JP4283071B2 - Toner for developing electrostatic image, manufacturing method thereof, image forming method, toner filling device, filling method, toner container, process cartridge, and image forming device - Google Patents

Description

  The present invention develops an electrostatic image in electrophotography, electrostatic recording method, electrostatic printing method, etc., and particularly for full-color electrostatic image development constituting electrophotographic image formation suitable for a tandem type color copying machine. Toner, image forming method using the toner, manufacturing method of the toner, filling device for the toner container, filling method, toner container containing the toner, process cartridge holding the toner, and toner container or The present invention relates to an image forming apparatus equipped with the process cartridge.

  In recent years, an electrophotographic apparatus is excellent in high-speed recording performance among image forming apparatuses, and thus is widely used not only for office use but also for personal use. Along with this, there is a strong demand from the market for the implementation of miniaturization of devices and suppression of machine troubles. In addition, with the remarkable development of information technology, electrophotographic devices are required to evolve accordingly. The development of information technology has made it easy for everyone to create color documents. For this reason, for example, there are frequent occurrences of scenes in which a plurality of color documents are to be printed out in a short time for conference purposes. However, there is currently a lack of means to respond to this.

  Furthermore, the development of information technology has made it possible for everyone to use image processing using digital cameras and image scanners. It is also becoming common to capture portraits, landscapes, etc. on a computer, process, save, and print out. For this reason, the image quality of the output image by the electrophotographic apparatus is strongly expected to shift from business color to natural color.

  In general, full-color copying systems that employ electrophotographic technology can be broadly divided into systems that use an intermediate transfer belt and systems that employ a quadruple tandem structure, but quadruple tandem systems can print at higher speeds than intermediate transfer systems. There is a feature. The configurations of digital color copiers and color printers that apply this electrophotographic technology use the same photoconductor for all four colors (yellow, magenta, cyan, and black) in terms of production.

  In order to obtain a high-definition image, the photosensitive layer of the photoconductor is thinned. However, the thinning of the photoconductive layer is very effective in obtaining a latent image with a small diameter, although the margin for photoconductor wear is reduced. Is. The reduction in the thickness of the photosensitive layer has problems such as a reduction in life due to film scraping of the photosensitive member, development at a low charging potential from the withstand voltage of the photosensitive member, and a reduction in background contamination. Under such circumstances, in the case of a digital color copying machine or color printer, an image is obtained by superimposing four development color toners on the same recording paper. However, as the copying frequency increases, The amount of film scraping becomes extremely large, and dirt is generated in non-image portions other than the image.

For example, according to Japanese Patent Laid-Open No. 9-319106, it has been proposed to improve the wear resistance of the photosensitive member by devising the material elements in the photosensitive layer of the photosensitive member. It has not yet been devised to fully consider the phenomenon. Background stains that are likely to occur when an attempt is made to form a high-definition latent image by making the photosensitive layer thin are more conspicuous as the copying frequency increases. In order to improve the background contamination, it is desired to increase the absolute value | V0−VB | of the difference between the charging potential V0 of the photosensitive member and the average developing potential VB. When used, the potential of the absolute value | V0−VB | cannot be increased because the charging potential V0 is set lower due to the withstand voltage of the photoreceptor.
Furthermore, as another countermeasure, there is a photosensitive member in which the photosensitive layer is not scraped, such as a known amorphous silicon photosensitive member. Such a photosensitive member may be used, but it is more expensive than an organic photosensitive member (OPC). In addition, even if such a photoconductor is used, the background stain of the image cannot be improved for the reasons described above.

  Many toners used in the electrophotographic process have a volume average particle size of about 10 μm. Considering that the pigment particle size of the printing ink is submicron, it can be said that the toner particle size is an extremely large image forming material. For example, when an image such as a landscape or a person is printed out with toner having a large particle size (around 10 μm), there is a limit in resolution and gradation, so that it is difficult to obtain a natural texture in the output image. This is an electrophotographic image quality (business color image quality) different from the image quality.

  For this reason, in order for the electrophotographic apparatus to obtain high image quality, it is necessary to use a small particle size toner. In general, it is said that the smaller the toner particle size, the more advantageous it is to obtain a high-resolution and high-quality image. However, the small particle size toner has a disadvantageous effect on the fluidity and the cleaning property of the transfer residual toner on the photoreceptor. In addition, toner filming on the surface of the photoreceptor is likely to occur. In order to solve such a problem, optimization of cleaning conditions such as a large amount of use of a fluidizing agent and an increase in the pressing force of the cleaning blade to the photoconductor is achieved. As a result, the surface of the photoconductor is severely worn by a large amount of additives as if it were polished by a cleanser. If no countermeasure is taken against this, a medaka-like abnormal image (black or white medaka-shaped abnormal image due to toner or developer) will be output or fog will soon occur.

  Therefore, in order to improve image quality in the electrophotographic process, it is necessary to form an image using a toner having a small particle size, and at the same time, it is also necessary to improve the durability of the photoconductor. It becomes.

  Smaller toner diameters tend to induce aggregation and adhesion of toner particles and are not supplied to the replenishment unit when developing an electrostatic latent image in the developing machine, causing problems such as image density reduction and development failure, and photosensitivity. Problems such as poor transfer from the body and the like are all caused by toner particle cohesion and adhesion due to toner particle size reduction.

  Especially in the image formation process of full-color images, a plurality of superimposed images are formed, so that worm-eaten image missing, dust-like stains around characters and images occur, and the photoconductor portion during image transfer There were technical problems that caused various quality problems such as the remaining amount increased, the transfer amount to the copy paper was small, transfer failure occurred, the image density decreased, and the white portion in the image area occurred. .

  According to Japanese Patent Application Laid-Open No. 10-293420 and Japanese Patent Application Laid-Open No. 2000-29241 (Patent Document 1), polymer fine particles having a specific molecular weight are deposited and fixed on the surface of a binder resin containing a colorant. However, the polymer fine particles adhering to the surface when the Tg of the toner core material is in the range of 40 ° C. to 65 ° C. and the Tg of the polymer fine particle of 150 ° C. after the adhesion are 150 are proposed. It is a toner formed by melting the surface modifier with heat in a heat treatment space having a heat treatment space of ℃ to 400 ° C, a heat treatment device having a supply port, and a manufacturing device having a cooling space downstream thereof, and its shape is It is disclosed that a circular powder can be fixed at a low temperature and is excellent in heat resistance, filming and toner scattering. However, this toner has a high processing temperature, and the shape of the base particles changes to a spherical shape, which causes a risk in the image forming process.

  Some toners have been dealt with from the local side in order to improve local transfer defects and dirt caused by toner dust. For example, a method of adding extender pigment to the toner surface is generally known. As proposed in Japanese Patent Application Laid-Open Nos. 56-92545 and 58-60754 (Patent Document 2), toner particles and additives are added. In general, this method mixes the additives uniformly on the particle surface, especially for particles with small particle size and strong agglomeration, or particles with low softness and high tackiness. It was difficult to do so and was insufficient to improve the above-mentioned drawbacks. On the other hand, in order to obtain higher fluidity, a method of increasing the amount of additive has also been proposed, which is disclosed in Japanese Patent Publication No. 54-16229. However, even in this method, there is a limit to the improvement in fluidity, and there are problems such as the occurrence of floating substances that do not adhere to the toner particle surface and contamination of the photoreceptor. Furthermore, in order to avoid this problem, methods such as intensifying mixing and lengthening the mixing time have been taken, but the problem of aggregation between toner particles due to heat generation and the problem of the additive being buried in the toner surface still remain. It was a solution.

  Japanese Patent No. 2791560 discloses a toner powder in which only silica fine particles are mixed on the surface of toner particles, and a toner particle in which metal oxide particles are mixed by mechanical strain and fixed on the toner surface. Proposals have been made to improve the stability and rise of charging by mixing both the body and the toner. If continuous copying, which is a quality issue, is made from several thousand to several tens of thousands of copies, the toner in the development section This solves the problem that the toner is attached to the non-image area on the copy paper and becomes dirty or thin. However, there is a drawback that a large number of mixing tanks such as a tank for mixing the toner powders individually and a tank for mixing both toners are required, which requires a large amount of manufacturing equipment. In addition, as a result of exploring this method, the charge of the toner mixed with silica particles increases, but the charge rising of the toner mixed with the metal oxide is delayed in the charge rising of the electrostatic charge of both toners. It has been found that there is a time difference, which particularly hinders the rising of charging of the initial image, and there is a problem that the toner floats and scatters in the copying machine.

  Japanese Patent No. 3216394 discloses a method in which fluidizing agent particles are uniformly mixed on the surface of toner particles, and a first step of stirring toner powder and a step of adding and mixing fluidizing agent particles under stronger stirring conditions than those described above. A method of uniformly mixing fluidizing agent particles on the toner particle surface in two steps has been proposed, but according to the present invention, the precondition that toner powder is aggregated in the first step is described in the description. Crushing is performed by stirring only the powder, and then the fluidizing agent particles are mixed with a stronger stirring force. Although the effects of the present invention can be seen, problems remain such that when the stirring force of the stirrer is strong, frictional heat is generated and toner aggregation is observed by melting of the toner.

  According to Japanese Patent Publication No. 5-56502, a fine powder having an average particle diameter of 2 μm or less is adhered to resin particles of a specific polyester resin, and then mechanically heated at a temperature of 48 ° C. or higher and lower than the melting point of the polyester resin. There is a disclosure of an improved toner for electrostatic development that is produced by applying a fine powder of 2 μm or less to the surface of resin particles by impact force. The impact surface treatment device used in the disclosure of the present invention uses an air flow to collide. The plate gives impact, but unlike mechanical impact force, in order to drive fine powder onto the surface of the toner particles, heat is better used than just mechanical impact force, such as iron powder. It is effective in embedding fine particles having a high specific gravity. However, since the mechanical impact force is applied to the toner base as a shearing force, the fine powder particles described can easily be buried from the surface, and with the combined use of heat, it is particularly difficult to adjust the embedding depth and the surface area protruding on the surface layer. Yes, and the specific adhesion state was unclear.

According to Japanese Patent Laid-Open No. 2000-267348 (Patent Document 3), a polymerized toner having a fusing process in which fine particles are dispersed and mixed in a polar dispersion liquid, charging aid fine particles and resin fine particles are adhered and fused with hot air. Related manufacturing methods are disclosed.
Japanese Patent Laid-Open No. 6-63387 (Patent Document 4) discloses a method in which a low-melting substance such as a wax compound is finely mixed and dispersed on the surface of the toner base particles, and then heat-treated and fixed on the toner surface. Has been.
Although these methods are common in that heat is used, they are broadly classified because the toner base production method and components are different, and the production method is also different.

  JP-A-2001-51465 (Patent Document 5) discloses a full-color electrophotographic toner obtained by adding hydrophobic silica fine particles having an average particle size of 0.05 μm or less and hydrophobic titanium oxide as a fluidity imparting agent. However, a sufficient fluidity imparting effect cannot be exhibited due to the inclusion of a free additive or the presence of an uncrushed additive agglomerate.

  Thus, high quality is desired and a toner shape is proposed for the problem of a copy image. In Japanese Patent Laid-Open No. 10-097095 (Patent Document 6), the number ratio of the endothermic peak to the temperature region and the circularity level is set. Although a proposed proposal has been made, when the circularity is 0.98 or more and less than 30% by number, aggregates are likely to be generated, and image defects such as fireflies cannot be suppressed. Further, in Japanese Patent Laid-Open No. 10-039537 (Patent Document 7), a proposal for defining the number ratio with respect to the level of circularity is made. In this publication, the number ratio of 0.90 or more and less than 0.94 is defined as 18% or less. However, when the worm-eating evaluation was performed, the improvement effect was insufficient. In particular, when the evaluation was performed using an image forming apparatus provided with an intermediate transfer member, no quality improvement effect was observed. Further, Japanese Patent No. 2862827 (Patent Document 8) proposes a toner that defines an average diameter ratio, a number ratio with respect to the level of circularity, and an average circularity. However, the publication describes that the number ratio with a circularity of 0.85 or less is 3.0% or less, but it is clearly included that the improvement effect for insect worms is not obtained. became.

