apparatus are improved, which is preferable to the single use.
Examples of the unmodified polyester include polycondensates of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) similar to the polyester component of the modified polyester, and preferable ones are the same as the modified polyester. .

The unmodified polyester is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example.
The modified polyester and the unmodified polyester are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance.
Therefore, the modified polyester component and the unmodified polyester preferably have similar compositions. When the unmodified polyester is contained, the weight ratio of the modified polyester to the unmodified polyester is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75. Particularly preferred is 7/93 to 20/80.
When the weight ratio of the modified polyester is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

The peak molecular weight of the unmodified polyester is usually 1000 to 10,000, preferably 2000 to 8000, and more preferably 2000 to 5000.
If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate.
The hydroxyl value of the unmodified polyester is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester is preferably 1 to 5, more preferably 2 to 4.
Since a high acid value wax is used for the wax, the binder is easily matched with the toner used for the two-component developer because the low acid value binder leads to charging and high volume resistance.

The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C., preferably 55 to 65 ° C. If it is less than 35 ° C., the heat resistant storage stability of the toner is deteriorated, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient.
Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner of the present invention tends to have good heat storage stability even when the glass transition point is low, as compared with known polyester-based toners. Show.
The glass transition point (Tg) can be measured with a differential scanning calorimeter (DSC).

Next, the colorant will be described.
As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher , Yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sayred, Parachlor Ortonito Aniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Lid Russian nin green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

The colorant can also be used as a master batch combined with a resin.
As binder resin kneaded with masterbatch production or masterbatch, styrene, such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and substituted polymers thereof, or co-polymerization of these with vinyl compounds Coalescence, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin , Aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes, and the like, which can be used alone or in combination.

The masterbatch can be obtained by mixing and kneading the masterbatch resin and the colorant under high shear.
At this time, an organic solvent is used to enhance the interaction between the colorant and the resin.
In addition, a so-called flushing method, which is a wet cake of colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

Next, the charge control agent will be described.
As the charge control agent, conventionally known ones can be used. For example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (fluorine) Modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.
Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts.
Of these, substances that control the negative polarity of the toner are particularly preferably used.
The amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as needed, and the dispersion method, and is not uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is lowered, and the image density is lowered. Invite.

Next, the release agent will be described.
As a release agent, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface, thereby fixing. Effective against high temperature offset without applying a release agent such as oil to the roller.
Examples of such a wax component include the following.
Waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline, and petrolatum. And petroleum wax.
In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used.
Furthermore, 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, fatty acid amides such as chlorinated hydrocarbons, and low molecular weight crystalline polymer resins, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .
The charge control agent and the release agent can be melt-kneaded together with the master batch and the binder resin, and of course, they may be added when dissolved and dispersed in the organic solvent.

  Next, a toner manufacturing method will be described. Here, although a preferable manufacturing method is shown, it is not limited to this.

(Production method of toner binder)
The toner binder can be produced by the following method.
Polyhydric alcohol (PO) and polycarboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxy titanate, dibutyltin oxide, etc., and water generated while reducing the pressure as necessary. Distill off to obtain a polyester having a hydroxyl group. Subsequently, at 40-140 degreeC, this is made to react with a polyvalent isocyanate compound (PIC), and the prepolymer (A) which has an isocyanate group is obtained. Further, (A) is reacted with an amine filler at 0 to 140 ° C. to obtain a polyester modified with a urea bond.
When reacting (PIC) and when reacting (A) with the filler, a solvent may be used as necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers Inactive to polyvalent isocyanate compounds (PIC) such as benzene (such as tetrahydrofuran).
When the unmodified polyester is used in combination, the unmodified polyester is produced in the same manner as the polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of the modified polyester and mixed.

Next, a toner manufacturing method will be specifically described.
The colorant, unmodified polyester, polyester prepolymer (A) having an isocyanate group, release agent, and inorganic filler are dispersed in an organic solvent to prepare a toner material liquid.
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 1-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 1-100 weight part, More preferably, it is 25-70 weight part.

The inorganic filler exists in the vicinity of the surface of the toner base particles, and plays a role of controlling the shape of the toner base particles during the manufacturing process.
Examples of the inorganic filler include silica, diatomaceous earth, alumina, zinc oxide, titania, zirconia, calcium oxide, magnesium oxide, iron oxide, copper oxide, tin oxide, chromium oxide, antimony oxide, yttrium oxide, cerium oxide, samarium oxide, Metal oxides such as lanthanum oxide, tantalum oxide, terbium oxide, eurobium oxide, neodymium oxide, ferrites, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, heavy carbonates Metal carbonates such as calcium, light calcium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalicite, metal sulfates such as calcium sulfate, barium sulfate, gypsum fiber, calcium silicate (wollastonite, zonotlite), kaolin, clay Metal silicates such as talc, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, glass flakes, metal nitrides such as aluminum nitride, boron nitride, silicon nitride, potassium titanate , Magnesium titanate, magnesium titanate, barium titanate, lead zirconate titanate aluminum borate, etc., metal borates such as zinc borate, aluminum borate, metal phosphates such as tricalcium phosphate, Examples thereof include metal sulfides such as molybdenum sulfide, metal carbides such as silicon carbide, carbons such as carbon black, graphite, and carbon fiber, and other fillers. Of these, silica, alumina, and titania are preferable.

In order to disperse the inorganic filler in the organic solvent, the inorganic filler is preferably used in the form of the following organosol.
In order to obtain an organosol of an inorganic filler, for example, a dispersion of a hydrogel of an inorganic filler synthesized by a wet method (hydrothermal synthesis method, sol-gel method, etc.) is hydrophobized with a surface treatment agent, and water is added. Examples of the method include substitution with an organic solvent such as methyl ethyl ketone and ethyl acetate.

