DEVELOPMENT DEVICE AND IMAGE FORMATION APPARATUS

专利摘要:
developing device and image forming apparatus. a developing device, including: a developer-containing element, which is disposed opposite an electrostatic latent image-containing element and which contains thereon a developer to reveal an electrostatic latent image formed in the electrostatic imaging-containing element and transfers the developer for a developing region, wherein the developer includes a toner and a carrier, the toner containing: a toner base containing a binder resin and a colorant; and an external additive, wherein the external additive comprises coalescing particles each composed of a plurality of primary coalescing particles, and wherein a carrier work function wc and a developer containing element work function ws meet a relationship of the following formula (1): ws - wc (greater equal) 0.4 ev ... (1)
公开号:BR102013028344B1
申请号:R102013028344-4
申请日:2013-09-12
公开日:2021-08-03
发明作者:Shingo Sakashita；Junichi Awamura；Tsuneyasu Nagatomo；Satoshi Kojima；Tomoki Murayama
申请人:Ricoh Company, Ltd.；
IPC主号:

专利说明:

Background of the invention field of invention
[0001] The present invention relates to a developing device and an image forming apparatus to be used for electrophotographic image formation such as a copier, electrostatic printing, a fax machine, a printer and electrostatic recording. Description of the related technique
[0002] In electrophotographic imaging, an electrostatic charge image (latent image) is formed on an element that contains electrostatic latent image, the latent image is developed by using a charged toner to form a toner image, and then the toner image is transferred onto a recording medium such as paper, and fixed by a method such as heating to obtain an output image.
[0003] Recently, electrophotography imaging devices have also been used in the field of commercial printing, called production printing, and imaging devices that are higher in speed and capable of forming high quality full color images have been required.
[0004] One of the important challenges to achieving a high quality full color image is to continuously supply an amount of toner in accordance with a desired image density onto an electrostatic imaging element to reproduce a latent image on the imaging element electrostatic latent exactly by toner.
[0005] For example, in terms of a one-component development system, a phenomenon (fading phenomenon) has been reported in which a band-like part with a low image density is produced when the same image patterns are continuously produced . This fading phenomenon occurs primarily because a low-charge toner, due to friction with the surface of a developer-containing element (development sleeve), slides through a concentrated magnetic field formed by magnets in the developer sleeve and a blade (developer blade). doctor) to regulate the thickness of the toner layer to be transferred to a developing region as part of a toner layer, and does not move on an element that contains electrostatic latent imaging even after it has received a developing electric field. Therefore, in Japanese patent no. 3005081 and Japanese patent no. 3126433, for using an imaging apparatus composed of a developing glove having a surface layer with a y slope of 10 or more in a work function measurement, formed of a resin layer containing conductive fine particles or a lubricant solid and toner whose weight average particle diameter, fine powder content by percent, coarse powder content by percent, and MI (melt index) value were controlled for specific ranges or a composite imaging apparatus of the developing glove and toner having an external additive treated with silicone varnish or silicone oil, the toner can be stably charged at a desired value even in an environment of high temperature and high humidity, and transferring to a developing region only one toner with a quantity of proper charge not by friction between the toner and the surface of the developing sleeve, but by an image force acting between the toner and the developing sleeve and v It is a fading phenomenon.
[0006] Also in terms of a two-component development system more suitable for higher speed imaging apparatus, it has been reported that when a developer is used for a long period of time, a hysteresis occurs in which performance development rate decreases to reduce image density (Japanese open-ended patent application (JP-A) No. 11-065247). Hysteresis in the two-component development system revealed therein is caused by the fact that the release of a two-component developer is not normally performed. Developer release is accomplished by providing odd-numbered magnets on a developing sleeve and providing a pair of magnets of the same polarity at a position lower than the geometric axis of rotation of the developing sleeve to form a release region that has almost zero magnetic force, and cause developer after development to fall naturally using gravity in the region. However, as a result of a counter charge being generated on a carrier during toner consumption for a preceding image, an image force is generated between the carrier and developer-containing element, and the developer is not normally released. Therefore, the developer with a decreased toner concentration due to toner consumption is transferred back to the developing region, and the developing performance decreases. That is, there is an issue where the image density is normal for one stroke of the glove, whereas the second stroke onwards results in a low image density. To deal with the same, JP-A no. 11-065247 mentioned above has proposed a method in which a draw-up roller having magnets inside is disposed close to a release region in the developing sleeve, and release of the developer after development is carried out by means of a magnetic force of the same. The released developer is drawn up by another draw-up roller and then transferred to a developer agitation chamber having screws, and a readjustment of toner concentration and toner charge is carried out therein. However, in the proposal described above, there was a problem that an initial hysteresis can actually be eliminated, but in the case of continued use over time, a sufficient effect cannot be exerted, and a hysteresis occurs.
[0007] The present inventors have discovered, in the course of studying an imaging apparatus that is of high speed and capable of forming high quality full color images, there is a problem, like another hysteresis in the two-component development system, that a toner remaining undeveloped in the developing region is not collected together with the carrier, and remains adhered to the developer-containing element, and when the remaining toner is again transferred as is to the developing region together with a newly developed developer stretched up in the next development, an image density difference occurs depending on whether there is toner remaining in the developer-containing element. This hysteresis is considered to occur when the adhesion force between the toner and developer-containing element becomes greater than the adhesion force between the toner and carrier. This tendency becomes prominent when a developer is continuously agitated over time under conditions where toner consumption is low, and becomes more prominent in the case of, particularly, a high-speed machine. Furthermore, in response to the recent demand for energy savings, low temperature fixation of toner has been promoted, and as one of the means for this, many proposals have been made to add a crystalline resin to the toner (particularly a polyester resin. crystalline) which indicates a sharp melting property at temperature, but this hysteresis tends to be more prominent in an imaging apparatus using such low temperature fixation toner. Invention Summary
[0008] It is an object of the present invention to provide a developing device that allows obtaining high quality full color images by effectively suppressing such hysteresis not only initially but also over time.
[0009] A developing device as a means of solving the problems mentioned above includes a developer-containing element, which is disposed opposite an electrostatic latent image-containing element and which contains a developer thereon to reveal a formed electrostatic latent image in the element that contains electrostatic latent image and transfers the developer to a developing region,
[00010] In which the developer comprises a toner and a carrier, the toner containing: a toner base which contains a binder resin and a coloring substance; and an external additive,
[00011] In which the external additive comprises coalescing particles each composed of a plurality of primary coalescing particles, and
[00012] In which a Wc work function of the carrier and a Ws work function of the element containing developer meet a relationship of the following formula (1):

[00013] The present invention can provide a developing device that can solve the various conventional problems mentioned above, and allows to obtain high quality full color images by effectively suppressing hysteresis in a two-component development system not only initially but also over time. Brief description of the drawings
[00014] Figure 1 is a photograph showing an example of an external toner additive in the present invention.
[00015] Figure 2 is a photograph showing an example of an external toner additive in the present invention.
[00016] Figure 3 is a photograph showing an example of an external toner additive in the present invention.
[00017] Figure 4 is a photograph showing an example of an external additive where the rate of broken or bent particles in 1000 coalescing particles is 30% or less. In the figure, the arrow scale indicates 300 nm.
[00018] Figure 5 is a photograph showing an example of an external additive where the rate of broken or bent particles in 1000 coalescing particles exceeds 30%. In the figure, the arrow scale indicates 300 nm.
[00019] Figure 6 is a schematic explanatory view showing an example of an imaging apparatus of the present invention.
[00020] Figure 7 is a schematic explanatory view showing the other example of an imaging apparatus of the present invention.