  In Japanese Patent Laid-Open No. 2000-010333 (Patent Document 9), the number ratio of circular equivalent number average diameter measured by a flow type particle image measuring apparatus and circularity in a range of 1 to 3 μm of circular equivalent diameter is less than 0.950. Toners that stipulate the above have been proposed. Although the toner of this publication has an effect on the transferability, the transferability of the transfer residual toner on the latent image carrier is insufficient, and a satisfactory image quality cannot be obtained.

  Further, in JP 2000-010334 A (Patent Document 10), the number ratio and the average circularity of coarse particles having an equivalent circle number average diameter and an equivalent circle diameter exceeding 10 μm, which are measured by a flow type particle image measuring apparatus. However, it has been clarified that the average circularity of the coarse particles is too wide to be applied, and an improvement effect in transferability cannot be obtained. Japanese Patent Application Laid-Open No. 2000-3063 (Patent Document 11) proposes a toner that defines an average circularity, a standard deviation of the circularity, a surface property of the toner, and an adhesion stress. Although a slight improvement in transferability was observed with the toner, the circularity with respect to the particle size distribution was not considered, and it was confirmed that no improvement effect was obtained in the cleaning properties on the latent image carrier. Further, the reduction in toner particle diameter is not taken into consideration, and satisfactory image quality has not been obtained.

  Further, according to Japanese Patent Application Laid-Open No. 2002-293301 (Patent Document 12), there is a disclosure of a method and apparatus for mixing and fluidizing a gas such as air together with a toner powder at the time of toner filling. Is a revolutionary one that applies fluidization of powders that suppresses agglomeration between particles, but has a high friction coefficient, for example, in the case of toner particles not containing additives, a large amount of air The problem is that sufficient fluidity for powder transportation cannot be obtained unless mechanical vibration is applied, and the airflow is retained because the airflow blowing gas separation sieve in the powder storage device is installed at the bottom. There remains a problem that the toner particle size becomes non-uniform.

JP 2000-29241 A JP 58-60754 A JP 2000-267348 A JP-A-6-63387 JP 2001-51465 A Japanese Patent Laid-Open No. 10-097095 Japanese Patent Laid-Open No. 10-039537 Japanese Patent No. 2862827 JP 2000-010333 A JP 2000-010334 A JP 2000-3063 A JP 2002-293301 A

  The present invention has been made in view of the actual state of the prior art described above, and is a local transfer defect (worm erosion) caused by an image forming method of an electrophotographic process, or an image reproducibility defect (ground) due to toner dust. In particular, the tandem type is capable of high-speed printing compared to the intermediate transfer belt method, but image misalignment tends to occur. In this case, there are inherent problems such as worm erosion and image background contamination. However, a toner for developing a full-color electrostatic charge image that solves such a problem and is particularly suitable for an image forming method of a tandem type copying process, an image forming method using the toner, a method for producing the toner, and a container for the toner Filling device, filling method, toner container containing the toner, process cartridge holding the toner, and image equipped with the toner container or the process cartridge It is an object to provide a formed device.

As a result of sincere research from the pulverized particle condition of the extender pigment in the mixing process, the present invention simply prevents the suspended solids from being evaded because the extender pigment is interposed between the toner particles simply by mixing with a mixer. It was found that the effect of can not be fully demonstrated. In other words, the problem of the present invention is that the local transfer failure (worm worming) and poor image reproducibility are dealt with by the structure of the extender pigment adhering to the toner particle surface from the sea-island structure. In addition, it has been found that it has an effect on lowering the toner fluidity, and by proposing a new filling device when filling the toner powder, the extender pigment adhering to the toner particle surface is mechanically generated during toner transportation. By solving the problems such as detachment and embedding of the extender pigment by abrasion, and by providing a stirring blade on the lid of the toner powder storage device, it was possible to prevent the stagnation of the air flow and make it uniform. Therefore, it has been found that the toner powder can be fluidized smoothly, and even with toner having a large surface coverage of extender pigment , it is possible to suppress the mechanical wear stress that easily occurs during filling as much as possible. It came to be completed.

That is, according to the present invention, the following (1) to (25) are provided.
(1) In a toner for developing a full-color electrostatic charge image, at least two or more types of extender pigments are present on the surface of toner particles obtained by crushing a kneaded material containing at least a binder resin and a colorant. foremost surface primary particles of at most 20 grains, the minimum up to 3 grains Tsugari, an independent island structure in the chain or bunching, in the area occupied by the extender pigment to be island area ratio of 10% to 70% A toner for developing a full-color electrostatic charge image, wherein the extender pigment fixed to the surface and released from the toner powder is 0.01% or less in terms of toner weight percentage.
(2) The toner for developing a full-color electrostatic image according to (1), wherein the toner does not contain extender pigments released from toner powder.
(3) When the charge amount obtained when stirring and mixing for 20 seconds under the same condition is Q20 with respect to the charge amount Q60 obtained when stirring and mixing with carrier particles for 1 minute at a toner concentration of 5% by weight, the following equation is obtained. The toner for developing a full-color electrostatic image according to (1) or (2), wherein the calculated charge rising ratio Y is 80% or more.
Y = (Q20 / Q60) × 100
(4) The average circularity measured by the flow type particle image measuring apparatus of the toner is 0.92 or more, and the average circularity Df in the range of 1 μm to 3 μm in the equivalent circle diameter (weight basis) and 10 μm or more. Any of the above (1) to (3), wherein 0.940 ≦ Df and 0.910 ≦ Dc ≦ 0.950 when the average circularity in the range of 20 μm or less is Dc A full-color electrostatic image developing toner according to claim 1.
(5) The extender pigment is adhered to the toner particle surface layer in an amount of 2.5% by weight or less based on the toner particles as the amount of the cationic element contained therein. The toner for developing a full color electrostatic image according to any one of the above.
(6) Any one of (1) to (5) above, wherein the extender pigment is adhered to the toner particle surface layer in an amount of 0.1% by weight or more based on the toner particles as the amount of the cationic element contained. A full-color electrostatic image developing toner according to claim 1.
(7) The toner for developing a full-color electrostatic image according to any one of (1) to (6), wherein the toner particles have a volume average particle diameter of 8 μm or less.
(8) The toner for developing a full-color electrostatic charge image according to any one of (1) to (7), wherein the primary particles of the extender mixed with the toner are 0.02 μm or more.
(9) The toner for developing a full-color electrostatic image according to any one of (1) to (8), wherein the primary particles of the extender pigment mixed with the toner are 0.5 μm or less.
(10) The toner for developing a full-color electrostatic image according to any one of (1) to (9), wherein the extender mixed with the toner contains silica fine particles subjected to a hydrophobic treatment.
(11) The toner for developing a full-color electrostatic image according to any one of (1) to (10), wherein the extender pigment mixed in the toner contains fine particles of titanium oxide subjected to hydrophobic treatment.
(12) The toner for developing a full-color electrostatic image according to any one of (1) to (11) above, wherein the extender mixed with the toner contains aluminum oxide fine particles subjected to hydrophobic treatment.

(13) After electrostatic latent images are individually formed on a plurality of image carriers, each is individually developed with the full-color electrostatic charge image developing toner according to any one of (1) to (12), Tandem-type image forming method using an electrophotographic process in which toner images formed on each image carrier are sequentially transferred onto a recording medium to be conveyed on a common carrier for the image carrier to obtain a superimposed image A full-color image forming method, wherein the toner adhesion amount on the image carrier is 1.5 g / cm ² or less, and the absolute value of the charge amount of the developer is 1.5 μC / g or more.
(14) After pulverizing the kneaded material containing at least the binder resin and the colorant, the fine particles of the extender pigment are mixed, and then the powder temperature of 35 ° C. or higher and lower than 48 ° C. is controlled by the air flow temperature. The method for producing a toner for developing a full-color electrostatic charge image according to any one of (1) to (12), wherein the airflow mixing treatment is performed in an atmosphere.
(15) The method for producing a toner for developing a full-color electrostatic charge image according to (14), wherein the extender pigment is fixed to the toner particle surface by an air flow heat atmosphere treatment.
(16) The method for producing a full-color electrostatic charge image developing toner as described in (14) or (15) above, wherein the heat-receiving atmosphere temperature of the powder temperature is supplied from an air flow method.
(17) In addition to the air flow method, the mixing tank has a frequency of 500 r.s in an amplitude range of 0.5 mm to 10 mm. p. m to 3000 r. p. The method for producing a full-color electrostatic charge image developing toner according to any one of (14) to (16), wherein vibration less than m is applied.
(18) Production of toner for full-color electrostatic image development according to any one of (14) to (17), wherein the extender pigment is crushed to secondary particles by mechanical impact force and mixed. Method.
(19) The toner powder according to any one of (1) to (12) is hermetically sealed and fluidized with an air flow, and a storing means for storing the fluidized toner powder, and the air flow is made uniform. A full-color electrostatic charge image developing toner filling device, comprising at least stirring means and means for discharging and fluidizing the fluidized toner powder into a toner container.
(20) The full color as described in (19) above, wherein the stirring means for mechanically homogenizing the air flow is provided with a stirring blade on the lid portion of the sealed toner powder container. An electrostatic charge image developing toner filling device.
(21) The toner powder according to any one of the above (1) to (12) is stored in a hermetically sealed container and fluidized with an air current. At that time, the air current is homogenized by a mechanical stirring means, and then the fluid is flowed. A method for filling a toner for developing a full-color electrostatic image, wherein the toner powder is discharged into a toner container and deaerated.
(22) The toner for developing a full-color electrostatic charge image according to (21), wherein the air flow is made uniform by stirring the air flow by driving a stirring blade provided on a lid portion of the hermetically sealed container. Filling method.
(23) A toner wherein the full-color electrostatic image developing toner according to any one of (1) to (12) is filled by the toner filling method according to (21) or (22). container.
(24) In a process cartridge that integrally supports a photosensitive member and a unit including at least a developing unit selected from a charging unit, a developing unit, and a cleaning unit, and is detachable from the main body of the image forming apparatus, the developing unit includes toner. A process cartridge, wherein the toner is a full-color electrostatic image developing toner according to any one of (1) to (12).
(25) An image forming apparatus comprising the toner container according to (23) or the process cartridge according to (24).

The toner for developing a full-color electrostatic image of the present invention requires a high-quality image in a color image, and is a unique technology possessed by an image forming method of a tandem copying process, in particular, in a technology flow in which full-color toner is reduced in size. It is possible to prevent problems such as local transfer defects (worm eaters) and poor image reproducibility (soil stains) due to toner dust from being identified by a sea-island structure with extender pigments fixed on the toner surface. When the charge amount obtained by stirring and mixing for 20 seconds under the same conditions as the charge amount Q60 obtained when the carrier particles are stirred and mixed for 1 minute with a concentration of 5% by weight is Q20,
Y = (Q20 / Q60) × 100
As a result, the charge rise ratio calculated in step (1) can reach 80% or more. As a result, the image forming method of the present invention, particularly the tandem image formation, has a great effect. The toner fluidity that can be controlled to 5 g / cm ² or less is ensured, the absolute value of the charge amount as a developer is 15 μC / g or more, the electrostatic image forming process is stable, and the image quality is improved. I can plan.

Then the full color electrostatic method for producing a charge image developing toner of the present invention is the immobilization of a body pigment, 35 ° C. or higher, the stream mixing process under controlled atmosphere in the powder temperature and air flow temperature below 48 ° C. This makes it possible to softly fix the toner and to easily remove the free (non-adhered) additive by an air flow method.
In particular, when an air flow type vibration flow tank that fluidizes toner powder by an air flow and gives a specific frequency is used, a short processing effect is exhibited.

Further, in the toner for developing a full color electrostatic image of the present invention, when the content of the cationic element when the extender pigment is immobilized on the surface of the toner particle is within the specific range, the extender pigment is interposed between the toner particles. Instead, it is sufficiently fixed on the surface of the toner particles.
Further, the image quality can be further improved by reducing the volume average particle size of the toner to 8 μm or less.