Examples of the surface treatment agent include silicon oil, coupling agents (for example, silane coupling agents, titanate coupling agents and aluminate coupling agents), amine compounds, and various commercially available pigment dispersants. Silicon oil, silane coupling agents, and amine compounds are preferably used.
Examples of silicone oil include straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil, methacrylic acid modified silicone oil, epoxy modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, amino Examples include modified silicone oil such as modified silicone oil. Examples of the silane coupling agent include organoalkoxysilane, organochlorosilane, organosilazane, organodisilazane, organosiloxane, organodisiloxane, and organosilane.
As the amine compound, a compound that is compatible with an organic solvent and has at least one of a primary amine group, a secondary amine group, and a tertiary amine group can be used. The amine compound is a polyester prepolymer. In particular, it is preferable to use a compound having a tertiary amine group that does not contain active hydrogen. Examples of such tertiary amine compounds include triethylamine, N, N′-dimethylaminodiethyl ether, tetramethylhexamethylenediamine, tetramethylethylenediamine, dimethylethanolamine, N-methyl-N ′-(2-dimethylamino). ) Ethylpiperazine, 1,2-dimethylimidazole, triethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriami, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine , Tetramethylguanidine, 1,8-diazabicyclo [5,4,0] undecene-7, bis (2-morpholinoethyl) ether, and the like may be used in combination. Of these, triethylamine, 1,8-diazabicyclo [5,4,0] undecene-7, and bis (2-morpholinoethyl) ether are particularly preferable.

As a method for producing an inorganic sol organosol, for example, the method described in JP-A No. 11-43319 can be applied. As a commercially available organosol, for example, an organosilica sol (all manufactured by Nissan Chemical Industries, Ltd.) can be mentioned.
The particle size of the inorganic filler is preferably 5 to 100 nm, more preferably 10 to 30 nm. The addition amount is 1 to 10 parts by weight, preferably 2 to 7 parts by weight, based on 100 parts by weight of the toner resin component (including a binder and a wax component as a release agent). When added as an organosol, the addition amount is adjusted so that the solid content is in the above range.
The toner of the present invention, that is, the toner having a surface shape in which the A / S value is in a specified range and the contact with the member is a line contact, is adjusted by adjusting the kind of inorganic filler and the addition amount thereof. To obtain the toner.

The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.

Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, fatty acid amide derivatives, polyhydric alcohols Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount.
Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  In addition, as the cationic surfactant, aliphatic quaternary ammonium such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt which has a fluoroalkyl group right Salt, benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (Daikin Industries) Smoke), Megafuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.) and the like.

The resin fine particles are added to stabilize the toner base particles formed in the aqueous medium. For this reason, it is preferable to add so that the coverage existing on the surface of the toner base particles is in the range of 10 to 90%. For example, polymethyl methacrylate fine particles 1 μm and 3 μm, polystyrene fine particles 0.5 μm and 2 μm, poly (styrene-acrylonitrile) fine particles 1 μm, trade names are PB-200H (manufactured by Kao), SGP (manufactured by Soken), Techno Examples include polymer SB (manufactured by Sekisui Chemical Co., Ltd.), SGP-3G (manufactured by Sokensha), and micropearl (manufactured by Sekisui Fine Chemical Co., Ltd.).
In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid.
For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, polyoxy Propylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene Polyoxyethylenes such as nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be applied.

The dispersion method is not particularly limited, and any of known techniques such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied.
Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm.
When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm.
The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes.
The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

Simultaneously with the preparation of the emulsion, an amine filler is added to cause a reaction with the polyester prepolymer (A) having an isocyanate group.
This reaction involves molecular chain crosslinking and / or elongation.
Although reaction time is selected by the reactivity of the isocyanate group structure and amine filler which polyester prepolymer (A) has, it is 10 minutes-40 hours normally, Preferably it is 2 to 24 hours.
The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C.
Moreover, a well-known catalyst can be used as needed.
Specific examples include dibutyltin laurate and dioctyltin laurate.

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

A charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner.
The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained.
In addition, the surface morphology can be controlled between smooth and umeboshi shapes.

The toner is mixed with a magnetic carrier and used as a two-component developer.
In this case, the carrier to toner content ratio in the developer is preferably 1 to 10 parts by weight of toner with respect to 100 parts by weight of carrier.
As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used.
Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin.
Polyvinylidene and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Polyester resins such as halogenated olefin resins such as vinyl chloride, polyethylene terephthalate resins, and polybutylene terephthalate resins, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, poly Hexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro terpolymers such as the non-fluoric monomers including, and silicone resins.
Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner can also be used as a one-component magnetic toner that does not use a carrier, or a non-magnetic toner.

Further, when preparing the developer, in order to improve the fluidity, storage stability, developability, and transferability of the developer, the hydrophobic silica mentioned above is further added to the developer produced as described above. Inorganic fine particles such as fine powder may be added and mixed.
For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature.
In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually.
Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc.
A strong load may be given first, then a relatively weak load, and vice versa.
Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.

Next, a method for manufacturing the photoreceptor will be described.
The photoreceptor applied in the present invention is not particularly limited, and can be produced by a conventionally known method.
The method of setting the photoreceptor surface friction coefficient to 0.3 or less may be performed using a conventionally known method.
For example, a method of providing a protective layer of a resin having a low friction coefficient on the outermost surface of the photoconductor, a method of dispersing fine particles having a low friction coefficient such as a fluorine-containing resin in the photoconductor, a fatty acid metal salt, etc. on the surface of the photoconductor The method of apply | coating the lubricant of this is mentioned.