[00021] Figure 8 is a schematic explanatory view showing an example using a tandem-type color imaging apparatus of an imaging apparatus of the present invention.
[00022] Figure 9 is a partially enlarged schematic explanatory view of the imaging apparatus shown in Figure 8.
[00023] Figure 10A is a view that shows an example of a normal image by a vertical bar graph.
[00024] Figure 10B is a view that shows an example of an abnormal image by a vertical bar graph. Detailed description of the invention
[00025] A toner, a carrier, a developer-containing element that constitute a developing device of the present invention will be described. Also, it is easy for so-called persons skilled in the art to modify and alter the present invention in the scope of the claims in order to carry out another modality, such modifications and changes are included in that scope of claims, and the following description is an example of the best way to present invention, and in no way limits that scope of the claims. developing device
[00026] The developing device of the present invention includes: a developer made of at least a toner and a carrier; and an element that contains revealer.
[00027] As a result of intensive studies made in view of the problems mentioned above, the present inventors have found that hysteresis can be suppressed not only initially but also over time by a developing device including a developer-containing element that is disposed opposite. to an electrostatic latent image containing element, and contains therein a developer to develop an electrostatic latent image formed in the electrostatic latent image containing element and transports the developer to a developing region, where the developer includes a toner and a carrier, toner containing: a toner base containing a binder resin and a coloring substance; and an external additive, and the external additive contains coalescing particles each composed of a plurality of primary coalescing particles, and a carrier work function Wc and a developer containing element Ws work function meet a relationship of the following formula (1) :

[00028] In the developing device of the present invention, the work function Wc of a carrier and the work function Ws of an element containing developer meets the relationship of the above formula (1).
[00029] It is considered that the occurrence of a hysteresis in a two-component system as a problem in the present invention refers to an adhesion force Ftc between the toner and the carrier and an adhesion force Fts between the toner and containing element developer, and it is considered that when Fts has become greater than Ftc, a toner remaining undeveloped in the developing region is not normally retained in the carrier, and remains adhered to the developer-containing element, and when the remaining toner is again transported as it is to the developing region along with the newly stretched-up developer in the next development, an image density difference occurs depending on whether there is toner remaining in the developer-containing element, which appears as a hysteresis. Wc in the above formula (1) refers to an electrostatic adhesion force between the toner and carrier, and Ws refers to an electrostatic adhesion force between the toner and developer-containing element. Wc contributes the value of a charge amount when the toner and carrier are frictionally charged, and has a tendency, as a result of becoming smaller in value, to increase the charge amount of the toner due to friction charge so as to increase the electrostatic adhesion force between the toner and carrier, thereby making it easy to retain the toner in the carrier normally. On the other hand, Ws is considered to contribute to a charge movement between the toner and developer-containing element when a charged toner held in the carrier has made contact with the developer-containing element, and has a tendency, as a result of it, to become larger. in value, that the amount of moving charge from the toner to the developer-containing element increases near a point of contact between the charged toner and the developer-containing element, which reduces the electrostatic adhesion force between the toner and the developer-containing element. As a result of these relationships given the relationship of the above formula (1), the adhesion force between toner and carrier becomes greater than the adhesion force between toner and developer-containing element, and the occurrence of a hysteresis can be suppressed .
[00030] The work function of conveyor Wc and the work function of the element containing developer Ws can be measured by using, for example, a work function measuring device (AC-2 Surface Analyzer, manufactured by Riken Keiki Co., Ltd.) using a photoelectric effect. Specifically, a conveyor was filled into a recess portion of a sample measuring cell (one formed with a recess portion having a diameter of 10 mm and a depth of 1 mm in the center of a disc made of stainless steel with a diameter 13 mm and height 5 mm) and the surface is smoothed by the edge of a knife. After the full sample measurement cell of a conveyor is fixed at a defined position in a sample table, the amount of irradiation light is set to 500 nW, the irradiation area is given as 4 mm square, and a measurement is performed under a power sweep condition of 3.4 eV to 6.2 eV. Element containing developer
[00031] The developer containing element of the present invention is not particularly limited as long as it meets the relationship of formula (1) above, and various conventionally known developer containing elements may be used. The work function Ws of the developer-containing element in formula (1) above is determined by a surface material to form the developer-containing element, and as the material to form the developer-containing element, eg A1 (Ws: 3.7 eV), SUS (Ws:4.4 eV), TiN (Ws: 4.7 eV) etc. can be used. Toner
[00032] The toner of the present invention includes a toner base and an external additive, and further includes other components as needed. external additive
[00033] The external additive is not particularly limited as long as it contains coalescing particles composed of pluralities of primary coalescing particles, and can be appropriately selected according to the purpose.
[00034] By controlling the particle size distribution and breaking capacity of coalescent particles as an external additive in the following specific ranges, coalescent particles on the toner surface are retained without being buried or separated even against a direction stress over time. time, an increase in non-electrostatic adhesion force between the toner and developer-containing element is suppressed, and the occurrence of a hysteresis can be suppressed over time even in a high speed toner machine. coalescent particle
[00035] The coalescing particle is a non-spherical particle composed of a plurality of coalescing primary particles, that is, as shown in figure 1, a particle for which primary particles (reference signals 1A to 1D) coalesce in various numbers in one and those primary particles have coalescing parts overlapping each other, and it's different from a state of primary particles simply maintaining their shape while aggregating with each other. Furthermore, the "coalescent particle" is sometimes called a "secondary particle". primary particle
[00036] The primary particle is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include fine inorganic particles such as silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, colcotar, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate , barium carbonate, calcium carbonate, silicon carbide and silicon nitride and organic fine particles. These can be used individually or in combination of two or more. Among these, silica is preferable in consideration of being able to avoid burrowing and separation of an external additive into and from the toner base particles.
[00037] An average particle diameter (Da) of the primary particles is not particularly limited and may be appropriately selected according to the purpose, however that is preferably 20 nm to 150 nm, and more preferably 35 nm to 150 nm. Where the average particle diameter of the primary particles is less than 20 nm, there is a case where, as a result of that burying the external additive in the toner base due to an external stress, it cannot be sufficiently suppressed, which no longer allows for a function as spacers, the non-electrostatic adhesion force between toner and developer-containing element increases to cause hysteresis easily, which is not preferable. On the other hand, where it exceeds 150 nm, toner freedom is likely to occur, and this can easily cause photoconductive film formation, which is not preferable.
[00038] An average particle diameter (Da) of the primary particles is determined based on the particle diameters (lengths of all arrows shown in figure 1) of primary particles in the coalescing particles. The determination is carried out, with a sample in which the secondary particles are dispersed in an appropriate solvent (THF or similar), and then the solvent is removed for drying and hardening on a substrate, by measuring the particle diameters of primary particles in a field of view by using a field emission scanning electron microscope (FE-SEM, accelerating voltage: 5 kV to 8 kV, observation magnification: 8000x to 10,000x). The determination of particle diameters of primary particles is performed by estimating entire images from the outer shells of coalescing particles, and measuring an average value of the maximum lengths (lengths of all arrows shown in figure 1) of the entire images (the number of measured particles: 100 or more and 200 or less). secondary particle
[00039] The secondary particle is not particularly limited and can be appropriately selected according to the purpose, however as shown by reference sign 1 of figure 3, this is preferably a particle (aggregate secondary particle) for which the primary particles are chemically bonded by a treating agent to be described later, and more preferably, a particle to which the primary particles are chemically bonded by a sol-gel method, and specifically, sol-gel silica and the like can be mentioned.