In addition, the extender pigment is fixed to the primary particles with the energy required for crushing, so that the fixative of the extender pigment is improved. Therefore, after the extender pigment is fixed, the toner has excellent wear resistance and collision resistance between the particles. It is particularly effective at the rise of charging characteristics.
In addition, toner using hydrophobically treated silica, titanium oxide, and aluminum oxide as the extender pigment is adhered and fixed on the toner surface in a sea-island structure, so that the anti-blocking performance between the toner particles is increased and the toner flow is increased. Excellent in properties.

In addition, when the toner for developing an electrostatic charge image of the present invention is filled in a container using the toner filling apparatus of the present invention, the toner does not have a decrease in average circularity or an increase in fine powder area, and transfer dust, ground Excellent in terms of dirt and transferability.
Further, by providing a stirring means on the lid of the toner storage device in the toner filling device, it is possible to prevent the stagnation of the air current, smooth the fluidization of the toner, uniform the toner particle size in the toner storage device, and the constitution of the toner surface. Even in a toner having a high pigment coverage, it is possible to stably fill a container with a toner that is free from the removal or burying of extender pigment .

  Furthermore, the same effect as described above can be exhibited by the toner container filled with the full color electrostatic charge image developing toner of the present invention using the filling device or the image forming apparatus equipped with the process cartridge holding the toner. .

The present invention is described in detail below.
[Definition of sea-island state on toner surface of the present invention]
A part of the three-dimensional polyhedron of the toner particles is analyzed by FE-SEM (field emission scanning electron microscope, S-2400, manufactured by Hitachi, Ltd.). By enlarging to 1 square micron and sampling at least two arbitrary faces of the polyhedron, the state of adhesion of the extender pigment is verified. When primary particles continue and are connected to a maximum of 20 particles and a minimum of 3 particles, and the continuation of primary particles is 10 or more in a chain-like or dumpling-like state, the chain is linearly doubled and stacked. When the primary particles are 3 or more and less than 10 particles, they may be in a dumpling state, and an independent chain shape or dumpling state (island shape) is taken as the number unit.

The fixed particle structure (sea island structure) of the extender pigment adhered and fixed to the toner particles of the present invention, that is, in order to understand the present invention, a toner particle surface photograph is attached to FIG. 1 (of Example 1). In terms of the sea-island structure, the island is an extender particle, and the sea is the area where the extender is not attached to the toner base surface. Moreover , the occupation area of the extender pigment which becomes an island by area ratio is 10%-70%. Accordingly, the extender pigment is crushed to primary particles and is independent in the form of chains or dumplings. If evenly distributed, the toner base is fixed to the extent that the bottom is buried in the toner base in a state where 30 islands to 10 islands are dispersed. It is in the state.

  In the analysis and evaluation method of the present invention, 3 g of a sample is randomly sampled, and at least about 5000 particles are sampled from at least three of them, and two sides of toner particles in total of 30 particles are measured by 10 particles.

The size of the aggregate of the extender pigment according to the present invention, namely the fact that crushing degree is greatly affected the adhesion state, crushing processes extender pigments to obtain a state of being attached to the toner particles for the purpose of the present invention And classification processing is indispensable.

  In the tandem type image forming method targeted by the present invention, when the development potential is set to be higher than an appropriate level, transfer dust tends to occur, and the development potential becomes lower than the appropriate level. When set to, there is a problem that the image density tends to decrease and image defects such as worm-eating and white spots occur. Factors for the toner that generates dust include the charge retention amount of the toner, the thickness of the toner layer on the photoreceptor, etc. If the development potential is too high, toner particles having a high charge amount in the developer It became clear that the toner tends to be developed and the toner layer thickness tends to increase, and transfer dust tends to occur.

  If the development potential is too low, the image density is lowered by reducing the thickness of the toner layer, and the margin of the transfer nip pressure is reduced, so that insect bite and white spots are likely to occur. That is, by applying an appropriate development potential, the toner charge retention amount and toner thickness can be controlled at appropriate levels. In addition, it is desirable that the charge amount of the developer is ideally unchanged, but in reality, the charge amount of the developer tends to vary depending on the use environment of the copying machine, the frequency of use, and the number of copies. is there.

Therefore, the development density pattern detector follows the charge amount of the developer and determines the development potential to be an appropriate value, but the toner adhesion amount on the image carrier (photoconductor) is 1.5 mg / cm ² or less, and the absolute value of the charge amount of the developer used is at 15 .mu.C / g or more, still and the developing bias VB, the absolute value when the photoreceptor light portion potential was VL | VL-VB | = 300 V is set to be larger than the absolute value | VL−VB | = 250 V value of the post-exposure potential VL−the average development potential VB of other yellow, cyan, and magenta photoconductors.

In view of the above, the average circularity of the toner is preferably 0.920 or more. When the average circularity is less than 0.920, the transfer efficiency is lowered, such as inferior charge rising characteristics, and toner scattering becomes apparent.
In addition, it is preferable to provide a step of removing these foreign matters with a sieve having an opening of 500 mesh (opening of 27 μm). The residual weight after sieving 100 g of toner with 500 mesh should be 10 mg or less. For example, quality improvement effects can be seen against image defects such as insect eaters and fireflies.

The full color electrostatic image developing toner of the present invention and the production method thereof will be described in detail below.
According to the present invention, an extender pigment is obtained by mixing a dry toner particle having a weight average particle diameter of 5 to 10 μm, which is obtained by pulverizing a kneaded material composed of at least a binder resin and a colorant, with a mixing device having a stirring blade. The mixing state of the extender pigment is improved by providing a step of mixing the extender pigment with a mixer that crushes the aggregate with a crushing force of, for example, 0.01 N or more before mixing the extender pigment. The heading and the agitation before mixing the extender pigment (hereinafter referred to as additive) are as follows: mixer rotation speed n (1 / second), blade diameter d (m), mixing time t (second), number of blades h (sheets) N ² × d × t × h is preferably 5 × 10 ^{3 to} 25 × 10 ⁴ , more preferably 15 × 10 ³ to 18 × 10 ^4. I found. By adjusting to the above range, the additive before mixing with the toner is appropriately unwound and the additive is easily mixed uniformly. If the numerical value is small, the unraveling effect is weak, and if it is too large, the additive floats out of the tank and is not efficient.
Next, after classifying with a vibrating sieve or the like, for example, it is collected with fine particles of 20 μm or less, pulverized again with a mixer, and then transferred to a toner powder and mixing step with a mixer.

  According to the present invention, in a state where the aggregate of the additive is sufficiently crushed to a target particle size, the mixture is pulverized by a mechanical shearing force or impact force with the mixer described above, and then mixed with the toner. The adhering force of the additive on the surface of the initial toner particles is van der Waals force, but gradually increases and uniformly mixes with the surface as the shearing force of the rotating blades increases. Since sticking unevenness occurs, it is preferable to quantitatively grasp the rotation speed, time, etc. of the mixer and determine the conditions.

That is, according to the present invention, the state in which the additive is uniformly adhered is determined, and then the additive is mixed while adjusting the toner powder temperature with an air flow to fix the additive.
In the present invention, the step of uniformly adhering the additive and the step of fixing are individually provided. After evenly adhering, the toner particles are uniformly suspended by an air flow method without applying mechanical shearing force to the toner particles, and the additive is added to the toner surface while maintaining an air flow temperature of 35 ° C. or higher and lower than 48 ° C. It sticks.
During this fixation, the mechanical impact force and excessive heat amount are caused by the toner particles that have already adhered detached or buried by the mechanical impact force, or the non-adhered toner is mixed due to the shear force distribution of the rotating blades, resulting in uneven adhesion. And the toner particle shape and toner particle composition are also changed.

  In the toner of the present invention, the extender pigment (floating additive) released from the toner powder is 0.01% by weight or less, particularly preferably 0% by weight (not including the floating additive) with respect to the toner weight.

For detection of the floating additive, first, a toner sample sampled randomly is separated by a sieve having an opening of 10 μm. The uncrushed additive in the remainder of the sieve can be discriminated with a microscope equipped with a CCD equipped with an optical lens. Further, the detection of the floating additive that has passed through the sieve with the openings described above can be similarly determined up to 1 μm size.
If these shapes become clear, the weight of the toner powder can be calculated from the specific gravity of the additive and the content can be measured.

In the present invention, the object can be achieved when the coverage of the additive is 10% or more and 70% or less with respect to the surface area of the toner particles, calculated from the specific surface of the additive. In addition, some of the additives of the present invention have an effect of imparting electrification, and the particle size varies depending on the additive. For silicon dioxide, a particle size of 0.15 μm to 0.5 μm is effective. It is.

  Quantification of these additives can be analyzed mainly using cationic elements as quantitative elements. For example, an analytical instrument such as EPMA or XPS that uses X-rays is used to detect characteristic X-rays generated from the toner surface, and the amount of adhesion is detected from the intensity using a calibration curve. In addition, for a wide range of measurements, it is also preferable to create a calibration curve based on the analysis value with the fluorescent X-ray and maintain the measurement accuracy between the analysis methods.

  Next, although the fixing temperature is affected by the Tg of the thermoplastic resin used as the raw material for the toner particles, it is desirable that the processing temperature difference be about 10 ° C. to 20 ° C. lower than the Tg. At a temperature lower than that, there is a problem that the immobilization process takes a long time or the immobilization does not proceed. Further, when the temperature is higher than that, problems such as changes in the composition and structure of the toner particles (resin) occur, or the additives are buried, and the intended effect of the present invention cannot be exhibited sufficiently.

A more specific toner production method of the present invention will be described.
A jet-type pulverizer comprising a compressed resin and a collision plate as main constituents of a pulverized product obtained by melting and kneading a thermoplastic resin as a binder resin, a colorant, a charge control agent, etc. After the primary pulverization, a rotor-type pulverizer comprising a fixed container as an outer wall and a rotating piece having the same central axis as that of the fixed container as a main component is connected to an air classifier, The fine powder can be produced by classifying with an airflow classifying means by a counter jet mill pulverizing classifier or the like that performs secondary pulverization while circulating the rotor type pulverizer and the airflow classifier.

As described above, as a result of the study by the present inventors, the factors of toner that generates transfer dust include the charge retention amount of the transfer toner, the thickness of the toner layer on the transfer body, and the like, but the development potential is too high. In this case, it has been clarified that toner particles having a high charge amount in the developer are easily developed, the thickness of the toner layer tends to be increased, and transfer dust onto the photoreceptor is likely to occur. On the other hand, when the development potential is too low, the image density is lowered by reducing the thickness of the toner layer, and the margin of the nip pressure is reduced. That is, by applying an appropriate development potential, it is possible to control the charge retention amount of the toner and the toner thickness on the photoreceptor at an appropriate level. In addition, it is desirable that the charge amount of the developer is ideally unchanged, but in reality, the charge amount of the developer tends to vary depending on the use environment of the copying machine, the frequency of use, and the number of copies. is there.
Therefore, as described above, the development density pattern detector follows the charge amount of the developer so that the development potential becomes an appropriate value, but the toner adhesion amount on the image carrier is 1.5 mg / kg. cm ² or less, the absolute value of the charge amount of the developer used and is improved by a 15 .mu.C / g or more.

  In addition, regarding the transfer efficiency to the photoconductor, a great improvement tendency was recognized by setting the charge rising ratio of the toner to 80% or more. That is, factors on the toner side that contribute to transfer efficiency include developer charge amount, fluidity, electrical resistance, toner shape, etc. Among these factors, developer charge amount, fluidity, toner shape, etc. Is a particularly important factor. In particular, the excellent charge rise characteristics means that the electrostatic force and van der Waals force act on the carrier and blade in a short time, and the desired charge amount can be obtained, making the development process very efficient. It will be done well. At the same time, it is possible to suppress toner blowing.