  Materials used for the protective layer include ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether resin, allyl resin, phenol resin, polyacetal resin, polyamide resin, polyamideimide resin, polyacrylate resin, Polyallylsulfone resin, polybutylene resin, polybutylene terephthalate resin, polycarbonate resin, polyethersulfone resin, polyether resin, polyethylene terephthalate resin, polyimide resin, acrylic resin, polymethylpentene resin, polypropylene resin, polyphenylene oxide resin, polysulfone resin, AS Examples thereof include resins such as resin, AB resin, BS resin, polyurethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, and epoxy resin.

A filler is added to the protective layer for the purpose of improving wear resistance and filming resistance.
The amount of these fillers added to the protective layer is usually 10 to 40%, preferably 20 to 30% on a weight basis.
If the amount of the filler is less than 10%, the wear is large and the durability is inferior. If it exceeds 40%, the bright portion potential during exposure is remarkably increased, and the decrease in sensitivity cannot be ignored.
The average particle size of the filler is 0.3 to 1.2 μm, preferably 0.3 to 0.7 μm. When the particle size is small, the wear resistance is not sufficient, When the particle size is large, writing light is scattered, which is not preferable.

A dispersion aid may be added to the protective layer in order to improve the dispersibility of the filler.
As the dispersion aid, those used for coatings and the like (for example, modified epoxy resin condensate, unsaturated polycarboxylic acid low molecular weight polymer, etc.) can be used as appropriate, and the amount is usually the amount of filler contained on a weight basis. Is 0.5 to 4%, preferably 1 to 2%.

In addition, it is very effective to add the above-described charge transporting material to the protective layer, and the amount of addition may be the same as that of the charge transporting layer, and the characteristics for exposure such as reduction of residual potential can be improved.
In the case of a low molecular charge transport material on a weight basis, the amount of the charge transport material added is preferably 20 to 60% of the solid content excluding the filler, and the exposure characteristics are within the range where the mechanical characteristics of the protective layer are not impaired. Add to the extent to improve.
In the case of the polymer charge transporting material, since it has a function as a binder itself, the addition amount can be further increased, and the solid content excluding the filler can be 20 to 95%.
In general, it is known that a film in which a low-molecular charge transport material is added to a binder resin has a film strength that decreases according to the amount of the material added.
Furthermore, when the inorganic fine particles are added, it is necessary to maintain good adhesion with the binder, and in particular, the retention of the inorganic fine particles on the surface layer is important from the viewpoint of wear resistance. Usually, when an inorganic fine particle whose surface is treated is used, the affinity with the binder is improved and the strength of the film itself can be improved.
Further, an antioxidant can be added as necessary. The antioxidant will be described later.

  As a method for forming the protective layer, a normal coating method such as a spray method is adopted, and the thickness of the protective layer is suitably about 0.5 to 10 μm, preferably about 4 to 6 μm.

Another intermediate layer may be formed between the photosensitive layer and the protective layer constituting the photoreceptor.
In the intermediate layer, a binder resin is generally used as a main component.
Examples of the binder resin include polyamide resin, alcohol-soluble nylon, water-soluble polyvinyl butyral resin, polyvinyl butyral resin, and polyvinyl alcohol resin.
As the method for forming the intermediate layer, the above-described normal coating method is adopted, and the thickness of the intermediate layer is suitably about 0.05 to 2 μm.

  In addition, for the purpose of improving environmental resistance, antioxidants, plasticizers, lubricants, UV absorbers, low-molecular charge transporting substances and leveling agents are added to each layer, particularly for the purpose of preventing a decrease in sensitivity and an increase in residual potential. can do.

Antioxidants that can be added to each layer include phenol compounds such as 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, n -Octadecyl-3- (4-hydroxy-3,5-di-tert-butylphenol), 2,2-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2-methylene-bis- ( 4-ethyl-6-tert-butylphenol), 4,4-thiobis- (3-methyl-6-tert-butylphenol), 4,4-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1 , 3-Tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4 − Droxybenzyl) benzene, tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, bis [3,3-bis (4-hydroxy-3-tert-butyl) Phenyl) butyric acid] glycol ester, tocopherols and the like.
As paraphenylenediamines, N-phenyl-N-isopropyl-p-phenylenediamine, N, N-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N , N-di-isopropyl-p-phenylenediamine, N, N-dimethyl-N, N-di-t-butyl-p-phenylenediamine, and the like.
As hydroquinones, 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2- (2-octadecenyl) -5-methylhydroquinone and the like.
Examples of organic sulfur compounds include dilauryl-3,3-thiodipropionate, distearyl-3,3-thiodipropionate, and ditetradecyl-3,3-thiodipropionate.
Examples of the organic phosphorus compounds include triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, and tri (2,4-dibutylphenoxy) phosphine.