[00040] An average particle diameter (Dba) of the secondary particles, i.e. a numerical average particle diameter of the coalescing particles is not particularly limited and can be appropriately selected according to the purpose, however this is preferably 80 nm to 200 nm, and more preferably 100 nm to 180 nm, and particularly preferably 100 nm to 160 nm. When the numerical mean particle diameter is less than 80 nm, there is a case where as a result of this burial of the external additive in the toner base due to an external stress it cannot be sufficiently suppressed, which no longer allows to present a function as spacers, the non-electrostatic adhesion force between the toner and developer-containing element increases to easily cause hysteresis, which is not preferable. On the other hand, where it exceeds 200 nm, freedom from toner is likely to occur, and this can easily cause photoconductor film formation, which is not preferable.
[00041] The determination of the numerical mean particle diameter (Dba) of the secondary particles is carried out, with a sample to which the secondary particles are dispersed in an appropriate solvent (THF or similar), and then the solvent is removed for drying and hardening on a substrate, by measuring the particle diameters of secondary particles in a field of view by using a field emission scanning electron microscope (FE-SEM, accelerating voltage: 5 kV to 8 kV, observation magnification: 8000x to 10,000x), and is specifically performed by estimating entire images of the outer shells of secondary coalescing particles, and measuring the maximum lengths (length of the arrow shown in Figure 2) of the entire images (the number of measured particles: 100 or more) . Production method for coalescing particles
[00042] A method for producing the coalescent particles is not particularly limited and may be appropriately selected according to the purpose, however it is preferably a method for production by a sol-gel method, and specifically, preferably a method for production by bonding chemical by mixing or burning primary particles and a treating agent to cause secondary aggregation to provide secondary particles (coalescing particles). Furthermore, in the case of synthesis by the sol-gel method, coalescing particles can be prepared in a single-stage reaction under the coexistence of the treating agent. A production example will be mentioned below, but the production method is not limited to it. treatment agent
[00043] The treatment agent is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include silane-based treatment agents and epoxy-based treatment agents. These can be used individually or in combination of two or more. When silica is used as the primary particles, a silane-based treating agent is preferable in view of the fact that Si-O-Si bonds formed by the silane-based treating agents are more heat stable than Si-OC bonds formed. by epoxy-based treatment agents. In addition, an auxiliary treatment medium (water, a 1% aqueous solution by mass of acetic acid, or the like) can be used as needed. Silane-based treatment agent
[00044] The silane-based treatment agent is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include mixtures of alkoxy silanes (tetramethoxy silane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane , methyldiethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, and the like); silane coupling agents (y-aminopropyltriethoxysilane, y-glycidoxypropyltrimethoxysilane, y-glycidoxypropylmethyldiethoxysilane, y-methacryloxypropyltrimethoxysilane, y-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, methylvinyldimethoxysilane, and the like); vinyltrichlorosilane, dimethyldichlorosilane, methyl vinyl dichlorosilane, methyl phenyl dichlorosilane, phenyltrichlorosilane, N,N'-bis(trimethylsilyl)urea, N,O-bis(trimethylsilyl)acetamide, dimethyltrimethylsilylamine, hexamethyldisilazane, and cyclic silazane.
[00045] The silane-based treating agent causes, as follows, chemical bonding of primary particles (eg primary silica particles) to form a secondary aggregation.
[00046] When primary silica particles are treated using alkoxy silanes, silane-based coupling agents, and the like as the silane-based treating agent, as shown in the following formula (A), linking silanol groups to primary silica particles and alkoxy groups bonding to the silane-based treatment agent react, and due to dealcoholization, form new Si-O-Si bonds to cause secondary aggregation.
[00047] When primary silica particles are treated using chlorine silanes as the silane-based coupling agent, chlorine groups of chlorine silanes and silanol groups binding to primary silica particles, due to a dehydrochlorination reaction, and new Si-O-Si bonding silanol groups, due to a dehydration reaction, form new Si-O-Si bonds to cause secondary aggregation. On the other hand, when the primary silica particles are treated using the chlorine silanes as the silane-based coupling agent, under coexistence of water in the system, the chlorine silanes are first hydrolyzed in water to provide silanol groups, and the groups of silanol and silanol groups binding to primary silica particles, due to a dehydration reaction, form new Si-O-Si bonds to cause secondary aggregation.
[00048] When primary silica particles are treated using silazanes as the silane-based coupling agent, amino groups and silanol groups bonding to primary silica particles, due to the removal of ammonia, form new Si-O- bonds. Themselves to cause secondary aggregation.

[00049] In formula (A) above, R indicates an alkyl group. Epoxy-based treatment agent
[00050] The epoxy-based treating agent is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins phenol, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol A type epoxy resins, glycidyl amine type epoxy resins, and alicyclic epoxy resins.
[00051] The epoxy-based treating agent causes, as shown in the following formula (B), chemical bonding of primary silica particles to form a secondary aggregation. When primary silica particles are treated using the epoxy-based treating agent, silanol groups bond to the primary silica particles, due to the addition of oxygen atoms from the epoxy group of the epoxy-based treating agent and carbon atoms bond to the epoxy groups form new Si-O-Si bonds to cause secondary aggregation.

[00052] A mass mixing ratio (primary particles: treatment agent) of the treatment agent and the primary particles is not particularly limited and can be appropriately selected according to the purpose, however this is preferably 100:0.01 a 100:50. Also, there is a tendency that the greater the amount of the treating agent, the higher the degree of coalescence.
[00053] A method for mixing the treatment agent and the primary particles is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a method for mixing by a known mixer (spray dryer or similar) . Also in the case of mixing, the primary particles can be prepared and then mixed with the treating agent for preparation, or the treating agent can coexist in preparation of the primary particles to carry out the preparation in a single-stage reaction.
[00054] A burning temperature of the treating agent and the primary particles is not particularly limited and can be appropriately selected according to the purpose, however this is preferably 100°C to 2,500°C. Also, there is a tendency that the higher the amount of burn temperature, the higher the degree of coalescence.
[00055] A burning time of the treating agent and the primary particles is not particularly limited and can be appropriately selected according to the purpose, however this is preferably 0.5 hours to 30 hours. Coalescent Particle Size Distribution Index
[00056] Using particles that meet the following formula (2) as an index of particle size distribution of coalescing particles results in a sharp particle size distribution of coalescing particles. Therefore, the rate of particles that act as spacers without being buried in the toner base due to an external stress is increased, which allows to more effectively suppress an increase in non-electrostatic adhesion force between the toner and developer containing element, thereby suppressing the occurrence of a hysteresis.

[00057] In formula (2) above, in a distribution diagram in which particle diameters (nm) of the coalesced particles are on the horizontal axis and cumulative percentages (% by number) of the coalesced particles are on the vertical axis and where coalesced particles are accumulated from coalesced particles having smaller particle diameters to coalesced particles having larger particle diameters, Db50 indicates a particle diameter of the coalesced particle in which the cumulative percentage is 50% by number, and Db10 indicates a diameter particle size of the coalesced particle in which the cumulative percentage is 10% by number.
[00058] The Db50 is determined based on the distribution diagram where the particle diameters of the coalesced particles (nm) are on the horizontal axis and the cumulative percentages (% by number) are on the vertical axis. When the number of coalesced particles measured is 200, the Db50 is a particle diameter of the 100th largest particle. When the number of coalesced particles measured is 150, the Db50 is a particle diameter of the 75th largest particle.