Here, the charge rising ratio (Y) of the toner is defined as Q60, which is obtained by stirring and mixing with carrier particles at a toner concentration of 5% by weight for 1 minute. When the charge amount sometimes obtained is Q20, it is calculated by the following formula.
Y = (Q20 / Q60) × 100

The additive of the present invention can be mainly used as a fluidity-imparting agent, but those having primary particles of 0.02 to 0.5 μm are preferable, and as additives , hydrophobized silica fine particles, hydrophobized Examples thereof include finely divided titanium oxide fine particles and hydrophobized aluminum oxide fine particles, and it is preferable to use hydrophobic silica fine particles and hydrophobic titanium oxide fine particles in combination. In particular, when stirring and mixing are performed using particles having a primary particle size of 0.05 μm or less, both electrostatic force and van der Waals force with the toner are remarkably improved. Since the fluidity-imparting agent is not detached from the toner by the stirring and mixing in the developing machine to obtain the level, and the flow of the heated airflow is not removed from the toner at the same time, the unadhered suspended matter can be quickly removed. It has been clarified that good image quality with no omission and the like can be obtained, and further reduction of residual toner can be achieved.

  Titanium oxide fine particles, calcium carbonate, etc. are excellent in environmental stability and image density stability, but have a tendency to deteriorate the charge rise characteristics, and if the amount added is larger than that of silica fine particles, the effect of side effects increases. Can be considered. Therefore, when the surface of the toner particles is in the range of 0.1 to 2.5% by weight of the hydrophobic silica fine particles and 0.1 to 1.2% by weight of the hydrophobic titanium oxide fine particles and the like, the charge rising characteristics are large. It has been found that the desired charge rise characteristics can be obtained by applying an appropriate spherical treatment without damage. That is, it has been clarified that even when copying is repeated, stable image quality can be obtained and toner blowing can be suppressed.

  In order to prevent image defects such as white spots and fireflies, it is effective to remove coarse particles (uncrushed materials) of toner particles with a sieve. According to the present invention, the equivalent circle diameter (weight basis) ), The average circularity (Df) of fine powder particles of 1 μm or more and 3 μm or less and the average circularity (Dc) of coarse powder particles of 10 μm or more and 20 μm or less are effective for cleaning transfer defects such as worm-eating images, and transfer residual toner. Show the effect.

Examining this phenomenon, the average circularity (Df) of fine particles having a particle size of 1 μm or more and 3 μm or less is also involved in the transfer property, and it is preferable to keep the average circularity (Df) at 0.940 or more, Even in the case of a copying machine equipped with an intermediate transfer member, the pressing force applied to the toner on the latent image carrier at the time of the transfer nip is dispersed during the primary transfer and the secondary transfer, and the generation of the worm-eating image is suppressed. I found out.
If the average circularity (Df) of the fine particles is less than 0.940, transfer defects such as worm-eating images are generated due to pressing applied during transfer. In particular, in the case of color toner, since the color tone is reproduced by superimposing the three basic colors, a transfer defect such as a worm-eaten image becomes a fatal image defect.

  Next, the average circularity (Dc) of coarse particles having a particle size of 10 μm or more and 20 μm or less is preferably in the range of 0.910 or more and 0.950 or less, and the average circularity (Dc) of the particles is larger than 0.950. In this case, the frictional load between the transfer residual toner on the latent image carrier and the cleaning blade is increased, and toner contamination of the non-image area, so-called cleaning failure, occurs, and good image quality cannot be obtained. Further, when the circularity (Dc) is smaller than 0.910, toner aggregation is likely to occur, and transfer defects such as fireflies and worm-eating images occur.

Another important factor is the absence of toner aggregates and coarse particles in the toner. In the present invention, it is preferable to provide a step of removing these foreign substances with a sieve of 500 mesh (aperture 27 μm) after mixing the additive and finishing the heated air flow process.
In order to prevent image defects (fireflies, white spots), which is an object of the present invention, it is effective to remove the above-described coarse particles (uncrushed materials) of the toner particles with a sieve. For example, the above-mentioned problem can be solved if the amount of the sample toner is 100 g by sieving with a 500 mesh sieve and the upper residue weight is 10 mg or less.

In the mixing step of the toner particles and the additive, attention was paid to a rotary blade type mixer. If the stress applied during mixing in the rotary blade mixer is too high, the toner surface is melted by the heat generated in the mixer, and the spheroidizing phenomenon or the embedding of the fluidity-imparting agent in the toner particles occurs. In particular, in the case of color toner, since the color tone is reproduced by superimposing the basic colors of yellow, magenta, and cyan, a binder resin of a relatively low softening type that contains many low molecular weight components is used. The above problems are important.
As a method for producing the full color toner of the present invention, the weight of the toner to be stirred and mixed is determined by a mixer at the time of mixing the additives, for example, the stirring blade peripheral speed is V (m / sec) and the stirring and mixing time is T (sec). When M (kg) was used, stirring and mixing were performed under conditions that satisfied 50 ≦ (V · T) / M ≦ 200, and a further quality improvement effect against image defects was observed.

  Next, the toner powder subjected to the mixing treatment is transferred to the airflow type and vibration airflow flow tank, and dry air 40 L / min dehumidified from the airflow is fed from the bottom of the airflow flow tank adjusted at 45 ° ± 3 ° C. Toner surface treatment (adhesion to immobilization) is performed at a mim amount. In the upper part of the fluid tank, the additive suspended in the mixing process is separated by a dust collector that collects dust on a filter.

  In the present invention, it is desirable that the toner has a volume average particle size of 8 μm or less, and it is indispensable to increase the resolution of the toner. However, on the other hand, the flowability and storage stability tend to deteriorate. Therefore, even if the volume average particle size is 8 μm or less, a good level in fluidity and storage stability can be obtained by uniformly adding and fixing the additive to the toner particles of the present invention after pulverization. In addition, the resolution is improved and a high-quality image can be obtained. If the toner circularity at this time is adjusted to 0.93 to 0.97, a higher effect can be obtained. As for the fine powder content, by making the fine powder content of 5 μm or less 20% or less, the effect on fluidity and storage stability becomes remarkable, and a good level in the toner replenishment property to the developing machine and the charge rising characteristics of the toner. can get.

  The particle size distribution of the toner can be measured by various methods. In the present invention, the particle size distribution is performed using a small hole passage method (Coulter counter method). A Coulter counter TAII (manufactured by Coulter Inc.) was used as a measuring device, and the measurement was performed with 1% saline as an electrolytic solution and an aperture of 100 μm.

  The circularity can be measured by various methods. In the present invention, the circularity was measured using a flow type particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics. The degree of circularity of the residue on the mesh was measured by diluting the aggregate in an electrolyte solution of 1% saline.

The additive (extreme pigment) used in the present invention can be used alone or in combination of two or more. Examples of the additive used include talc, kaolin, silica, silica gel, colloidal silica, calcium carbonate, calcium hydroxide, zinc oxide, titanium dioxide, barium sulfate, magnesium hydroxide, zinc sulfide, zinc carbonate, zeolite, alumina, Inorganic pigments such as alumina sol and carbon black, mineral needle pigments such as sepiolite, potassium titanate, wollastonite, zonolite and gypsum fiber can be used, but the most preferred additive is silicon dioxide .

  In general, particles whose surface has been surface-treated with a silane coupling agent or the like are used, and as commercially available products, HDK H-2000, HDK H-2000 / 4, HDK H-2050EP, There are HVK21 (manufactured by Hoechst), R972, R974, RX200, RY200, R202, R805, R812 (manufactured by Nippon Aerosil Co., Ltd.), and TS720 (manufactured by Cabot).

  Further, as titanium oxide fine particles, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), MT-150W, MT- 500B, MT-600B (manufactured by Teica), etc. As the hydrophobized titanium oxide fine particles, anatase type or rutile type crystalline or non-crystalline type can be used, and T-805 (Nippon Aerosil Co., Ltd.) or rutile type MT-100S, MT- There are 100T, MT150A, MT150AFM (Taika), STT-30A, STT-62S-S (Titanium), MT-100S, MT-100T (Taika), IT-S (Ishihara Sangyo).

  The addition amount of these additives is suitably 0.1 to 3.5% by weight, more preferably 0.2 to 3.0% by weight, based on the pulverized and classified toner particles. Not all adhere to the toner particle surface, and non-adhered matter (remaining amount) is removed by a sieve or an air flow method.

The surface adhering amount of the additive to the toner particles obtained in this way is analyzed by quantification of a cationic element by an analytical method such as EPMA or XPS, and the adhesion state of the sea-island structure of the present invention is analyzed by FE-SEM. Is possible.
Therefore, it is quantified as a cation element, and its content is preferably 0.1% by weight to 2.5% by weight. As described above, this content is calculated by measuring at least two sides of the toner particles by sampling about 10 to 5000 toner particles at 3 locations in the SEM photograph.

  The present invention can be applied to all color toners, and can also be applied to one-component and two-component development systems.

Any known toner materials can be used in the present invention.
As the binder resin, styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and the like, and its substituted polymer; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer Polymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacrylic acid Methyl copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer , Styrene-butadiene copolymer, steel -Isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, and other styrene copolymers; polymethyl methacrylate, polybutyl methacrylate, polychlorinated Vinyl, 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 resin, aromatic Group petroleum resin, chlorinated paraffin, paraffin wax and the like. Incompatible combinations include styrene-butyl acrylate copolymers and resins with greatly different characteristics such as polyester, epoxy resin, and epoxy polyol resin, or those with a greatly different molecular weight distribution or substitution even in the same resin system. Even very different combinations of groups can be obtained.

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 Se Red, parachlor ortho nitro Nirin Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, 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, Toulouse Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, Riazo 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, Phthalo Cyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used.
The amount used is generally 0.1 to 50 parts by weight per 100 parts by weight of the binder resin.

  As the charge control agent used in the toner of the present invention, either a positive charge control agent or a negative charge control agent can be used. In the case of a color toner, a transparent to white one that does not impair the color tone. Is preferably used. For example, quaternary ammonium salts, imidazole metal complexes, salts, and the like are used as positive polarity, and salicylic acid complexes, salts, organic boron salts, calixarene compounds, and the like are listed as negative polarity.

  In the toner of the present invention, in addition to synthetic waxes such as low molecular weight polyethylene and polypropylene, candelilla wax, carnauba wax, rice wax, wax, jojoba oil, etc. Plant waxes; animal waxes such as beeswax, lanolin and whale wax; mineral waxes such as montan wax and ozokerite; fat waxes such as hardened castor oil, hydroxystearic acid, fatty acid amide, phenol fatty acid ester These may be used alone or in admixture of two or more.

  Further, the toner used in the present invention includes various plasticizers (dibutyl phthalate, dioctyl phthalate) for the purpose of adjusting the thermal characteristics, electrical characteristics, and physical characteristics of the toner as necessary in addition to the above-mentioned release agent. Etc.), and auxiliary agents such as resistance adjusting agents (tin oxide, lead oxide, antimony oxide, etc.) can be added. Furthermore, the toner of the present invention can be mixed with a fluidity-imparting agent other than the above-mentioned release agent, auxiliary agent and the like, if necessary. Examples of the fluidity-imparting agent include aluminum stearate fine particles, magnesium stearate fine particles, zinc stearate fine particles, fluorine resin fine particles, and acrylic resin fine particles. These may be used alone or in combination of two or more. Is possible. As the fluidity-imparting agent, those having a primary particle size of less than 0.1 μm, a surface hydrophobized with a silane coupling agent, silicone oil or the like, and a hydrophobization degree of 40 or more are preferable.