Plasticizers that can be added to each layer include phosphate ester plasticizers such as triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, Examples include tri-2-ethylhexyl phosphate and triphenyl phosphate.
As phthalate ester plasticizers, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, phthalic acid Dinonyl, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, methyl oleyl phthalate, octyl decyl phthalate, dibutyl fumarate, dioctyl fumarate, etc. Is mentioned.
Examples of the aromatic carboxylate plasticizer include trioctyl trimellitic acid, tri-n-octyl trimellitic acid, octyl oxybenzoate, and the like.
As an aliphatic dibasic ester plasticizer, dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, di-n-octyl adipate, adipate-n-octyl-n-decyl, Diisodecyl adipate, dicapryl adipate, di-2-ethylhexyl azelate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, di-2-ethylhexyl sebacate, di-2-sebacate Examples thereof include ethoxyethyl, dioctyl succinate, diisodecyl succinate, dioctyl tetrahydrophthalate, and di-n-octyl tetrahydrophthalate.
Examples of the fatty acid ester derivative plasticizer include butyl oleate, glycerin monooleate, methyl acetylricinoleate, pentaerythritol ester, dipentaerythritol hexaester, triacetin, and tributyrin.
Examples of the oxyester plasticizer include methyl acetyl ricinoleate, butyl acetyl ricinoleate, butyl phthalyl butyl glycolate, and tributyl acetyl citrate.
Epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, butyl epoxy stearate, decyl epoxy stearate, octyl epoxy stearate, benzyl epoxy stearate, dioctyl epoxy hexahydrophthalate, didecyl epoxy hexahydrophthalate, etc. Is mentioned.
Examples of the dihydric alcohol ester plasticizer include diethylene glycol dibenzoate and triethylene glycol di-2-ethylbutyrate.
Examples of the chlorine-containing plasticizer include chlorinated paraffin, chlorinated diphenyl, chlorinated fatty acid methyl, and methoxychlorinated fatty acid methyl.
Examples of the polyester plasticizer include polypropylene adipate, polypropylene sebacate, polyester, and acetylated polyester.
As sulfonic acid derivative plasticizers, p-toluenesulfonamide, o-toluenesulfonamide, p-toluenesulfoneethylamide, o-toluenesulfoneethylamide, toluenesulfone-N-ethylamide, p-toluenesulfone-N-cyclohexylamide Etc.
Examples of the citric acid derivative plasticizer include triethyl citrate, triethyl acetyl citrate, tributyl citrate, tributyl acetyl citrate, tri-2-ethylhexyl acetyl citrate, and acetyl citrate-n-octyldecyl.
Other examples include terphenyl, partially hydrogenated terphenyl, camphor, 2-nitrodiphenyl, dinonylnaphthalene, methyl abietic acid, and the like.

Examples of ultraviolet absorbers that can be added to each layer include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2,4-trihydroxybenzophenone, 2,2,4,4-tetrahydroxybenzophenone as benzophenone-based ultraviolet absorbers. 2,2-dihydroxy 4-methoxybenzophenone and the like.
Examples of the salicylate ultraviolet absorber include phenyl salicylate, 2,4 di-t-butylphenyl 3,5-di-t-butyl 4-hydroxybenzoate, and the like.
As a benzotriazole ultraviolet absorber, (2-hydroxyphenyl) benzotriazole, (2-hydroxy5-methylphenyl) benzotriazole, (2-hydroxy5-methylphenyl) benzotriazole, (2-hydroxy-3-tert-butyl) 5-methylphenyl) 5-chlorobenzotriazole and the like.
Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3-diphenyl acrylate, methyl 2-carbomethoxy 3 (paramethoxy) acrylate, and the like.
Examples of the quencher (metal complex salt) ultraviolet absorber include nickel (2,2thiobis (4-t-octyl) phenolate) normal butylamine, nickel dibutyldithiocarbamate, nickel dibutyldithiocarbamate, cobalt dicyclohexyldithiophosphate and the like.
As HALS (hindered amine) -based ultraviolet absorbers, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1 -[2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionyloxy] -2,2,6,6-tetramethylpyridine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2 , 4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine and the like.

The image forming apparatus of the present invention will be described.
FIG. 1 shows a schematic configuration diagram of an example of an image forming apparatus according to the present invention.
In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) mounted thereon.

The copying apparatus main body 100 has a tandem type in which four image forming units 18 each having various units for performing an electrophotographic process such as charging, developing, and cleaning are arranged in parallel around a photosensitive member 40 as a latent image carrier. An image forming apparatus 20 is provided.
Above the tandem type image forming apparatus 20, there is provided an exposure apparatus 21 that exposes the photoreceptor 40 with laser light based on image information to form a latent image.
Further, an intermediate transfer belt 10 made of an endless belt member is provided at a position facing each photoreceptor 40 of the tandem type image forming apparatus 20. A primary transfer unit 62 for transferring the toner images of the respective colors formed on the photoconductor 40 to the intermediate transfer belt 10 is disposed at a position facing the photoconductor 40 via the intermediate transfer belt 10.
A secondary transfer device 22 that collectively transfers the toner images superimposed on the intermediate transfer belt 10 onto transfer paper conveyed from the paper feed table 200 is disposed below the intermediate transfer belt 10. The secondary transfer device 22 is configured by spanning a secondary transfer belt 24 that is an endless belt between two rollers 23, and is disposed by pressing against the support roller 16 via the intermediate transfer belt 10. The toner image on 10 is transferred onto a transfer sheet. A fixing device 25 for fixing the image on the transfer paper is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt.
The secondary transfer device 22 described above also has a sheet transport function for transporting the transfer paper after image transfer to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveyance function together.
In the illustrated example, a reversing device 28 for reversing the transfer paper so as to record images on both sides of the transfer paper is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. .

The developing device 4 of the image forming unit 18 uses a developer containing the above toner.
In the developing device 4, the developer carrying member carries and conveys the developer, and an alternating electric field is applied at a position facing the photoconductor 40 to develop the latent image on the photoconductor 40. By applying the alternating electric field, the developer is activated, the toner charge amount distribution can be narrowed, and the developability can be improved.

  Further, the developing device 4 can be a process cartridge that is integrally supported together with the photoreceptor 40 and is detachably formed on the main body of the image forming apparatus. In addition, the process cartridge may include a charging unit and a cleaning unit.

Next, the operation of the above-described image forming apparatus will be described.
First, a document is set on the document table 30 of the automatic document feeder 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed. Hold it down.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. At that time, the scanner 300 is immediately driven, and the first traveling body 33 and the second traveling body 34 travel. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34 and reflects by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.

When a start switch (not shown) is pressed, one of the support rollers 14, 15, 16 is rotated by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer belt 10 is rotated and conveyed. To do.
At the same time, the individual image forming means 18 rotates the photoconductors 40 to form black, yellow, magenta, and cyan single color images on the photoconductors 40, respectively.
Then, along with the conveyance of the intermediate transfer belt 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer belt 10.