[00059] The Db50 is measured as follows. First, the coalesced particles are dispersed in an appropriate solvent (eg tetrahydrofuran (THF)). The resulting dispersion liquid is subjected to solvent removal to dryness and a measurement sample is observed under a field emission-type scanning electron microscope (FE-SEM, accelerating voltage: 5 kV to 8 kV, observed magnification: 8,000 to 10,000), and measured for particle diameters of the coalesced particles in a field of view to thereby determine a particle diameter of a coalesced particle in which the cumulative percentage is 50% by number. Particle diameters of the coalesced particles are determined by measuring maximum aggregate particle diameters (length of an arrow shown in Figure 2) (the number of aggregate particles measured: 100 or more and 200 or less).
[00060] The Db10 is determined based on the distribution diagram in which the particle diameters of the coalesced particles (nm) are on the horizontal axis and the cumulative percentages (% by number) are on the vertical axis. When the number of coalesced particles measured is 200, the Db50 is a particle diameter of the 20th largest particle. When the number of coalesced particles measured is 150, the Db10 is a particle diameter of the 15th largest particle.
[00061] Db10 is measured as follows. First, the coalesced particles are dispersed in an appropriate solvent (eg tetrahydrofuran (THF)). The resulting dispersion liquid is subjected to solvent removal to dryness on a substrate to thereby obtain a measurement sample. The measurement sample is observed under a field emission-type scanning electron microscope (FE-SEM, accelerating voltage: 5 kV to 8 kV, observed magnification: 8,000 to 10,000), and measured for particle diameters of the coalesced particles in a field of view to thereby determine a particle diameter of a coalesced particle in which the cumulative percentage is 10% by number. Particle diameters of the coalesced particles are determined by measuring maximum aggregate particle diameters (length of an arrow shown in Figure 2) (the number of aggregate particles measured: 100 or more and 200 or less).
[00062] The "Db50/Db10" is preferably 1.2 or less, and more preferably 1.15 or less. Where the “Db50/Db10” exceeds 1.2 the particle size distribution of coalescing particles is wide, and many small diameter particles are included, ie it means at least “small diameter A particles” (particles whose coalescence has not proceeded, and which exists in a state of primary particles) or “particles of small diameter B” (particles whose coalescence has continued, but the primary particles themselves have small diameters) exist in large numbers. Where "small diameter A particles" exist in large numbers, because coalescing particles cannot sufficiently perform the function as a non-spherical external additive and are inferior in burial strength, there is a case where an increase in non-electrostatic adhesion strength between the toner and the developer-containing element particularly over time cannot be suppressed, and a hysteresis easily occurs, which is therefore not preferable. On the other hand, where "small diameter B particles" exist in large numbers, because coalescent particles cannot perform the function as spacers, there is a case where an increase in non-electrostatic adhesion force between the toner and developer-containing element it cannot be suppressed, and a hysteresis easily occurs even initially, which is therefore not preferable. Therefore, it is necessary to reduce the “small diameter A particles” and the “small diameter B particles.”
[00063] A method for reducing "small diameter particles A" and "small diameter particles B" is not particularly limited and may be appropriately selected according to the purpose, however this is preferably a method in which particles of diameter small are removed in advance by sorting. Coalescent Particle Resistance Break
[00064] The coalescing particle preferably meets the following formula (3), and more preferably meets the following formula (3-1). Therefore, the aggregation force (coalescing force) between primary particles to compose a coalescing particle is maintained even against an agitating force in the developing device, so that burial in the toner base does not occur, which allows to suppress more effectively an increase in non-electrostatic adhesion strength between the toner and developer-containing element, thereby suppressing the occurrence of a hysteresis not only initially but also over time.

[00065] In formulas (3) and (3-1), Nx indicates the number of broken or bent particles in 1,000 of the coalescing particles. The broken or bent particles are selected by stirring 0.5 g of the coalescing particles and 49.5 g of a conveyor placed in a 50 mL flask by using an oscillating mill, (manufactured by Seiwa Giken Co., Ltd.) under conditions at 67 Hz and for 10 minutes, and then observe the stirred coalescent particles through a scanning electron microscope.
[00066] When coalescing particles have a strong aggregation force (as shown in figure 4, when the rate of broken or bent particles (for example, the particle shown in a black box in figure 4) in the 1000 coalescent particles is 30% or less), particles (broken or bent particles) whose external additive in the toner breaks or yields due to a charge of the developing device and the like exist in small numbers, and burial and tipping of the external additive is suppressed, and the occurrence of a hysteresis over time it can be suppressed, which is therefore preferable.
[00067] When coalescing particles have a weak aggregation force (as shown in figure 5, where the rate of broken or bent particles (for example, the particles shown in the black frames in figure 5) in the 1,000 coalescing particles exceeds 30%) particles (broken or bent particles) whose external additive in the toner breaks or sags due to a charge from the developing device and the like exist in large numbers, the spherical particle rate increases, movement and burial of the external additive easily occurs, and the occurrence of a hysteresis over time can no longer be suppressed in some cases, which is therefore not preferable.
[00068] Formula conditions (3)
[00069] In formula (3) below, broken or bent particles mean particles that exist by themselves as primary particles, and include particles that have become primary particles as a result of a breakage or collapse having occurred after agitating the coalescing particles under the agitation conditions by the use of the oscillating mill and particles that existed independently as the primary particles before performing the agitation, and examples thereof include, as the particles shown by reference sign 2 of figure 3 and in the black boxes of figure 4a Figure 5, particles as the primary particles that exist by themselves without being coalesced.
[00070] In the above formula (3), the shape of the broken or bent particles is not particularly limited as long as it is a shape in which particles are not coalesced with each other, and can be properly selected according to the purpose, and for example As shown by reference sign 2 of Figure 3, broken or bent particles often exist in substantially spherical states.
[00071] In formula (3) above, a method to confirm that broken or bent particles exist is not particularly limited and may be appropriately selected according to the purpose, but this is preferably a method to confirm that particles exist by themselves by observation through a scanning electron microscope (SEM).
[00072] A method to determine an average particle diameter of the broken or bent particles is not particularly limited and may be appropriately selected according to the purpose, however the determination is performed by measuring an average value of the particle diameters of the broken or broken particles. folded into a field of view using a scanning electron microscope (FE-SEM, accelerating voltage: 5 kV to 8 kV, observation magnification: 8000x 10,000x) (the number of measured particles: 100 or more).
[00073] In formula (3) above, as a count of broken or folded particles in the 1,000 particles, as the particles shown by reference sign 2 of figure 3 and in the black boxes of figure 4 to figure 5, a particle that exists by itself is only counted as a broken or bent particle by observation through a scanning electron microscope after shaking.
[00074] In formula (3) above, when counting the number of broken or folded particles in the 1,000 particles, where a coalescing particle composed of a plurality of coalescing particles is confirmed by the scanning electron microscope, the coalescing particle is counted as one particle.
[00075] As a carrier to be used in formula (3) above, a resin coated ferrite carrier which is obtained by coating and drying a coating layer-forming solution of an acryl resin and silicone resin containing particles of alumina to the surface of burnt ferrite powder (weight average particle diameter: 35 µm) is used.
[00076] In formula (3) above, the 50 mL bottle is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include commercially available bottles (manufactured by NICHIDEN-RIKA GLASS CO., LTD. ).
[00077] Coalescent particle characteristics:
[00078] The degree of coalescence is determined by the following formula, in a measurement of the first particle diameter and second particle diameter of the coalescing particle, by determining the secondary particle diameter of a single coalescing particle and an average value of the particle diameters of a plurality of primary particles that make up the coalescing particle.
[00079] Degree of coalescence = secondary particle diameter/mean primary particle diameter
[00080] By observing 100 or more coalescing particles, the degrees of coalescence of the respective particles are determined, and an average value of the degree of coalescence and a rate where the degree of coalescence is less than 1.3 are determined.