  As the toner production method of the present invention, a known method is used. For example, as described above, a Henschel mixer with a binder resin, a colorant, a charge control agent, and a release agent, if necessary, in an appropriate ratio, After sufficiently mixing using a mixer such as a ball mill, melt kneading is performed using a screw-type extrusion continuous kneader, a two-roll mill, a three-roll mill, a pressure heating kneader or the like. The kneaded product is cooled and solidified, and then coarsely pulverized using a pulverizer such as a hammer mill. In the case of a color toner, for the purpose of improving the dispersibility of the pigment, it is common to use a master batch obtained by previously melt-kneading a part of the binder resin and the pigment as the colorant. Furthermore, after the coarsely pulverized product is pulverized by a jet mill pulverizer, surface treatment is performed using a rotor pulverizer connected to an airflow classifier or the like. For example, as a collision pulverizer, a hammer mill, a ball mill, A tube mill, a vibration mill, and the like can be mentioned. I type and IDS type collision type pulverizers (manufactured by Nippon Pneumatic Industry Co., Ltd.) are used as jet type pulverizers comprising compressed air and collision plates as main components. It can be preferably used. Further, examples of the rotor pulverizer include a roll mill, a pin mill, a fluidized bed jet mill, and the like. In particular, the rotor pulverizer includes a fixed container as an outer wall and a rotating piece having the same central axis as the fixed container as main components. As the rotor type pulverizer, turbo mill (manufactured by Turbo Industry Co., Ltd.), kryptron (manufactured by Kawasaki Heavy Industries Co., Ltd.), fine mill (manufactured by Nippon Pneumatic Industrial Co., Ltd.), etc. can be used. As the machine, a dispersion separator (DS) classifier (manufactured by Nippon Pneumatic Kogyo Co., Ltd.), a multi-division classifier (Elbow Jet; manufactured by Nittetsu Mining Co., Ltd.) and the like can be used. Furthermore, fine particles can be classified using an airflow classifier or a mechanical classifier to obtain fine particles.

Furthermore, when adding a fluidity imparting agent to the fine particles obtained by the above method, known equipment such as a Henschel mixer, a supermixer, or a ball mill can be used.
In this invention, when mixing a fluidity imparting agent, it crushes with the mixer etc. which were equipped with the above-mentioned mechanical impact force. That is, a commercially available additive (extreme pigment) is crushed and pulverized to secondary particles, so that it can be uniformly attached to the surface of the toner base.
A mixing method that also serves as crushing in the additive mixing process has been proposed due to simplification of the manufacturing process, etc., but commercially available additives have insufficient crushing energy because their aggregation states are different from each other, A state of being mixed in the toner powder without being crushed occurs.

As a factor for controlling the circularity, the residence time in the rotor-type pulverizer can be mentioned. For example, in a kryptron system that does not include a classifier, the pulverized particles are sent to the next step without the jet pulverized product remaining in the rotor pulverizer. The particle shape is not changed at all from that of a jet-type pulverized product, and the level difference is extremely small in terms of fluidity and agglomeration. In this case, the improvement effect on the image quality is insufficient. In addition, when the residence time in the rotor-type pulverizer is too long, that is, when the return amount of the pulverizer from the classifier is increased, the spheronization proceeds, but the spheroidization is too advanced as described above. As described above, toner aggregates are liable to occur and cause image defects.
The method of the present invention is clearly different from the method of performing surface modification in Japanese Patent Publication No. 8-20762 in a short time, and in the present invention, an airflow classifier is indispensable, and the powder particles are rotor-type. It is necessary to perform surface treatment so as to obtain a desired circularity by circulating between the pulverizer and the airflow classifier.

  Further, as a classifier that can be connected to a rotor-type pulverizer, a known airflow type, mechanical classifier or the like can be used. However, in the production method of the present invention, it is important to use an airflow type classifier. . In particular, it is preferable to use a dispersion separator (DS) type airflow classifier (manufactured by Nippon Pneumatic Industry Co., Ltd.). This is because the powder particles containing the release agent are classified very efficiently by the swirling airflow supplied into the classification chamber, and in the multi-division classifier using the Coanda effect, the powder particles are sufficiently dispersed. Since it is not made, it has a disadvantage that it is disadvantageous in classification accuracy. In addition, mechanical classifiers are inferior in classification accuracy compared to airflow classifiers, and because there are few adjustment factors when changing conditions, it is very difficult to adjust the particle size, and maintenance such as switching work is also very complicated. There is a problem that accompanies.

In the present invention, after mixing and fixing the additive, it is passed through a sieve of 300 to 100 mesh (aperture 50 to 150 μm) to separate coarse particles, and the toner powder is transferred to the toner filling device of the present invention.
The toner filling device of the present invention is hermetically sealed and fluidized with an air flow, and contains storage means (also referred to as a storage device) for storing the fluidized toner powder, and stirring means for mechanically homogenizing the gas, A filling device comprising a degassing means for discharging and degassing the fluidized toner powder, wherein the gas provided at the bottom of the toner storage device is allowed to pass but the powder is not allowed to pass. A stirrer blade as mechanical stirring means is provided in the powder storage device lid portion to prevent the airflow ejected from the body separation sieve from being driven.

Details of the toner filling device of the present invention will be described below with reference to FIG.
FIG. 6 is a block diagram of the toner filling device of the present invention. FIG. 7 is a configuration diagram in which an agitator is attached to the lid of the toner storage device 10. As shown in FIGS. 6 and 7, the toner filling device of the present invention includes a stirring blade 8, a toner storage device lid 9, a filling toner storage device 10, an air header 11, a vent porous plate 12, a toner outlet tube 13, Toner filling container 14, filling nozzle 15, soft packing 16, perforated porous plate 17, pressure release valve 18, toner flow rate adjusting valve 19, toner inlet 20, fluid toner transport pipe 21, first pressure gauge 22, second A pressure gauge 23, a third pressure gauge 24, a fourth pressure gauge 25, a first pressure reducing valve 26, a second pressure reducing valve 27, an air flow meter 28, an introduction gas control valve 29, a compressed air pipe 30, and scales 32 and 33 are provided. Configured as follows.

  The filling toner storage device 10 normally stores the filling toner 31 in a sealed manner. The air header 11 serving as a gas introduction means has a connection flange that is attached to and detachably coupled to the lower flange of the filling toner storage device 10 at the upper portion, and is used for forming a fluidized bed of the filling toner 31. The ventilation porous plate 12 is detachably accommodated, and the compressed air pipe 30 is fitted and detachably fitted. The vent porous plate 12 is a sieve that separates gas and toner, and is composed of a sintered metal plate, a sintered resin plate, a fine wire mesh, or the like.

  The toner inlet 20 with the closing valve is an inlet for the filling toner 31 stored in the charging toner storage device 10. The pressure release valve 18 is for releasing or sealing the internal pressure in the filling toner storage device 10. The toner flow rate adjustment valve 19 finely adjusts the internal pressure in the filling toner storage device 10. The compressed air pipe 30 is made of, for example, a stainless steel pipe.

  The fluid toner transport pipe 21 is a transport path for transporting the fluidized filling toner 31 to the filling nozzle 15, and is connected to the filling nozzle 15 so as to be detachable. The fluid toner transport pipe 21 is formed of a urethane tube or the like. The filling nozzle 15 is detachably connected to the fluid toner transport pipe 21 and is composed of, for example, a stainless steel filling pipe.

  The 1st-4th pressure gauges 22-25 measure the pressure of a predetermined part. The first and second pressure reducing valves 26 and 27 are valves for depressurizing a predetermined portion. The air flow meter 28 measures the flow rate of air flowing into the air header 11. The introduction gas adjustment valve 29 is for adjusting the amount of gas flowing into the air header 11.

  The toner filling device in FIG. 6 fluidizes the filling toner 31 in the filling toner storage device 10 and fluidizes it through the toner outlet tube 13, the fluid toner transport tube 21, the vent porous plate 17, and the filling nozzle 15. The filled toner 31 is filled in the toner filling container 14.

  FIG. 8 is a configuration diagram of an embodiment of a small toner filling device according to the present invention. Filling toner storage device 10, air header 11, vent porous plate 12, toner outlet tube 13, toner filling container 14, filling nozzle 15, soft packing 16, vent porous plate 17, pressure release valve 18, toner flow rate adjustment valve 19, toner inlet 20, fourth pressure gauge 25, introduction gas regulating valve 29, power plug 40, motor 41, holding frame 42, pump 43, check valve 44, vent pipe 45, gas distribution plate 46, conduit 47, It is comprised so that the scales 48 and 49 may be provided.

  The filling toner storage device 10 normally stores the filling toner 31 in a sealed manner. The filling toner storage device 10 is made of, for example, a flexible material. The air header 11 has a connection flange that is attached to and detachably connected to the lower flange of the filling toner storage device 10, and has an air vent perforated plate 12 for forming a fluidized layer of the filling toner 31. The vent pipe 45 is fitted and detachably fitted.

  The toner inlet 20 with the closing valve is an inlet for the filling toner 31 stored in the charging toner storage device 10. The pressure release valve 18 is for releasing or sealing the internal pressure in the filling toner storage device 10. The toner flow rate adjustment valve 19 finely adjusts the internal pressure in the filling toner storage device 10.

  The conduit 47 is a transport path for transporting the fluidized filling toner 31 to the filling nozzle 15, and is connected to the filling nozzle 15 so as to be detachable. The conduit 47 is composed of a urethane tube or the like. The filling nozzle 15 is detachably connected to the conduit 47, and is composed of, for example, a stainless filling tube. At the base of the filling nozzle 15, a vent porous plate having a size enough to fit in the mouth of the toner filling container 14, for example, a perimeter-wrapped soft packing 16 made of a truncated conical polypropylene ring. 17 is provided.

  The fourth pressure gauge 25 measures the pressure of the filling toner storage device 10. The introduction gas adjustment valve 29 is for adjusting the amount of gas flowing into the air header 11.

  The motor 41 to which the power plug 40 is connected expands and contracts the bellows structure pump 43. The pump 43 is attached to the holding frame 42 and is detachably fixed, and sends air to the air header 11 via the check valve 44 and the vent pipe 45 by expansion and contraction. Further, the expansion and contraction of the pump 43 causes the filling toner storage device 10 to vibrate via the holding frame 42 to fluidize the filling toner 31 in the filling toner storage device 10.

  In the small toner filling device shown in FIG. 8, the filling toner 31 in the filling toner storage device 10 is fluidized and fluidized through the toner outlet tube 13, the conduit 47, the vent porous plate 17, and the filling nozzle 15. The filled toner 31 is filled in the toner filling container 14.

  In the toner filling device of the present invention, the amount of toner (powder developer) filled in the toner filling container 14 is reduced by the amount of toner stored in the filling toner storage device 10 and flows from the filling toner storage device 10. Measurement is performed based on the amount of toner discharged to the toner transport pipe 21 or the conduit 47 and the amount of toner filled in the toner filling container 14.

  Such a measurement of the amount of toner can be performed by a weight measuring means or a measuring means using an optical sensor. That is, the amount of toner filled in the toner filling container 14 can be measured by providing the toner filling device of FIG.

  In FIG. 6, the amount of toner filled in the toner filling container 14 is measured by providing scales 32 and 33. In FIG. 8, the amount of toner filled in the toner filling container 14 is measured by providing scales 48 and 49 in a small filling device. The amount of toner measured by the scales 32, 33, 48 and 49 is automatically recorded on a recording means in the toner filling device. The contents can be expanded to a system in which the situation is known from a remote location using a communication cable or a wireless LAN.

The present invention may be a toner container filled with the toner according to the toner filling method of the present invention, or may be a process cartridge holding the toner. The toner container and the process cartridge are configured to be attachable to the image forming apparatus.
FIG. 9 shows a schematic configuration of an image forming apparatus having a process cartridge for holding the toner according to the present invention.
In FIG. 9, 1 indicates the entire process cartridge, 2 indicates a photosensitive member, 3 indicates a charging unit, 4 indicates a developing unit, and 5 indicates a cleaning unit.
In the present invention, among the constituent elements such as the photosensitive member 2, the charging device means 3, the developing means 4 and the cleaning means 5, a plurality of components including at least the developing means 4 are integrally combined as a process cartridge. The process cartridge is configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Here, the part is based on weight.

Example 1
(Toner component)
Binder resin: Polyester-based polymer 100.0 parts Colorant: Phthalocyanine pigment 3.7 parts Charge control agent: Salicylic acid zinc salt A mixture having a composition of 3.2 parts is melt-kneaded with a biaxial kneader, and the kneaded product Was finely pulverized with a jet mill pulverizer to a volume average particle size of 8 μm, and further subjected to surface treatment using a turbo mill connected to a DS type airflow classifier to obtain fine particles with a volume average particle size of 7.5 μm. . Furthermore, fine powder classification was performed to obtain fine particles having a fine powder content of 5 μm or less and 22% by number.