On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped.
Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.
Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer belt 10, the sheet is fed between the intermediate transfer belt 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.

The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge image. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and the image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.
On the other hand, the intermediate transfer belt 10 after image transfer is removed by the intermediate transfer belt cleaning device 17 to remove residual toner remaining on the intermediate transfer belt 10 after image transfer, and is prepared for re-image formation by the tandem image forming apparatus 20.

Next, the present invention will be described with specific examples, but the present invention is not limited to the following examples.
(Prototype cleaning blade)
A polyurethane-based flat-plate cleaning blade was prototyped.
The characteristic values of the blade are shown in Table 1 below.
(Production of photoconductor)
As a photoconductor, a multilayer photoconductor in which a charge generation layer and a charge transport layer are sequentially laminated on a photoconductor substrate of Ricoh's ImagioNeoC385 was made as an experiment.
In addition, a prototype in which a protective layer containing 25% by weight of alumina fine particles (AA-03 manufactured by Sumitomo Chemical Co., Ltd., average particle size 0.3 μm) was laminated to a thickness of 5 μm on the obtained photoreceptor was made as a prototype.
The coefficient of friction of the photoconductor was controlled by adjusting the supply amount of the solid lubricant arranged together with the rotating nylon brush in the vicinity of the photoconductor of Ricoh Co., Ltd. ImagioNeoC385.

[Example 1]
A cleaning blade having the physical properties shown in Table 1 below was produced.
Regarding the photoreceptor, those having the physical properties shown in Table 1 below were prepared.
(Synthesis of organic fine particle emulsion)
In a reaction vessel equipped with a stir bar and thermometer, water 683 parts, sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts styrene, 83 parts methacrylic acid Then, 110 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, whereby a white emulsion was obtained. This was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours.
Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion was obtained.
This is referred to as (fine particle dispersion 1).
The volume average particle diameter of LA-920 (manufactured by HORIBA) measured using the above (fine particle dispersion 1) as a sample was 105 nm.
Further, a part of (fine particle dispersion 1) was dried to isolate the resin component.
The Tg of the resin component was 59 ° C., and the weight average molecular weight was 150,000.
(Preparation of aqueous phase)
990 parts of water, 80 parts of (fine particle dispersion 1), 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This is designated as (aqueous phase 1).
(Synthesis of ketimine)
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain a blocked amine. This is referred to as (ketimine compound 1). The amine value of this (ketimine compound 1) was 418.
(Preparation of masterbatch)
1200 parts water, 40 parts carbon black (manufactured by Cabot, Regal 400R), 60 parts polyester resin (manufactured by Sanyo Chemical Industries, RS801), 30 parts water, and mixed with a Henschel mixer (manufactured by Mitsui Mining) The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain a carbon black masterbatch.
This is referred to as (master batch 1).
(Preparation of oil phase)
A container equipped with a stir bar and a thermometer was charged with 400 parts of (low molecular weight polyester 1), 110 parts of carnauba wax, and 947 parts of ethyl acetate, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Thereafter, it was cooled to 30 ° C. over 1 hour.
Next, 500 parts of (Masterbatch 1) and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain a dissolved product. This is referred to as (raw material solution 1).
(Raw material solution 1) Transfer 1324 parts to a container and use a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed: 1 Kg / hr, disk peripheral speed: 6 m / sec, 0.5 mm zirconia bead filling amount : The wax was dispersed under the conditions of 80% by volume and the number of passes: 3 times.
Next, 1324 parts of a 65% ethyl acetate solution of (low molecular weight polyester 1) was added, and a dispersion was obtained using a bead mill under the same conditions as described above, with the number of passes being one time. This is designated as (Pigment / Wax Dispersion 1).
(Emulsification)
(Pigment / Wax Dispersion 1) 1772 parts, 50% ethyl acetate solution of (Prepolymer 1) (number average molecular weight 3800, weight average molecular weight 15000, Tg 60 ° C., acid value 0.5, hydroxyl value 51, and free isocyanate contained The amount is 1.53 wt%) 100 parts, (ketimine compound 1) 8.5 parts, and filler 6.9 parts in a container and 1 at 5,000 rpm using a TK homomixer (made by Tokushu Kika). After mixing for 1 minute, 1200 parts of (aqueous phase 1) was added to the container, and the mixture was mixed with a TK homomixer at 10,000 rpm for 20 minutes to obtain an aqueous medium dispersion. This is designated as (Emulsified slurry 1).
(Deorganic solvent)
(Emulsion slurry 1) is put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging is carried out at 45 ° C. for 4 hours to obtain a dispersion in which the organic solvent is distilled off. It was. This is referred to as (dispersed slurry 1).

(Washing → drying)
(1) 100 parts of (Dispersion Slurry 1) were filtered under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(2) 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake obtained in (1) above, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3) To the filter cake obtained in (2) above, 100 parts of 10% hydrochloric acid was added, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(4) After adding 300 parts of ion-exchanged water to the filter cake obtained in the above (3) and mixing with a TK homomixer (10 minutes at a rotation speed of 12000 rpm), the filtration operation was performed twice (filter cake 1 )

The above (filter cake 1) was dried at 45 ° C. for 48 hours in a circulating dryer.
Thereafter, a sieve (toner base particle 1) was obtained with a mesh having an opening of 75 μm.

(External additive treatment)
100 parts of the above obtained (toner base particles 1), 2 parts of hydrophobized silica (HDKH2000, Clariant Japan), 1 part of hydrophobized silica with a primary particle diameter of 80 nm, titanium oxide (MT-150A, Taca) One part was mixed with an aster mixer at 12000 rpm for 1 minute, and then a sieved toner was obtained with a mesh having an opening of 75 μm.