[00081] An average of the coalescence degrees of coalescing particles is not particularly limited and may be appropriately selected according to the purpose, however this is preferably 1.5 to 4.0. Where the average degree of coalescence is less than 1.5, coalescing particles cannot sufficiently perform the function as a non-spherical external additive, coalescing particles easily transfer to recesses in the toner base surface, and there is a case where an increase in non-electrostatic adhesion strength between the toner and developer-containing element particularly over time cannot be sufficiently suppressed, and a hysteresis easily occurs, which is therefore not preferable. On the other hand, where the average exceeds 4.0, coalescing particles easily detach from the toner base to cause carrier contamination and damage to the photoconductor, which can therefore result in image defects over time, and is not preferable .
[00082] The content of coalescing particles whose coalescence degree is less than 1.3 is not particularly limited and can be appropriately selected according to the purpose, however this is preferably 10% by number or less. The degree of coalescence has a distribution in production and particles whose degree of coalescence is less than 1.3 are particles whose coalescence has not proceeded, and exist substantially in a state of nearly spherical shapes. Therefore, the particles have a problem and perform the function as a non-spherical additive characterized by suppressing burial. In addition, to determine the coalescent particle content, the coalescence degree is less than 1.3, the average particle diameters of primary particles of a coalescent particle and the secondary particle diameter are measured, by the above method, by 200 or more and 200 or less particles, and then the coalescence degrees of the respective coalescing particles are calculated from the measurements obtained, and the number of particles whose coalescence degree is less than 1.3 is divided by the number of particles measured for calculation.
[00083] A method for confirming that primary particles of the coalescing particle are coalesced with each other is not particularly limited and may be appropriately selected according to the purpose, but this is preferably a method for confirming that primary particles are coalesced with each other by observation through of a scanning electron microscope (SEM).
[00084] The content of the external additive is not particularly limited and can be appropriately selected according to the purpose, however this is preferably 0.5 parts by mass to 4.0 parts by mass for 100 parts by mass of base particles. toner.
[00085] Other external additives
[00086] To toner, various external additives can be added for the purpose of improving fluidity, an adjustment of charge amount, an adjustment of electrical characteristics in addition to coalescing particles. External additives are not particularly limited and may be appropriately selected from those known according to the purpose, and examples thereof include fine silica particles, hydrophobized silica fine particles, fatty acid metal salts (eg, stearate zinc and aluminum stearate); metal oxides (eg titania, alumina, tin oxide and antimony oxide) or those that have been hydrophobized, and fluoropolymers. Among these, fine hydrophobized silica particles, titania particles, and hydrophobized titania particles are suitable.
[00087] The content of other external additives is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 0.3 parts by mass to 3.0 parts by mass to 100 parts by mass of toner base particles .
[00088] Examples of hydrophobized silica fine particles include HDK H2000 HDK H2000/4, HDK H2050EP, HVK21, HDK H1303 (all of which are manufactured by Hoechst AG); and R972, R974, RX200, RY200, R202, R805, R812 (all of which are manufactured by Nippon Aerosil Co., Ltd.). Examples of the fine titania particles include P-25 (Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both of which are manufactured by Titan Kogyo Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); and MT-150W, MT-500B, MT-600B, MT-150A (all of which are manufactured by Tayca Corporation). Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both of which are manufactured by Titan Kogyo Ltd.); TAF-500T, TAF-1500T (both of which are manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both of which are manufactured by Tayca Corporation); and IT-S (manufactured by Ishihara Sangyo Kaisha Ltd.).
[00089] Toner base particles
[00090] The toner base particles contain at least one binder resin and one coloring substance. The toner base particles can further contain a release agent, a charge control agent, a layered inorganic mineral and others as needed.
[00091] Binder resin
[00092] The binder resin is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include polyester resins, silicone resins, acrylic-styrene resins, styrene resins, acrylic resins, epoxy resins, diene based resins phenol resins, terpene resins, coumarin resins, amide-imide resins, butyral resins, urethane resins, and ethylene vinyl acetate resins. These can be used individually or in combination of two or more. Among these, a polyester resin and a resin for which a polyester resin and the other binder resin described above are combined are preferable in view of being excellent in low temperature setting ability to allow flattening of the image surface and in consideration of having sufficient flexibility even at a lower molecular weight.
[00093] Polyester resin:
[00094] The polyester resin is not particularly limited and can be appropriately selected according to the purpose, however it is preferably an unmodified polyester resin and a modified polyester resin. These can be used individually or in combination of two or more.
[00095] Unmodified polyester resin
[00096] Unmodified polyester resin is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include resins for which polyol expressed by the following general formula (1) and polycarboxylic acid expressed by the following general formula (2) are made of polyester resins and crystalline polyester. The present invention can provide a developing device and an image forming apparatus which allow to similarly suppress the occurrence of a hysteresis over time also in a high speed machine loaded with a toner using a crystalline polyester resin and excellent in low temperature fixation capability at which a hysteresis becomes more prominent.
[00097] A - [OH]m ... general formula (1)
[00098] B - [COOH]n... general formula (2)
[00099] In the general formula (1) above, A indicates an alkyl group, an alkylene group, or an aromatic group or heteroaromatic ring group which may have a substituent group having 1 to 20 carbon atoms, in indica an integer from 2 to 4.
[000100] In the general formula (2) above, B indicates an alkyl group, an alkylene group, or an aromatic group or heteroaromatic ring group which may have a substituent group having 1 to 20 carbon atoms, and n indicates an integer from 2 to 4.
[000101] The polyol expressed by the general formula (1) above is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1 ,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexane dimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanotetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2- methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene, bisphenol A, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, hydrogenated bisphenol A, adducts of ethylene oxide of hydrogenated bisphenol A, and propylene oxide adducts of hydrogenated bisphenol A. These can be used singly or in combination of two or more.
[000102] The polycarboxylic acid expressed by the common formula (2) is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include maleic acids, fumaric acids, citraconic acids, itaconic acids, glutaconic acids, phthalic acids , isophthalic acids, terephthalic acids, succinic acids, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid, isodecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl acid succinic, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, 1,2,4-benzene tricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,2 acid ,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, 1,3-dicarboxylic acid-2-methyl-2-methylene-carboxyl propane, 1,2,4-cyclohexane tricarboxylic acid, tetra(methylene carboxyl)methane, 1,2,7,8-o acid tetracarboxylic ethane, pyromellitic acid, empol trimer acid and the like, cyclohexane dicarboxylic acid, cyclohexene dicarboxylic acid, butane tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, and ethylene glycol bis (trimelytic acid). These can be used individually or in combination of two or more.
[000103] Crystalline polyester resin
[000104] Like polyester resin, a crystalline polyester resin can be contained.
[000105] Examples of crystalline polyester resin are preferably crystalline polyesters which are synthesized using as alcohol components, saturated aliphatic diol compounds having 2 to 12 carbon atoms, particularly 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, and derivatives thereof and at least as acid components, dicarboxylic acid having 2 to 12 carbon atoms having a double bond (C=C bond) or acid saturated dicarboxylic acid having 2 to 12 carbon atoms, particularly fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid and derivatives of these.
[000106] Among these, in consideration of making smaller the difference between the endothermic peak temperature and endothermic shoulder temperature, a crystalline polyester resin is preferably composed only of an alcohol component of any one of the group consisting of 1.4 -butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol, and a dicarboxylic acid only from one of the group consisting of fumaric acid, 1,4-butanedioic acid, acid 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid.