Next, 100 g of hydrophobic silica fine particles having an average particle size of 70 μm and 100 g of hydrophobic titanium fine particles having an average particle size of 50 μm are added and put into a Henschel mixer (FM-20B, Mitsui Mining Co., Ltd.), and the additives are crushed. For 300 seconds. At this time, the mixer rotation speed n = 30 (1 / second), the blade diameter d = 0.265 (m), the number of blades h = 2 (sheets), and n ² × d × t × h = 14.3. × 10 ⁴ At this time, the average particle size of the crushed hydrophobic silica was crushed to 5 μm. The average particle size of the hydrophobic titanium oxide was also crushed to 5 μm.

Two types of additives crushed in the above pulverization step and 20 kg of the fine particles obtained in the above pulverization and classification step are transferred to a super mixer, the additive is added, and blade peripheral speed V = 20 (m / sec), Under the conditions of stirring and mixing time T = 100 (sec) and V · T / M = 100, a pulverized and mixed toner for developing a cyan electrostatic charge image was obtained.
This pulverized and mixed toner for developing a cyan electrostatic charge image was bagged for 15 minutes in an airflow type mixing tank that had been heated to 45 ° C. at a flow rate of 300 L / min to obtain the cyan electrostatic image developing toner of the present invention.

3 g of the cyan electrostatic image developing toner of the present invention obtained in the above step was sampled, and 3 spots from a magnification of 0.5 mm ² on a FE-SEM (field emission scanning electron microscope Hitachi S-2400) sample stage. As a result of expanding the toner particle surface by 110,000 times and analyzing two surfaces of the arbitrarily-determined polyhedron surface, the crushing of the additive to primary particles progresses to 1 square micron, and the 0.03 μm size and primary particles of 0. It was observed that two types of 05 μm were dumpling (island-like) continuous with 3 to 5 grains, and about 12 were fixed on the surface. Next, as a result of the same analysis on the remaining arbitrary surfaces, two kinds of additives having a primary particle size of 0.05 μm and a primary particle size of 0.03 μm per square micron are continuously and linearly continued. In the state of being stacked in two layers, three dumplings (island shape) within 20 grains were observed, which was observed to be fixed to the toner particle base like an island, and the area occupied by the additive was 44%. (FIG. 1. Toner adhesion amount is 1.5 g / kg).

Next, a qualitative analysis was performed with EPMA 8705 X-ray microanalysis made by Shimadzu Corporation, and the additive fixed on the toner particle surface was observed with EPMA. It was done.
The cationic element (Si, Ti) having an additive attached to the toner particle surface was quantified by an average value obtained by measuring the surface of 30 toner particles obtained in Example 1 from a calibration curve of the adhesion amount and characteristic X-ray intensity. The Si and Ti cation element contents were both about 0.48 wt% and 0.47 wt%.

The obtained toner powder was charged from the toner charging port 20 shown in FIG. 6, the toner storage device was sealed, air was compressed by 0.1 mPa from the outside, and 85 g was filled in the toner filling container 14.
When a developer was prepared using the above toner, the charge amount was 30 μC / g and the charge rise was 82%. This is mounted on a full color copier Ipsio 8000 manufactured by Ricoh, and the development bias Vb = 466V and the photoreceptor white portion potential Vl = 172V are set, and image evaluation and durability evaluation of the full color toner obtained by the above method are performed. It was.

Example 2
20 kg of the toner powder obtained by pulverization and mixing obtained in Example 1 and having two kinds of additives attached thereto is supplied with an air volume of 600 L / min and a frequency of 1500 r.s. p. m The toner for developing a cyan electrostatic image of the present invention was obtained in the same manner as in Example 1 except that the toner was put into a vibration flow tank having an amplitude of 2.7 mm and treated for 10 minutes under the condition of an airflow temperature of 45 ° C.

3 g of the electrostatic charge image developing toner obtained in the above process was sampled, and the surface of the toner particle was measured at three locations from a magnification of 0.5 mm ² on an FE-SEM (field emission scanning electron microscope, S-2400, manufactured by Hitachi, Ltd.) sample stage. As a result of analyzing 2 sides of the polyhedral surface of an arbitrary irregular shape by enlarging 110,000 times, the additive progresses to primary particles per square micron unit area, resulting in 0.03 μm size and 0.05 μm primary particles. These were two dumplings (island-like) continuous with 3 to 5 grains, and around 14 were fixed on the surface. Next, as a result of analyzing the remaining arbitrary surfaces in the same manner, two kinds of additives having a size of primary particles of 0.05 μm and primary particles of 0.03 μm per square micron per unit area continue randomly and partially. In the state of being stacked in two layers, five dumplings (island shapes) of about 20 grains were observed, which were fixed to the toner particle matrix just like islands. At this time, the area occupied by the additive was 40% (FIG. 2).

Next, the additive fixed on the toner particle surface was subjected to the same qualitative analysis as in Example 1. As a result, the main component of the cationic element was detected.
An average value obtained by measuring the surface of 30 toner particles obtained in Example 2 from a calibration curve of adhesion amount and characteristic X-ray intensity with respect to a cationic element (Si, Ti) having an additive adhered to the toner particle surface. The contents of the quantified Si and Ti cation elements were both about 0.48% by weight and about 0.47% by weight.

The obtained toner powder was charged from the toner charging port 20 shown in FIG. 6, the toner storage device was sealed, air was compressed by 0.1 mPa from the outside, and 85 g was filled in the toner filling container 14.
When a developer was prepared using the above toner, the charge amount was 29 μC / g and the charge rise was 81%. This was mounted on a full color copier Ipsio 8000 manufactured by Ricoh Co., Ltd., and the image development and durability evaluation were performed under the same development conditions as in Example 1.

Example 3
(Toner component)
Binder resin: Polyester-based polymer 100.0 parts Colorant: Hansa Yellow G Rhodamine 6C lake pigment 3.7 parts Charge control agent: Zinc salicylate 3.2 Mixture of a composition comprising 3.2 parts is melt-kneaded with a twin-screw kneader. The kneaded product is finely pulverized with a jet mill pulverizer to a volume average particle size of 8 μm, and further subjected to surface treatment using a turbo mill connected to a DS type airflow classifier, and the volume average particle size of 7.5 μm. Fine particles were obtained. Furthermore, fine powder classification was performed to obtain fine particles having a fine powder content of 5 μm or less and 22% by number.

Next, 100 g of hydrophobic silica fine particles having an average particle size of 70 μm and 100 g of hydrophobic titanium fine particles having an average particle size of 50 μm are added and put into a Henschel mixer (FM-20B, Mitsui Mining Co., Ltd.), and the additives are crushed. For 300 seconds. At this time, the mixer rotation speed n = 30 (1 / second), the blade diameter d = 0.265 (m), the number of blades h = 2 (sheets), and n ² × d × t × h = 14.3. × 10 ⁴ At this time, the average particle size of the crushed hydrophobic silica was crushed to 5 μm. The average particle size of the hydrophobic titanium oxide was also crushed to 5 μm.

Two types of additives crushed in the above pulverization step and 20 kg of the fine particles obtained in the above pulverization and classification step are transferred to a super mixer, the additive is added, and blade peripheral speed V = 20 (m / sec), Under the conditions of stirring and mixing time T = 100 (sec) and V · T / M = 100, a pulverized and mixed toner for developing a yellow electrostatic image was obtained.
The pulverized and mixed toner for yellow electrostatic charge image development was bagged for 15 minutes in an airflow type mixing tank that was heated to 45 ° C. at a flow rate of 300 L / min to obtain the yellow electrostatic charge image developing toner of the present invention.

As a result of analyzing the yellow electrostatic charge image developing toner of Example 3 by the same analysis method as in Example 1, the additive was crushed to primary particles per square micron unit area, 0.03 μm, 0.05 μm. These two types were observed, and a state where 5 to 7 particles continued in a state where 0.03 μm particles were stacked on 0.05 μm particles was fixed in a sea island shape with 25 dumplings (island shapes). The area occupied by the additive at this time was 42%.
When the qualitative analysis was performed on the toner particle surface with EPMA (8705 manufactured by Shimadzu Corporation) similar to that in Example 1, a cation element was detected as a main component. From the same calibration curve, the contents of Si and Ti cation elements were both about 0.47 wt% and 0.47 wt%.

The obtained toner powder was charged from the toner charging port 20 shown in FIG. 6, the toner storage device was sealed, air was compressed by 0.1 mPa from the outside, and 85 g was filled in the toner filling container 14.
When a developer was prepared using the above toner, the charge amount was 30 μC / g and the charge rise was 82%. This is mounted on a full color copier Ipsio 8000 manufactured by Ricoh, and the development bias Vb = 466V and the photoreceptor white portion potential Vl = 172V are set, and image evaluation and durability evaluation of the full color toner obtained by the above method are performed. It was.

Example 4
(Effect of vibrating fluid tank)
20 kg of the toner powder obtained in Example 3 with two kinds of additives adhering to the mixture after pulverization and mixing is supplied with an air volume of 600 L / min and a frequency of 1500 r.s. p. The toner for developing a yellow electrostatic image of the present invention was obtained in the same manner as in Example 3 except that the toner was put in a vibrating fluid tank having a diameter of 2.7 mm and processed for 10 minutes under the condition of an airflow temperature of 45 ° C.

The toner obtained in Example 4 was analyzed in the same manner as in Example 1. As a result, the additive was pulverized to primary particles per square micron unit area, and two types of 0.03 μm and 0.05 μm were observed. A state where 5 to 7 particles continued in a state where 0.03 μm particles were stacked on 05 μm particles was fixed in a sea island shape with 28 dumplings (island shapes) was observed. The area occupied by the additive at this time was 44%.
When the same qualitative analysis as in Example 1 was performed, the cation element was detected as the main component, and the content of Si and Ti cation elements was 0.49% by weight and 0. The value was around 47% by weight.

The obtained toner powder was charged from the toner charging port 20 shown in FIG. 6, the toner storage device was sealed, air was compressed by 0.1 mPa from the outside, and 85 g was filled in the toner filling container 14.
When a developer was prepared using the above toner, the charge amount was 32 μC / g and the charge rise was 87%. This was mounted on a full color copier Ipsio 8000 manufactured by Ricoh Co., Ltd., and the image development and durability evaluation were performed under the same development conditions as in Example 1.

Example 5
(Toner component)
Binder resin: Polyester polymer 100.0 parts Colorant: Quinacridone pigment 3.7 parts Charge control agent: Salicylic acid zinc salt A mixture having a composition of 3.2 parts is melt-kneaded with a biaxial kneader and the kneaded. The product is finely pulverized with a jet mill to a volume average particle size of 6 μm, and further subjected to surface treatment using a turbo mill connected to a DS type airflow classifier to obtain fine particles with a volume average particle size of 7.5 μm. It was. Furthermore, fine powder classification was performed to obtain fine particles having a fine powder content of 4 μm or less of 20% by number.

Next, 400 g of hydrophobic silica fine particles having an average particle size of 70 μm and 100 g of hydrophobic titanium fine particles having an average particle size of 50 μm are added and put into a Henschel mixer (FM-20B, Mitsui Mining Co., Ltd.), and the additives are crushed. For 300 seconds. At this time, the mixer rotation speed n = 30 (1 / second), the blade diameter d = 0.265 (m), the number of blades h = 2 (sheets), and n ² × d × t × h = 14.3. × 10 ⁴ At this time, the average particle size of the crushed hydrophobic silica was crushed to 5 μm. The average particle size of the hydrophobic titanium oxide was also crushed to 5 μm.