[Example 2]
The blade and photoconductor were prepared with the physical properties shown in Table 1 below.
A toner was obtained in the same manner as in Example 1 except that the steps from washing to external additive mixing in Example 1 were changed to the following conditions.
(Washing)
(Dispersion slurry 1) After filtering 100 parts under reduced pressure,
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(2) 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake obtained in (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake obtained in (2) and mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), followed by filtration.
(4) 300 parts of ion-exchanged water was added to the filter cake obtained in (3), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice to obtain a filter cake.
(Mixing of external additives 1)
To 100 parts of the filter cake, 500 parts of ion-exchanged water was added (redispersion slurry 1).
On the other hand, 2 parts of silica having a hydrophobized primary particle size of 80 nm was gradually added with stirring to a solution of 0.2 parts by weight of stearylamine acetate, 70 parts by weight of ion-exchanged water, and 30 parts by weight of methanol. A fine particle dispersion) was obtained.
The obtained silica fine particle dispersion was mixed with the previous redispersion slurry, then stirred at room temperature for 1 hour and filtered to obtain a filter cake.
(Dry)
The filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh of 75 μm to obtain toner particles.
(Mixing of external additives 2)
100 parts by weight of (toner base 1) obtained above and 1.0 part by weight of hydrophobic silica (HDK 2000H, manufactured by Clariant Japan) as an external additive were mixed by a Henschel mixer (blade rotation speed 2000 rpm, mixing time 30). Second, 5 cycles), and agglomerates were removed by passing through a sieve having an aperture of 38 μm to obtain a toner. This is referred to as (Toner 2).

Example 3
Regarding the blade and the photoreceptor, those having physical properties shown in Table 1 below were prepared.
A toner was obtained in the same manner as in Example 1 except that the following conditions were changed in Example 1.
(Emulsification, solvent removal)
(Pigment / Wax Dispersion 1) 749 parts, (Prepolymer 1) 115 parts, (Ketimine Compound 1) 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of (Aqueous Phase 1) was added to the container and mixed with a TK homomixer at 13,000 rpm for 10 minutes (Emulsion slurry 2).
(Emulsion slurry 2) was charged into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 6 hours, aging was carried out at 45 ° C. for 5 hours to obtain (dispersed slurry 2).

Example 4
Regarding the blade and the photoreceptor, those having physical properties shown in Table 1 below were prepared.
A toner was obtained in the same manner as in Example 1 except that the steps from emulsification to solvent removal were changed to the following conditions.
(Emulsification, solvent removal)
(Pigment / wax dispersion 1) 749 parts, 115 parts of (prepolymer 1) and 2.9 parts of (ketimine compound 1) were placed in a container and mixed for 2 minutes at 5000 rpm with a TK homomixer (manufactured by Tokushu Kika). Thereafter, 1200 parts of (Aqueous Phase 1) was added to the container, and mixed with a TK homomixer at a rotational speed of 13000 rpm for 40 minutes to obtain (Emulsion slurry 3).
(Emulsion slurry 3) was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 5 hours to obtain (dispersed slurry 3).

Example 5
Regarding the blade and the photoreceptor, those having physical properties shown in Table 1 below were prepared.
The toner of Example 1 was used.

Example 6
Regarding the blade and the photoreceptor, those having physical properties shown in Table 1 below were prepared.
The same toner as in Example 1 was used.

Example 7
Regarding the blade and the photoreceptor, those having physical properties shown in Table 1 below were prepared.
The same toner as in Example 1 was used.

Example 8
Regarding the blade and the photoreceptor, those having physical properties shown in Table 1 below were prepared.
The same toner as in Example 1 was used.

[Comparative Example 1]
Regarding the blade and the photoreceptor, those having physical properties shown in Table 1 below were prepared.
In the toner, no organosilica sol was added during the oil phase adjustment in the process shown in Example 1. The other conditions were the same as in Example 1 to produce a toner.

[Comparative Example 2]
Regarding the blade and the photoreceptor, those having physical properties shown in Table 1 below were prepared.
In the toner, no hydrophobic silica having a primary particle diameter of 80 nm was added when the external additive was mixed in the process shown in Example 1. The other conditions were the same as in Example 1 to produce a toner.

[Comparative Example 3]
Regarding the blade and the photoreceptor, those having physical properties shown in Table 1 below were prepared.
(Production of strontium titanate)
Titanium oxide and strontium carbonate were sufficiently stirred with a wet ball mill, dried, fired at 900 ° C., and then pulverized with a jet mill to obtain strontium titanate having a number average particle diameter of 310 nm.
100 parts of the above (toner base particles 1), 2 parts of hydrophobized silica (HDKH2000, Clariant Japan), 1 part of strontium titanate, 1 part of titanium oxide (MT-150A, Teica) are 1 at 12000 rpm in an aster mixer. After mixing for a minute, a sieving toner was obtained with a mesh having an opening of 75 μm.

[Comparative Example 4]
Regarding the blade and the photoreceptor, those having physical properties shown in Table 1 below were prepared.
A toner raw material consisting of 100 parts of a styrene-n-butyl acrylate copolymer resin, 10 parts of carbon black, and 4 parts of polypropylene is premixed with a Henschel mixer, melted and kneaded with a twin screw extruder, and placed in a hammer mill. The resulting powder was dispersed in a hot air stream of a spray dryer to obtain particles whose shape was adjusted.
This particle was repeatedly classified with an air classifier until the desired particle size distribution was obtained.
To 100 parts of the obtained colored particles, 2 parts of hydrophobized silica (HDKH2000, Clariant Japan), 1 part of hydrophobized silica with a primary particle diameter of 120 nm, 1 part of titanium oxide (MT-150A, Taker), The toner was obtained by mixing with a Henschel mixer.