[000107] In addition, as a method to control the crystallinity and softening point of a crystalline polyester resin, such a method can be mentioned as designing and using non-linear or similar polyester for which higher trivalent or multivalent alcohol such as glycerin is added to an alcohol component and higher trivalent or multivalent carboxylic acid such as trimellitic anhydride is added to an acid component for condensation polymerization in polyester synthesis.
[000108] The molecular structure of a crystalline polyester resin of the present invention can be confirmed by X-ray diffraction, GC/MS, LC/MS, and IR measurements, and the like, in addition to an NMR measurement in a solution or state solid.
[000109] The toner content of the crystalline polyester resin is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 3% by mass to 15% by mass, and more preferably 5% by mass to 10% by mass. Where the content is less than 3% by mass, there is a case where a fact on the low temperature setting ability cannot be sufficiently obtained, which is not preferable and where the content exceeds 15% by mass, the stability of image density over time, particularly the stability of image density over time on a high-speed machine tends to deteriorate, which is therefore not preferable. Modified polyester resin
[000110] The modified polyester resin is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include resins that are obtained by allowing a compound containing active hydrogen group and polyester (hereafter sometimes referred to as a "polyester prepolymer") capable of reacting with the compound containing active hydrogen group is subjected to an elongation reaction and/or a crosslinking reaction. The elongation reaction and/or crosslinking reaction can be stopped, as required, by a reaction stop (diethyl amine, dibutyl amine, butyl amine, laurel amine, a blocked mono amine such as ketimine compound or the like). Compound containing active hydrogen group
[000111] The active hydrogen group-containing compound acts as a stretching agent, a crosslinking agent and the like when the polyester prepolymer is subjected to an stretching reaction, crosslinking reaction or the like in an aqueous phase.
[000112] The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and may be appropriately selected according to the purpose, but are preferably amines in consideration to allow a higher molecular weight where the pre Polyester polymer is an isocyanate group-containing polyester prepolymer to be described later.
[000113] The active hydrogen group is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include hydroxyl groups (alcoholic hydroxyl groups or phenol hydroxyl groups), amino groups, carboxyl groups and mercapto groups. These can be contained individually or in combination of two or more.
[000114] The amines being the active hydrogen group-containing compound are not particularly limited and may be appropriately selected according to the purpose, and examples thereof include diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, and blocked products in which amino groups of these amines are blocked. Examples of the diamine include aromatic diamines (phenylene diamine, diethyl toluene diamine, 4,4'-diamino diphenyl methane, and the like); alicyclic diamines (4,4'-diamino-3,3'-dimethyl dicyclohexyl methane, cyclohexane diamine; isophorone diamine, and the like); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, and the like). Examples of the trivalent or higher polyamine include diethylene triamine and triethylene tetraamine. Examples of the amino alcohol include ethanol amine and hydroxy ethyl aniline. Examples of the amino mercaptan include amino ethyl mercaptan and amino propyl mercaptan. Examples of the amino acid include aminopropionic acid and aminocaproic acid. Examples of blocked products in which amino groups of these amines are blocked include ketimine compounds obtained from any of these amines (diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid and the like) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone and the like) and oxazolidine compounds. These can be used individually or in combination of two or more. Among those, like amines, diamine and a mixture of diamine and a small amount of trivalent or higher polyamine are particularly preferable.
[000115] Polymer capable of reacting with compound containing active hydrogen group
[000116] A polymer capable of reacting with the compound containing active hydrogen group is not particularly limited as long as it is a polymer having at least one group capable of reacting with the compound containing active hydrogen group, and can be appropriately selected according to the purpose, however, is preferably a polyester resin containing urea binding group (RMPE), and more preferably a polyester prepolymer containing isocyanate group, in consideration of high melt flow, to be excellent in transparency, and allow easy adjustment of molecular weight of polymeric components, thereby excelling in oil-free low-temperature fixation and release capability with a dry toner.
[000117] Polyester prepolymer containing isocyanate group is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include polyol polycondensates with polycarboxylic acid, which are obtained by allowing polyester resins containing active hydrogen group react with polyisocyanate.
[000118] The polyol is not particularly limited and appropriately selected according to the purpose, and examples thereof include diols such as alkylene glycols (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butane diol, 1,6-hexane diol, and the like), alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like), alicyclic diols (1,4-cyclohexane dimethanol, hydrogenated bisphenol A, and the like), bisphenols (bisphenol A, bisphenol F, bisphenol S and the like), alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, and the like) adducts of alicyclic diols, and alkylene oxide (ethylene oxide, propylene oxide, butylene oxide and the like) adducts of bisphenols: trivalent or higher polyols such as multivalent aliphatic alcohols (glycerin, trimethyl oletane, trimethylol propane, pentaerythritol, sorbitol, and the like) trivalent or higher phenols dos (phenol novolac, cresol novolac and the like) and alkylene oxide adducts of trivalent or higher polyphenols; and mixtures of trivalent or higher diols and phenols. These can be used individually or in combination of two or more. Among those, such as the polyol, the diol individually and a mixture of the diol and a small amount of the trivalent or higher phenol are preferable. As the diol, alkylene glycols having 2 to 12 carbons and alkylene oxide adducts of bisphenols (a 2 mole ethylene oxide adduct of bisphenol A, a 2 mole propylene oxide adduct of bisphenol A, an adduct of 3 moles of propylene oxide from bisphenol A, and the like) are preferred.
[000119] The content of a polyester prepolymer containing isocyanate group of the polyol is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 0.5% by mass to 40% by mass, more preferably , 1% by mass to 30% by mass, and particularly preferably 2% by mass to 20% by mass, for example. Where the content is less than 0.5% by mass, where the resistance to hot offset can determine, thereby making it difficult to obtain both the storage capacity and the low temperature setting capacity of the toner, and where the content exceeds 40 % by mass, the low temperature holding capacity may deteriorate.
[000120] The polycarboxylic acid is preferably not limited and may be appropriately selected according to the purpose, and examples thereof include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, and the like); alkenylene dicarboxylic acids (maleic acid, fumaric acid, and the like); aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and the like); and trivalent or higher polycarboxylic acids (aromatic polycarboxylic acids and the like having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid). These can be used individually or in combination of two or more. Among those, like polycarboxylic acid, alkenyl dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable. Furthermore, in place of polycarboxylic acid, acid anhydrides of polycarboxylic acids, lower alkyl esters (methyl ester, ethyl ester, isopropyl ester and the like) and the like can be used.
[000121] A mixing ratio of polyol and polycarboxylic acid is not particularly limited and can be appropriately selected according to the purpose, however this is preferably 2/1 to 1/1 as an equivalent ratio [OH]/[COOH] of hydroxyl group [OH] in the polyol to carboxyl group [COOH] in the polycarboxylic acid, more preferably 1.5/1 to 1/1 and particularly preferably 1.3/1 to 1.02/1.
[000122] The polyisocyanate is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate , tetradecamethylene diisocyanate, trimethyl hexane diisocyanate, tetramethyl hexane diisocyanate and the like); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexyl methane diisocyanate, and the like); aromatic diisocyanates (tolylene diisocyanate, diphenyl methane, diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyl diphenyl, 3-methyl diphenyl methane-4, 4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, and the like); aliphatic aromatic diisocyanates (α, α, α’, a’-tetramethyl xylylene diisocyanate and the like); isocyanurates (tris-isocyanate alkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, and the like); phenol derivatives thereof; and those blocked with oximes, caprolactams or the like. These can be used individually or in combination of two or more.