Two types of additives crushed in the above pulverization step and 20 kg of the fine particles obtained in the above pulverization and classification step are transferred to a super mixer, the additive is added, and blade peripheral speed V = 20 (m / sec), Under the conditions of stirring and mixing time T = 100 (sec) and V · T / M = 100, a pulverized and mixed toner for developing a magenta electrostatic image was obtained.
The pulverized and mixed toner powder 20 kg was mixed with an air volume of 600 L / min and a frequency of 1500 r.s. p. m and an 2.7 mm amplitude fluidized flow tank and processed for 15 minutes under the condition of an airflow temperature of 45 ° C. to obtain a magenta electrostatic charge image developing toner of the present invention.

The toner obtained in the above process was analyzed in the same manner as in Example 1. As a result, the additive was pulverized to primary particles per square micron unit area, and two types of 0.03 μm and 0.05 μm were observed. .5 to 7 particles in a state where 0.03 μm particles are stacked on 0.05 μm particles, and 12 to 14 particles in a state of dumplings (island shape) with 12 primary particles partially overlapped. In this state, 7 were fixed in a sea island shape. The area occupied by the additive at this time was 67%.
The cation element was detected as the main component from the same analysis method as in Example 1, and the contents of Si and Ti cation elements were both 1.92 wt% and 0.47 wt% from the calibration curve.

The obtained toner powder was charged from the toner charging port 20 shown in FIG. 6, the toner storage device was sealed, air was compressed by 0.1 mPa from the outside, and 85 g was filled in the toner filling container 14.
When a developer was prepared using the above toner, the charge amount was 27 μC / g and the charge rise was 82%. This was mounted on a full color copier Ipsio 8000 manufactured by Ricoh Co., Ltd., and the image development and durability evaluation were carried out under the same development conditions as in Example 1.

Example 6
20 kg of the toner powder obtained in Example 5 and adhering two kinds of additives after pulverization and mixing was supplied with an air volume of 600 L / min and a frequency of 2000 r.s. p. The toner for developing a magenta electrostatic charge image of the present invention was obtained in the same manner as in Example 5 except that the toner was put in a vibrating tank having a diameter of 2.7 mm and treated for 20 minutes under the condition of an airflow temperature of 40 ° C.

The toner obtained in the above process was analyzed in the same manner as in Example 1. As a result, the additive was pulverized to primary particles per square micron unit area, and two types of 0.03 μm and 0.05 μm were observed. A state where 5 to 7 particles continued in a state where 0.03 μm particles were stacked on the particles was fixed in a sea island shape with 28 dumplings (island shapes) was observed. The area occupied by the additive at this time was 42%.
The cation element was detected as the main component from the same analysis method as in Example 1, and the contents of Si and Ti cation elements were both about 0.49 wt% and 0.47 wt% from the calibration curve.

The obtained toner powder was charged from the toner charging port 20 shown in FIG. 6, the toner storage device was sealed, air was compressed by 0.1 mPa from the outside, and 85 g was filled in the toner filling container 14.
When a developer was prepared using the above toner, the charge amount was 31 μC / g and the charge rise was 85%. This toner was evaluated with the same evaluation machine as in Example 5.

Example 7
(Toner component)
Binder resin: Polyester polymer 100.0 parts Colorant: Carbon black 3.7 parts Charge control agent: Salicylic acid zinc salt A mixture having a composition of 3.2 parts is melt-kneaded with a twin-screw kneader, and the kneaded product. Was finely pulverized with a jet mill pulverizer to a volume average particle size of 7 μm, and surface treatment was performed using a turbo mill connected to a DS type airflow classifier to obtain fine particles with a volume average particle size of 7.5 μm. . The fine powder was further classified to obtain fine particles having a fine powder content of 4 μm or less and 18% by number.

Next, 400 g of hydrophobic silica fine particles having an average particle size of 70 μm and 100 g of hydrophobic titanium fine particles having an average particle size of 50 μm are added and put into a Henschel mixer (FM-20B, Mitsui Mining Co., Ltd.), and the additives are crushed. For 300 seconds. At this time, the mixer rotation speed n = 30 (1 / second), the blade diameter d = 0.265 (m), the number of blades h = 2 (sheets), and n ² × d × t × h = 14.3. × 10 ⁴ At this time, the average particle size of the crushed hydrophobic silica was crushed to 5 μm. The average particle size of the hydrophobic titanium oxide was also crushed to 5 μm.

Two types of additives crushed in the above pulverization step and 20 kg of the fine particles obtained in the above pulverization and classification step are transferred to a super mixer, the additive is added, and blade peripheral speed V = 20 (m / sec), Under the conditions of stirring and mixing time T = 100 (sec) and V · T / M = 100, a pulverized and mixed toner for developing a black electrostatic image was obtained.
20 kg of the pulverized and mixed toner powder was applied to an air volume of 600 L / min and a vibration frequency of 2800 r. p. The toner was developed for 10 minutes under a condition of an air flow temperature of 45 ° C. and a black electrostatic image developing toner of the present invention.

This toner was analyzed in the same manner as in Example 1. As a result, the additive was pulverized to primary particles per square micron unit area, and two types of 0.03 μm and 0.05 μm were observed. In the state in which 12 to 14 particles are in a dumpling state with the same primary particles as 28 dumplings (island shape) in which 5 to 7 particles are continued in a state where 0.03 μm particles are stacked. Seven of them were observed to be fixed in the shape of sea islands. At this time, the area occupied by the additive was 68%.
From the same analysis method as in Example 1, a cation element was detected as a main component, a cation element of Si and Ti was detected as a main component, and the contents of Si and Ti cation elements were both 1.92 wt. %, Values around 0.47% by weight.

The obtained toner powder was charged from the toner charging port 20 shown in FIG. 6, the toner storage device was sealed, air was compressed by 0.1 mPa from the outside, and 85 g was filled in the toner filling container 14.
When a developer was prepared using the above toner, the charge amount was 24 μC / g and the charge rise was 83%. Similarly, this toner was mounted on a full color copier Ipsio 8000 manufactured by Ricoh Co., Ltd., and under the same development conditions as in Example 1, image evaluation and durability evaluation were performed.

Comparative Example 1
(Additive uncracked and unfixed in Example 1)
100 g of hydrophobic silica fine particles having an average particle size of 300 μm and a primary particle size of 0.04 μm without pulverization treatment and 20 g of fine particles of the pulverized toner obtained in Example 1 were obtained. 100 g of 3 μm hydrophobic titanium fine particles were added after stirring for 300 seconds before adding the external additive, added to the Henschel mixer (FM-20B, Mitsui Mining Co., Ltd.), and the blade peripheral speed V = 20 ( m / sec), stirring and mixing time T = 100 (sec), and stirring and mixing were performed under the conditions of V · T / M = 100 to obtain a cyan electrostatic image developing toner.

As a result of carrying out the adhesion state on the surface of the toner particles by the same analysis method as in Example 1, the same hydrophobic silica was used, but some particles were not mixed until the primary particles were crushed. Among them, particles having a size of about 0.4 μm and a particle size of 0.15 μm adhered to about 7 particles, which deviated from the sea-island structure in units of 1 square micron of the present invention. At this time, the area occupied by the additive was 73%.
Further, regarding the adhesion amount of the additive on the toner surface, the content of Si and Ti elements was about 0.15% by weight and about 0.12% by weight according to a calibration curve from the same analysis method as in Example 1. .

The obtained toner powder was charged from the toner charging port 20 shown in FIG. 6, the toner storage device was sealed, air was compressed by 0.1 mPa from the outside, and 85 g was filled in the toner filling container 14.
When a developer was prepared using the toner, the charge amount was 13 μC / g. The rise of charge was 63%. Next, it is mounted on a full color copier Ipsio 8000 manufactured by Ricoh Co., Ltd., and development bias Vb = 466V and photosensitive member white portion potential Vl = 172V are set, and image evaluation and durability evaluation of the full color toner obtained by the above method are performed. It was.

Comparative Example 2
(In contrast to Example 1, the additive is not crushed)
The fine particles of 20 kg of the pulverized toner obtained in Example 1 were not crushed with additives, and 100 g of hydrophobic silica fine particles having an average particle size of 100 μm and 100 g of hydrophobic titanium fine particles having an average particle size of 500 μm were obtained. Stir for 300 seconds before adding the additive , add, add to a Henschel mixer (FM-20B, Mitsui Mining Co., Ltd.), mixer speed n = 30 (1 / second), blade diameter d = 0 .265 (m), the number of blades h = 2 (sheets), and stirring and mixing were performed under the conditions of n ² × d × t × h = 14.3 × 10 ⁴ . At this time, the time from the end of pre-stirring to the start of additive mixing was 3 minutes.
This cyan electrostatic image developing toner was bagged for 15 minutes in an airflow type mixing tank that had been heated to 25 ° C. at a flow rate of 300 L / min to obtain a cyan electrostatic image developing toner.

As in Example 1, the cyan electrostatic charge image developing toner of Comparative Example 2 was sampled, and 3 points from a magnification of 0.5 mm ² on the FE-SEM (field emission scanning electron microscope Hitachi S-2400) sample stage. As a result of analyzing the two sides of the arbitrarily-determined polyhedron surface by enlarging the toner particle surface by 50,000 times, it was found that hydrophobic silica and titanium oxide particles that were not crushed coexisted in a particle size of 1 μm to 3 μm. (FIG. 4).
Next, a cation element was detected by the same analysis method as in Example 1.
As a result of measuring the surface of the toner powder obtained in Comparative Example 2 from the calibration curve of the adhesion amount and the characteristic X-ray intensity of the cationic element (Si, Ti) having the additive attached to the toner particle surface, the Si, Ti cation was obtained. The element contents were both about 0.41% by weight and about 0.40% by weight.

The obtained toner powder was charged from the toner charging port 20 shown in FIG. 6, the toner storage device was sealed, air was compressed by 0.1 mPa from the outside, and 85 g was filled in the toner filling container 14.
When a developer was prepared using the above toner, the charge amount was 13 μC / g and the rising rate was 72%. The full color toner obtained by the above method was subjected to image evaluation and durability evaluation by mounting on a full color copier Ipsio 8000 manufactured by Ricoh Co., Ltd. and setting a developing bias Vb = 466V and a photoreceptor white portion potential Vl = 172V.

Comparative Example 3
(Change to intensify mixing conditions compared to Example 1)
The airflow temperature of the airflow mixing tank implemented in Example 1 was set to 60 ° C., and the mixture was fixed while bagging the toner powder for 15 minutes.
As a result of carrying out the adhesion state of the toner particle surface by the same analysis method as in Example 1, the same hydrophobic silica was used, but 0.5 μm to 0.15 μm particles were observed, but the primary particle state could not be confirmed. Traces of the toner particle surfaces being melted by heat were observed, and fibrous foreign matters were generated during mixing and stirring. Although it is similar to the sea-island structure in units of 1 square micron of the present invention, the primary particles were not confirmed, and some of the additives were buried, which hindered measurement of the area occupied by the additives. .
Further, the amount of the additive adhering to the toner particle surface was analyzed for the cation element as in Example 1, and the content of Si and Ti elements was found to be 0.30% by weight, 0.12 from the calibration curve. The value was around wt%.

The obtained toner powder was charged from the toner charging port 20 shown in FIG. 6, the toner storage device was sealed, air was compressed by 0.1 mPa from the outside, and 85 g was filled in the toner filling container 14.
When a developer was prepared using the toner, the charge amount was 13 μC / g. Further, the charge rising was 57%. Next, it is mounted on a full color copier Ipsio 8000 manufactured by Ricoh Co., Ltd., and development bias Vb = 466V and photosensitive member white portion potential Vl = 172V are set, and image evaluation and durability evaluation of the full color toner obtained by the above method are performed. It was.

Comparative Example 4
(Mechanical shock)
For the purpose of driving the additive while applying mechanical impact force to the fine particles of the pulverized toner obtained in Example 1 above, 20 kg is applied to the toner particle surface again using a turbo mill connected to a DS type airflow classifier. 100 g of hydrophobic silica fine particles with an average particle size of 300 μm and a primary particle size of 0.04 μm without pulverization treatment and 100 g of hydrophobic titanium fine particles with an average particle size of 0.3 μm without pulverization treatment were mixed with stirring. The time was 30 minutes and the airflow temperature of the airflow classification was adjusted to 55 ° C. to obtain a cyan electrophotographic toner.