Images were formed using the toners prepared in the above-mentioned [Examples 1 to 8] and [Comparative Examples 1 to 4], and the following items were evaluated.
(Evaluation item)
All evaluation items were evaluated under conditions of high temperature and high humidity (28 ° C./60%), room temperature (23 ° C./50%), and low temperature and low humidity (10 ° C./15%).

[Transfer rate]
After the image area ratio 20% chart is transferred from the photoconductor to the paper, the transfer residual toner on the photoconductor immediately before the cleaning process is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M) and measured with a Macbeth reflection densitometer RD514 type. The difference between the blank and the blank is less than 0.005 is evaluated as ◎, the one from 0.005 to 0.010 is evaluated as ２, the one from 0.011 to 0.02 is evaluated as △, and the one exceeding 0.02 is evaluated as ×. did.

[Transfer Chile]
For transfer dust, after confirming dust during development, the toner image on the photoreceptor was transferred to paper under the same conditions, and the presence or absence of toner on the thin white line of the unfixed image before fixing was visually determined.
Evaluations were evaluated as ○ when there was no problem in practical use, Δ when there was no problem in practical use, and Δ when there was a problem in practical use.

[Cleanability]
After outputting 10,000 sheets of a 95% image area ratio chart, the transfer residual toner on the photosensitive member that has passed through the cleaning process is transferred to a white paper with Scotch tape (manufactured by Sumitomo 3M), which is measured with a Macbeth reflection densitometer RD514 type, Evaluation was made with a difference of less than 0.005 as ◎, 0.005 to 0.010 as ○, 0.011 to 0.02 as Δ, and more than 0.02 as ×.

[Fixability]
Ricoh's imagio Neo 450 was remodeled as a belt fixing system, with a solid image on plain paper and cardboard transfer paper (Ricoh Type 6200 and NBS Ricoh's copy printing paper), 1.0 ± 0.1 mg / cm ² The fixing was evaluated by the toner adhesion amount.
The fixing test was performed by changing the temperature of the fixing belt, and the upper limit temperature at which hot offset did not occur on plain paper was defined as the upper limit fixing temperature. Also, the minimum fixing temperature was measured with paper.
The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.
The fixing upper limit temperature is 190 ° C. or higher, and the fixing lower limit temperature is 140 ° C. or lower.

[Image density]
After outputting the solid image on 6000 paper manufactured by Ricoh, the image density was measured by X-Rite (manufactured by X-Rite).
This was performed for four colors alone, and an average was obtained.
If this value is less than 1.2, x, if it is 1.2 or more and less than 1.4, Δ, if it is 1.4 or more and less than 1.8, ○, if it is 1.8 or more and less than 2.2 ◎.

[Abrasion amount of blade]
The blade after the evaluation was observed with a laser microscope (manufactured by VK-7500, Keyence Corporation), and the wear cross-sectional area was calculated by image processing.

[Filming]
The photoreceptor after evaluation was observed with the naked eye, and the one with the best level was set to 5, and the one with the poor level was set to 1.

[Blade chatter, squeal, turn over]
Judgment by silent or sound.

The physical property values of the toners of [Examples 1 to 8] and [Comparative Examples 1 to 4] are shown in Table 1, and the results of the evaluations are shown in Table 2.
As a representative value of the ratio of the total area (A, B, or C) of the portion in contact with the latent image carrier, the intermediate transfer member, or the fixing member with respect to the total projected area (S) of the toner, A / Only the value of S is shown.

As shown in Tables 1 and 2, the average circularity is 0.94 or more, and the ratio A / S of the total area (A) of the portion in contact with the latent image carrier to the total projected area (S) of the toner is The toners of Examples 1 to 8 having a value of 15 to 40% and externally added hydrophobized silica having a primary particle diameter of 80 nm are the members of the latent image carrier, the intermediate transfer member, and the fixing member. It was found that the transfer rate was high and no transfer dust was produced.
Moreover, good cleaning properties can be obtained by using a specific impact resilience and a specific contact condition, setting the blade hardness to 72 degrees or less, and setting the ratio between the blade thickness and the protruding amount within a specific range. At the same time, the amount of wear of the blade could be reduced.
With respect to the fixability, the image was not disturbed, and excellent results were also obtained in hot offset resistance and low temperature fixability.
Further, the ratio (L / M) of the major axis L to the minor axis M satisfies the relationship of L / M> 3 on the contact surface of the part in contact with the toner of Examples 1 to 8 and the latent image carrier. It was.

  On the other hand, in Comparative Example 1, when a substantially spherical toner having a high average circularity and a low A / S value of 7.1% was used, an extremely high transfer rate could be realized. It occurred and there was an image defect. Also, the cleaning property was deteriorated.

  In Comparative Example 2, the silica having a hydrophobized primary particle diameter of 80 nm was not added, and good evaluation was obtained for the fixing property, but the transfer rate and the cleaning property were inferior.

  In Comparative Example 3, the volume average particle size of the inorganic fine particles was as large as 310 nm, and good evaluation was obtained for the cleaning property, but the transfer dust, fixing property, particularly low temperature fixing property was inferior. .

In Comparative Example 4, since irregular toner having a low average circularity and a high A / S value of 47.1% was used, no transfer dust was observed, but the transfer rate was low and the image quality was low. It was low.
Further, the cleaning property was good, but the fixing property, particularly the low temperature fixing property, was inferior.

  Further, the ratio of the major axis L to the minor axis M (L / M) on the contact surface of the portion in contact with the toner and the latent image carrier in Comparative Examples 1 to 4 has a relationship of L / M ≦ 3. It was.

FIG. 1 shows a schematic diagram of an example of an image forming apparatus applicable to the method of the present invention.