[000123] A mixing ratio of polyisocyanate and active hydrogen group-containing polyester resin (hydroxyl group-containing polyester resin) is not particularly limited and can be appropriately selected according to the purpose, but is preferably 5/1 to 1 /1 as an equivalent ratio [NCO]/[OH] of isocyanate group [NCO] in the polyisocyanate to hydroxyl group [OH] in the hydroxyl group-containing polyester resin, more preferably 4/1 to 1.2/1 , and particularly preferably 3/1 to 1.5/1. Where the equivalent ratio [NCO]/[OH] is less than 1/, the offset resistance may deteriorate, and where the equivalent ratio exceeds 5/1, the low temperature clamping capability may deteriorate.
[000124] The polyisocyanate content in the polyester prepolymer containing isocyanate group is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 0.5% by mass to 40% by mass, more preferably 1 % by mass to 30% by mass, and particularly preferably 2% by mass to 20% by mass. Where the content is less than 0.5% by mass, the hot offset strength can deteriorate, thereby making it difficult to obtain both storage stability and low temperature fixation capacity, and where the content exceeds 40% by mass, low-temperature clamping ability may deteriorate.
[000125] The average number of isocyanate groups contained in a polyester prepolymer molecule containing isocyanate group is preferably 1 or more, more preferably 1.2 to 5, and even more preferably 1.5 to 4. Where the average number is less than 1, a polyester resin (RMPE) modified by a urea bond generating group can decrease in molecular weight to deteriorate hot offset resistance.
[000126] A mixing ratio of the polyester prepolymer containing isocyanate group and the amines is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 1/3 to 3/1 in an equivalent ratio of [NCO]/[NHx] mixture of isocyanate group [NCO] in polyester prepolymer containing isocyanate group to amino group [NHx] in amines, more preferably ^ to 2/1, and particularly preferably 1/1 .5 to 1.5/1. Where the equivalent mixing ratio ([NCO]/[NHx]) is less than 1/3, the low-temperature fixing ability may decrease, and where the equivalent ratio exceeds 3/1, a urea-modified polyester resin can decrease in molecular weight to determine hot offset resistance. Method for synthesizing polymer capable of reacting with compound containing active hydrogen group
[000127] A method for synthesizing a polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include, in the case of polyester prepolymer containing isocyanate group, a method for synthesis by heating the polyol and polycarboxylic acid to 150°C to 280°C in the presence of a known esterification catalyst (dibutyl tin oxide, titanium tetrabutoxide or the like), appropriately reducing the pressure if needed while performing generation, distilling water to obtain hydroxyl group-containing polyester, and then allowing the polyisocyanate to react with the hydroxyl group-containing polyester at 40°C to 140°C.
[000128] A weight average molecular weight (Mw) of a polymer capable of reacting with the compound containing active hydrogen group is not particularly limited and can be approximately selected according to the purpose, however it is preferably 3,000 to 40,000, and more preferably , 4,000 to 30,000 when a part soluble in tetrahydrofuran (THF) is determined for molecular weight distribution by GPC (gel permeation chromatography). Where the weight average molecular weight (Mw) is less than 3,000, storage stability may deteriorate. Where it exceeds 40,000, the low temperature holding capacity may deteriorate. The determination of the weight average molecular weight (Mw) is carried out, for example, as follows. First, a column is stabilized in a heat chamber kept at 40°C. At this temperature, tetrahydrofuran (THF) as column solvent is allowed to flow at a flow rate of 1 mL per minute, and a sample solution of tetrahydrofuran resin that has been adjusted to be 0.05% by mass to 0.6% in bulk at sample concentration is injected in an amount of 50 μl to 200 μl to make the determination. In determining sample molecular weights, a sample molecular weight distribution is calculated by referring to the relationship between the logarithms of a calibration curve prepared by various types of standard monodisperse polystyrene samples and the counts. The standard polystyrene sample to prepare the calibration curve includes those having the molecular weight of 6 x 102, 2.1 x 102, 4 x 102, 1.75 x 104, 1.1 x 105, 3.9 x 105, 8.6 x 105, 2 x 106, and 4.48 x 106 manufactured by Pressure Chemical Company or Toyo Soda Manufacturing Co., Ltd. At least approximately 10 samples of standard polystyrene are preferably used. It is observed that an RI detector (refractive index) can be used as a detector. Dyestuff
[000129] A coloring substance to be used for the toner of the present invention is not particularly limited and can be appropriately selected from known coloring substances according to the purpose.
[000130] The toner colorant is not particularly limited in color and can be appropriately selected according to the purpose. This can be supplied as at least one selected from a black toner, a cyan toner, a magenta toner, and a yellow toner. The respective color toners can be obtained by properly selecting the type of coloring substance, however color toners are preferable.
[000131] Examples of the colorant for black include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black and channel black, metals such as copper, iron (CI Pigment Black 11), and titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1).
[000132] Examples of coloring pigments for magenta include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48:1, 49, 50, 51, 52, 53, 53:1, 54, 55, 57, 57:1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; C.I. Pigment Violet 19; C.I. Vat Red 1, 2, 10, 13, 15, 23, 29, and 35.
[000133] Examples of coloring pigments for cyan include C.I. Pigment Blue 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 60; C.I.Vat Blue 6; C.I. Acid Blue 45 or copper phthalocyanine pigments having a phthalocyanine skeleton substituted with 1 to 5 phthalimidemethyl groups, Green 7 and Green 36.
[000134] Examples of color pigments for yellow include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65 , 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; C.I. Vat Yellow 1, 3, 20, and Orange 36.
[000135] The content of a coloring substance in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. Where the content is less than 1% by mass, the toner may decrease in coloring potency, and where the content exceeds 15% by mass, the pigment may be poorly dispersed in the toner to cause decrease in coloring potency and degradation in characteristics toner cartridges.
[000136] The coloring substance can be used as a master batch combined with a resin. Such a resin is not particularly limited, however in consideration of compatibility with a binder resin in the present invention, the binder resin or a resin having a structure similar to that of the binder resin is preferably used.
[000137] Master batch can be produced by mixing or kneading a resin and a coloring substance under a high shear force. In that case, to increase the interactions between the coloring substance and the resin, it is preferable to add an organic solvent. Furthermore, a so-called flushing method is also suitable in which a wet mass of coloring substance can be used, as is, to eliminate subsequent drying. The flushing method is a method in which an aqueous slurry containing water of the dyestuff is mixed or kneaded together with the resin and the organic solvent, whereby the dyestuff is transferred to the resin to remove water and the organic solvent. Mixing or kneading can be conducted by using, for example, a high shear dispersing apparatus such as a three-roll mill. release agent
[000138] The release agent is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include waxes such as vegetable-based waxes (carnauba wax, cotton wax, haze wax, rice wax and similar), animal waxes (beeswax, lanolin, and the like), mineral waxes (ozokerite, selsyn and the like) and petroleum waxes (paraffin wax, microcrystalline wax, eptrolate wax, and the like ); waxes other than natural waxes such as synthesized hydrocarbon waxes (Fischer Tropsch wax, polyethylene wax, and the like) and synthesized waxes (ester, ketone, ether and the like); fatty acid amides such as 12-hydroxy stearamide, stearamide, anhydrous phthalic acid imide, and chlorinated hydrocarbon; and crystalline high polymers having long alkyl groups in side chains including polyacrylate homopolymers or copolymers like poly-n-stearyl methacrylate and poly-n-lauryl methacrylate which are low molecular weight crystalline high polymers (n-acrylate copolymers). stearyl - ethyl methacrylate and the like). Among these, wax having a melting point of 50°C to 120°C is preferable on account of being able to act effectively as a release agent between the toner and fixing roller interface, thereby allowing to improve the hot offset resistance even without applying a release agent such as oil to the pinch roller.