Comparative Example 5
85 g of the toner powder obtained in Example 1 was filled in a toner filling container at a rotation speed of 500 rpm with an AMT auger type filling machine manufactured by Tokyo Automatic Co., Ltd. The toner container was attached to an IPSIO 8000 manufactured by Ricoh, and the development bias Vb = 466V and the photoreceptor white portion potential Vl = 172V were set, and image evaluation and durability evaluation of the full color toner obtained by the above method were performed.

Comparative Example 6
Image evaluation and durability evaluation of the full-color toner were performed in the same manner as in Comparative Example 5 except that the toner powder obtained in Example 2 was used.

When this toner powder was observed by the analysis method described in Example 1, 0.5 μm to 0.15 μm particles similar to the adhesion structure described in Comparative Example 3 were observed, but the primary particle state could not be confirmed, and it was buried. As a result, the primary particles of the additive described in the present invention could not be verified in a state where the shape of the toner was deformed and deviated from the sea-island structure.
Further, the amount of the additive adhering to the toner surface was analyzed in the same manner as in Example 1. As a result, the contents of Si and Ti elements were as low as 0.15 wt% and 0.12 wt%.

The obtained toner powder was charged from the toner charging port 20 shown in FIG. 6, the toner storage device was sealed, air was compressed by 0.1 mPa from the outside, and 85 g was filled in the toner filling container 14.
When a developer was prepared using the above toner, the charge amount was 12 μC / g. The rise of charge was 67%. Next, it is mounted on a full color copier Ipsio 8000 manufactured by Ricoh Co., Ltd., and development bias Vb = 466V and photosensitive member white portion potential Vl = 172V are set, and image evaluation and durability evaluation of the full color toner obtained by the above method are performed. It was.

  100 g of the toner powders obtained in Examples 1 to 7 and Comparative Examples 1 to 6 above were selected with a sieve having an opening of 10 μm, and the additive in the coarse powder region and the toner powder that passed through the sieve were measured once ( (Measurement of 3.5 g × 10 times) was measured at KEYENCE's MEGA, PIXEL 2.1 type, 1K to 3K magnification. The results are shown in Table 1.

[Evaluation method and evaluation criteria]
The image quality was evaluated by forming an image with IPSIO 8000.

(1) The bug-eating rank evaluation was performed based on the following.
Rank 5: No insect eater occurs.
Rank 4: There are a few small insect eaters that are difficult to see with the naked eye.
Rank 3: Many small insect eaters that are difficult to see with the naked eye.
Rank 2: A large insect eater can be seen clearly with the naked eye.
Rank 1: Many large insect eaters can be seen clearly with the naked eye.
* Rank 4 is acceptable level

(2) Transfer dust evaluation during transfer was performed based on the following.
Rank 5: Not generated.
Rank 4: Although it cannot be visually confirmed, slight dust can be confirmed with a loupe.
Rank 3: Although it can hardly be confirmed by visual observation, several dust spots can be confirmed with a loupe.
Rank 2: Chile can be visually confirmed.
Rank 1: The blur of characters due to Chile can be visually confirmed.
* Rank 4 is acceptable level

(3) For firefly evaluation, 10 full-color images were output in A3 size using a full-color copying machine, and the number of fireflies generated in the image was counted. That is, the smaller number is better.

(4) Transferability was evaluated from the number of copyable sheets per 100 g of full-color toner of each color and the amount of collected residual toner. That is, if the number of copies per 100 g of toner can be increased and the amount of recovered toner remaining is small, transferability is excellent.

The toner physical properties and the like of Examples and Comparative Examples are shown in Table 1 below.

The evaluation results are shown in Table 2.
The quality evaluation is as follows.
◎: Particularly excellent ○: Good △: Somewhat bad ×: Bad

<Description of Examples and Comparative Examples>
In Example 1 and Comparative Example 1, the toner components are the same, but in Comparative Example 1, the toner was manufactured without using the pulverized processing and immobilization processing without using the heated airflow type flow processing. In comparison, the undisintegrated amount of the additive (500 mesh sieve remaining amount) is 10 times or more, no decrease in the suspended matter of the additive is observed, and the toner charge rise is about 20% lower than the developer. The charge amount is also a low value of 13 μC / g. In addition, the transfer dust was conspicuous in terms of the quality of the mounting machine, resulting in noticeable worms and dirt.

  The difference between Example 1 and Comparative Example 2 is that the toner produced in Comparative Example 2 was obtained by unpulverizing the additive, and the processing temperature was about 25 ° C., so there was a problem in the rise of charging and the fixation did not proceed. For this reason, the transfer dust was conspicuous in the quality of the mounting machine, and the durability and soiling were conspicuous.

  The difference between Examples 1 and 2 is that in Example 2, the mixing tank was vibrated in the airflow type flow treatment, and there were few floating additives, and the immobilization treatment time was shortened. Further, in comparison with Comparative Example 3, Comparative Example 3 is a toner produced by performing a crushing treatment and performing a treatment for 15 minutes at a heating airflow treatment temperature of 60 ° C., generating a fibrous foreign matter, and raising the charge. The charge amount is also low. It can be determined that this development has a high temperature and the toner particle composition has been altered to act as a charge control agent, or the additive has been buried and deterioration at the temperature has progressed.

  Next, there is no difference in the toner composition in comparison between Example 1 and Comparative Example 4, but in Comparative Example 4, since the additive was not crushed and not fixed, the rise in charge and the charge amount were The value is low. In Comparative Example 4, the toner adheres to the toner in the mixing step with the additive, but then the additive easily detaches due to mechanical abrasion with the carrier particles and the container wall. Then, the durability was hindered, the transfer dust was conspicuous, and the background dirt was conspicuous.

  In the comparison between Examples 1 and 2 and Comparative Examples 5 and 6, there is no change in the toner component, but Comparative Examples 5 and 6 are filling machines constituted by mechanical auger transportation, while the auger frictionally rotates in the cylinder. The toner is transported and filled in the toner bottle container, which is the difference in the filling machine mechanism. In terms of toner physical properties, there was a decrease in average circularity and a decrease in fine powder area. In other cases, no significant difference was observed, but there was a difference in the quality of the mounting machine, the durability decreased by one rank, and transfer dust, background dirt, transferability, etc. decreased by one rank.

Sea-island structure diagram of the surface of toner particles for developing an electrostatic charge image obtained in Example 1 of the present invention (photograph of toner surface with primary particles of 0.03 μm being chain-like and independent, and fixed in an island-like form, × 100,000 Times). Sea-island structure diagram of the surface of toner particles for developing an electrostatic charge image obtained in Example 2 of the present invention (Photo of surface of toner with primary particles 0.03 μm in a dump-like shape, independently attached and fixed in an island shape, × 100,000) Times). Sea-island structure on the surface of toner particles for developing an electrostatic charge image obtained in Example 3 of the present invention (surface photograph of toner with primary particles of 0.03 μm in an abundant form, independently attached and fixed in an island form, × 100,000 Times). Structural diagram of the surface of toner particles for developing an electrostatic charge image obtained in Comparative Example 2 [Photo 4 of the surface of the mixed toner without using the additive crushing step (average particle size 0.3 μm, primary particle 0. 04 μm), × 100,000 times]. The surface photograph 5 of toner particles 11,000 times (Photo 4 above is an enlarged view of the vicinity of 0.45-μm-shaped particles). 1 is a schematic view of a toner filling device of the present invention. It is the top view and front view of a cover part of the toner filling apparatus shown in FIG. It is the schematic of the small filling apparatus of the toner of this invention. 1 is a schematic view of an image forming apparatus having a process cartridge of the present invention.

Explanation of symbols

(FIGS. 6 to 8)
8 Stirrer blade 9 Toner storage means (device) lid 10 Toner storage means (device)
DESCRIPTION OF SYMBOLS 11 Air header 12 Venting porous plate 13 Toner outlet tube 14 Toner filling container 15 Filling nozzle 16 Soft packing 17 Venting porous plate 18 Pressure release valve 19 Toner flow rate adjustment valve 20 Toner inlet 21 Flowing toner transport tube 22 First pressure gauge 23 2nd pressure gauge 24 3rd pressure gauge 25 4th pressure gauge 26 1st pressure reducing valve 27 2nd pressure reducing valve 28 Air flow meter 29 Introduction gas control valve 30 Compressed air piping 31 Filling toner 32 Electronic balance 33 Electronic balance 40 Power supply Plug 41 Motor 42 Holding frame 43 Pump 44 Check valve 45 Vent pipe 46 Gas distribution plate 47 Conduit 48 Electronic balance 49 Electronic balance

Claims (13)

In the toner for developing a full-color electrostatic image, the surface of the toner particles obtained by pulverizing a kneaded material containing at least a binder resin and a colorant has at least two types of hydrophobically treated extender pigments. Up to 20 primary particles and 3 minimum particles are connected to the surface of the three-dimensional polyhedron, and the island-occupied area is 10% to 70. %, The extender pigment fixed to the surface and released from the toner powder is a toner for developing a full-color electrostatic charge image, wherein the toner weight percentage is 0.01% or less,
After the kneaded product was crushed, mixed with at least two or more kinds of hydrophobized extender pigment fine particles having primary particles of 0.05 μm or less, which were crushed by a mechanical impact force, and then 35 ° C. or more, A method for producing a toner for developing a full-color electrostatic charge image, characterized in that an airflow mixing treatment is performed in an atmosphere in which a powder temperature of less than 48 ° C. is controlled by an airflow temperature. The average circularity measured by the toner flow type particle image measuring apparatus is 0.92 or more, and the average circularity Df in the range of 1 μm or more and 3 μm or less on the equivalent circle diameter (weight basis) and 10 μm or more and 20 μm or less. 2. The toner for developing a full-color electrostatic charge image according to claim 1, wherein 0.940 ≦ Df and 0.910 ≦ Dc ≦ 0.950 when the average circularity of the range is Dc. Manufacturing method. 3. The method for producing a full-color electrostatic charge image developing toner according to claim 1, wherein the toner does not contain extender pigments released from toner powder. The full color according to any one of claims 1 to 3, wherein the extender pigment is adhered to the toner particle surface layer in an amount of 2.5% by weight or less based on the toner particles as the amount of the cationic element contained. A method for producing a toner for developing an electrostatic image. 5. The full-color static pigment according to claim 1, wherein the extender pigment is adhered to the toner particle surface layer in an amount of 0.1% by weight or more based on the toner particles as the amount of the cationic element contained. A method for producing a toner for developing a charge image. 6. The method for producing a toner for developing a full color electrostatic charge image according to claim 1, wherein the toner particles have a volume average particle diameter of 8 [mu] m or less. The method for producing a toner for developing a full-color electrostatic charge image according to any one of claims 1 to 6, wherein the primary particles of the extender pigment mixed with the toner are 0.02 µm or more. The method for producing a toner for developing a full-color electrostatic charge image according to any one of claims 1 to 7, wherein the extender pigment mixed with the toner contains silica fine particles subjected to a hydrophobic treatment. The method for producing a toner for developing a full color electrostatic charge image according to any one of claims 1 to 8, wherein the extender pigment mixed in the toner contains fine particles of titanium oxide subjected to hydrophobic treatment. The method for producing a toner for developing a full-color electrostatic charge image according to any one of claims 1 to 9, wherein the extender pigment mixed with the toner contains aluminum oxide fine particles subjected to hydrophobic treatment. The method for producing a toner for developing a full-color electrostatic charge image according to any one of claims 1 to 10, wherein the extender pigment is fixed to the toner particle surface by an air flow heat atmosphere treatment. The method for producing a toner for developing a full-color electrostatic charge image according to any one of claims 1 to 11, wherein the heat-receiving atmosphere temperature of the powder temperature is supplied from an air flow system. In addition to the air flow method, the mixing tank has a frequency of 500 r.s. p. m to 3000 r. p. The method for producing a full-color electrostatic charge image developing toner according to claim 1, wherein vibration less than m is applied.

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