Explanation of symbols

4 Developing device 10 Intermediate transfer belt (intermediate transfer member)
14, 15, 16 Support roller 17 Intermediate transfer belt cleaning device 18 Image forming means 20 Tandem type image forming device 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Reverse Apparatus 30 Document base 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Photosensitive body (latent image carrier)
42 paper feed roller 43 paper bank 44 paper feed cassette 45 separation roller 46 paper feed path 47 transport roller 48 paper feed path 49 registration roller 50 paper feed roller 51 manual tray 52 separation roller 53 manual paper feed path 55 switching claw 56 discharge roller 57 Discharge tray 62 Primary transfer means 100 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder

Claims (25)

An image forming method for forming a toner image, comprising at least a charging step, an exposure step, a development step, a transfer step, and a cleaning step,
The cleaning step is performed by a blade cleaning method in which a cleaning blade is brought into contact with a photoconductor to remove transfer residual toner on the photoconductor,
The impact resilience at 23 ° C. of the cleaning blade is 60% or more and 90% or less,
The contact pressure of the cleaning blade against the photoreceptor is 0.20 N / cm or less,
The cleaning angle formed by the photoconductor and the cleaning blade is 80 degrees or more,
The toner has a filler layer at least near the surface of the binder resin,
The number average particle size of primary particles of the toner external additive is 20 to 100 nm, and the toner external additive includes fine particles having an average particle size of 10 to 20 nm and large particles having an average particle size of 200 to 300 nm. Containing particles,
An image forming method, wherein the toner has a circularity of 0.94 or more.   The image forming method according to claim 1, wherein the cleaning blade has a hardness of 72 degrees or less.   The image forming method according to claim 1, wherein an amount of protrusion of the cleaning blade is 6.0 mm or more.   4. The image forming method according to claim 1, wherein a ratio between the thickness of the cleaning blade and the protrusion amount is 1: 3 to 1: 5. 5.   5. The image forming method according to claim 1, wherein a peak temperature of a loss tangent tan δ in the measurement of tensile viscoelasticity at a frequency of 10 Hz of the cleaning blade is 0 ° C. or less.   The image forming method according to any one of claims 1 to 5, wherein a content of the filler in the toner particles is 0.01 to 20% by weight.   The image forming method according to claim 1, wherein a ratio of a volume average particle diameter of primary particles of the filler to a volume average particle diameter of the toner is 0.1 or less. The image forming method according to any one of claims 1 to 7, wherein the primary particles of the filler have a volume average particle diameter of 0.001 to 0.5 µm.   The filler is metal oxide, metal hydroxide, metal carbonate, metal sulfate, metal silicate, metal nitride, metal phosphate, metal borate, metal titanate, metal sulfide, carbons Inorganic fillers selected from the group consisting of: urethane resin, epoxy resin, vinyl resin, ester resin, melamine resin, benzoguanamine resin, fluororesin, silicone resin, azo pigment, phthalocyanine pigment, condensed polycyclic pigment, dyeing 9. The image forming method according to claim 1, wherein the image forming method is an organic filler selected from the group consisting of lake pigments and organic waxes.   2. The filler according to claim 1, wherein the filler is a filler treated with a surface treatment agent selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a tertiary amine compound. The image forming method according to claim 9.   The image forming method according to claim 1, wherein the filler is selected from the group consisting of silica, alumina, and titania.   The image forming method according to claim 1, wherein the filler is an organosol synthesized by a wet method.   The image forming method according to claim 1, wherein the inorganic fine particles are silica having a spherical shape.   The image forming method according to claim 1, wherein the inorganic fine particles are manufactured by a sol-gel method. The toner has a shape factor SF-2 of 120 to 150,
The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.01 or more and 1.30 or less, according to any one of claims 1 to 14. The image forming method described.   16. A color image formed on a latent image carrier is sequentially transferred to an intermediate transfer member, then transferred to a recording medium at a time, and fixed to form a full color image. The image forming method according to item.   The image forming method according to claim 1, wherein the toner contains a wax.   18. The image forming method according to claim 1, wherein the binder resin constituting the toner contains a modified polyester. The binder resin constituting the toner contains unmodified polyester together with the modified polyester,
The ratio between the weight A of the modified polyester and the weight B of the unmodified polyester is
The image forming method according to claim 1, wherein A / B = 5/95 to 80/20.   The toner base particles are obtained by dispersing a toner material liquid in which at least a polyester prepolymer having a functional group containing a nitrogen atom, polyester, and filler is dispersed and / or dissolved in an organic solvent in an aqueous medium. 20. The image forming method according to claim 1, wherein the image forming method is obtained by crosslinking and / or extending a toner material. In the development step,
21. A two-component development comprising a toner for developing an electrostatic latent image formed on a latent image carrier and applied in the image forming method according to claim 1 and a magnetic carrier. The image forming method according to claim 1, wherein an agent is applied.   The image forming method according to any one of claims 1 to 21, wherein the photoreceptor has a protective layer containing inorganic fine particles made of alumina or titanium oxide.   The image forming method according to any one of claims 1 to 22, wherein a friction coefficient of a surface of the photoconductor is 0.3 or less. A latent image carrier that carries a latent image and a developing unit that supplies toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize the latent image are integrally supported to form an image. A process cartridge formed detachably in the apparatus body,
24. A process cartridge which is applied to the image forming method according to any one of claims 1 to 23. A latent image carrier for carrying a latent image;
Charging means for uniformly charging the surface of the latent image carrier;
Exposure means for exposing the surface of the charged latent image carrier on the basis of image data and writing an electrostatic latent image;
Developing means for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier to make it visible;
Transfer means for transferring a visible image on the surface of the latent image carrier to a transfer target;
Cleaning means for cleaning the toner remaining on the photoreceptor;
An image forming apparatus comprising a fixing unit that fixes a visible image on a transfer target,
An image forming apparatus used in the image forming method according to any one of claims 1 to 24.

Images