[000139] A melting point of the release agent is not particularly limited and can be appropriately selected according to the purpose, however that is preferably 50°C to 120°C, and more preferably 60°C to 90°C. Where the melting point is less than 50°C, wax can adversely affect storage stability, and where it exceeds 120°C, it is prone to cause cold offset on low temperature fixation. A melting point of the release agent is determined by measuring the maximum endothermic peak using a differential scanning calorimeter (TG-DSC system, TAS-100, manufactured by Rigaku Denki Co., Ltd.).
[000140] A melt viscosity of the release agent is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 5 cps to 1000 cps as a measurement at a temperature that is 20°C higher than the melting point of the wax, and more preferably 10 cps to 100 cps. Where the melt viscosity is less than 5 cps, the release ability may decrease, and where the melt viscosity exceeds 1000 cps, improving effects on hot offset resistance and low temperature setting ability can no longer be obtained.
[000141] The release agent preferably exists in a dispersed state in the toner base particles, and for that purpose, it is preferable that the release agent and the binder resin are not mutually soluble. A method by which the release agent is finely dispersed in the toner base particles is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include a method for dispersing under shear force for kneading in production of toner.
[000142] A dispersion state of the release agent can be confirmed by observing a thin film section of a toner particle through a transmission electron microscope (TEM). The dispersion diameter of the release agent is preferably small, but slow flow in fixation may be insufficient if the dispersion diameter is too small. Therefore, if the release agent can be confirmed at a magnification power of 10,000x, this indicates that the release agent exists in a dispersed state. Where the release agent cannot be confirmed at 10,000x, this results in insufficient slow flow in fixation even when the release agent is finely dispersed.
[000143] The toner content of the release agent is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 1% by mass to 20% by mass, and more preferably 3% by mass to 10% by mass pasta. Where the content is less than 1% by mass, the hot offset resistance tends to deteriorate, and where the content exceeds 20% by mass, the heat resistant storage stability, load capacity, transfer capacity, and tensile strength tend to deteriorate, which is not preferable. Cargo Control Agent:
[000144] In addition, it is also possible to make toner containing a charge control agent as needed to impart proper charge performance to the toner.
[000145] As a load control agent, any of the known load control agents can be used. Since the use of colored material can change the color tone, a material that is colorless or close to white is preferable, and examples thereof include triphenyl methane based dyes, molybdic acid chelate pigments, dyes based on rhodamine, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkyl amides, a single body of phosphorus or compounds thereof, a single body of tungsten or compounds thereof, fluorine activators, salts of salicylic acid metal, and metal salts of salicylic acid derivatives. These can be used individually or in combination of two or more.
[000146] The charge control agent content is determined depending on a toner production method including the type and method of dispersion of a binder resin, and is not exclusively limited, but is preferably 0.01% by mass at 5 % by mass, and more preferably 0.02% by mass to 2% by mass for the binder resin. Where the amount of addition exceeds 5% by mass, the charge capacity of the toner is excessively large, which reduces the effect of charge control agent, the electrostatic attractive force with the developing roller increases, which can cause a decrease in developer fluidity and a decrease in image density. Where the add amount is minus 0.01% by mass, the charge lift property and charge amount are insufficient, which is prone to affect a toner image. Layered inorganic mineral
[000147] The layered inorganic mineral is not particularly limited as long as it is an inorganic mineral of a layered rolling mill a few nanometers thick, and can be appropriately selected according to the purpose. Examples thereof include montmorillonites, bentonites, hectorites, attapulgites, sepiolites and mixtures thereof. These can be used individually or in combination of two or more. Among these, a modified layered inorganic mineral is preferable in consideration of allowing deformation when granulating a toner to perform a charge adjustment function and being excellent in low temperature setting ability, and a modified layered inorganic mineral for which a Layered mineral having a basic crystal structure based on montmorillonite is modified with organic cations is more preferable, and organic modified bentonite and montmorillonite are particularly preferable in view of allowing to easily adjust viscosity without influencing toner characteristics.
[000148] For the modified layered inorganic compound, it is preferable to modify the layered inorganic mineral at least in part by organic ions. By modifying the layered inorganic mineral at least in part by organic ions, the modified inorganic layered compound has moderate hydrophobicity, has a non-Newtonian viscosity in an oil phase including a toner composition and/or a toner composition precursor, thereby allowing toner deformation.
[000149] The toner base particle content of the modified layered inorganic mineral is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 0.05% by mass to 5% by mass. Toner production method
[000150] As a production method and material for a toner in the present invention, any known production method and material can be used as long as they meet conditions, and there is no specific limitation, but examples thereof include a kneading and spraying method and a process called chemical in which toner particles are granulated in an aqueous medium.
[000151] Examples of the chemical process include a suspension spray method, an emulsion polymerization method, a seed polymerization method, a dispersion polymerization method, and others in which a monomer is used as a starting material to produce a toner; a suspension-dissolving method in which a resin or resin precursor is dissolved in an organic solvent or the like to effect dispersion or emulsification in an aqueous medium; a method (production method (I)) for which, in a dissolution suspension method, an oil phase composition including a resin precursor (reactive group-containing prepolymer) having a functional group reactive with a group of activated hydrogen is emulsified or dispersed in an aqueous medium including fine resin particles, and in the aqueous medium a compound containing active hydrogen group and the prepolymer containing reactive group are allowed to react; a phase inversion emulsification method in which phase inversion is allowed to occur by adding water to a solution composed of a resin or resin precursor and an appropriate emulsifying agent; and an aggregation method in which resin particles obtained by any of these methods are aggregated in a state of being dispersed in an aqueous medium and granulated into particles of a desired size by heat melting and the like. Among these, a toner produced by any of the dissolution suspension method, the production method (I) and the aggregation method is preferable in terms of granulation property due to a crystalline resin (particle size distribution control, control of particle format, and others) and a toner produced by the production method (I) is more preferable.
[000152] In the following, a detailed description will be given of these production methods.
[000153] The kneading spray method is a method for producing toner base particles, for example, by spraying and sorting a toner material containing at least one colorant, a binder resin and a release agent that has been kneaded by Fusion.
[000154] In fusion kneading, the toner material is mixed, and the mixture is loaded into a fusion kneader for fusion kneading. As a melting kneader, for example, a continuous single-screw or twin-screw kneader, or a batch-type kneader by a roller mill can be used. Examples thereof that are suitably used include a KTK model twin screw extruder manufactured by Kobe Steel, Ltd., a TEM model extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by KCK Co., Ltd. ., a PCM model twin-screw extruder manufactured by Ikegai Iron Works, Ltd., and a co-kneader manufactured by Buss AG. It is preferable to carry out such melt kneading under appropriate conditions so as not to cause molecular chain cutting of the binder resin. Specifically, melt kneading is carried out at a temperature with reference to a resin binder softening point, severe cutting can occur when the temperature is excessively higher than the softening point, and dispersion may not be in progress when the temperature is excessively low.
[000155] In spraying, a kneaded product obtained by kneading is sprayed. In spraying, it is preferable that the kneaded product is first coarsely pulverized and then finely pulverized. In this case, a method is preferably used in which the product is sprayed by collision with a collision plate in a jet stream, sprayed by allowing particles to collide together in the jet stream, or sprayed into a narrow gap between a mechanically rotating rotor and a stator.
[000156] In classification, a powdered product obtained by spraying is classified and fitted into particles with a predetermined particle diameter. Classification can be accomplished by removing the fine particles of particles with the use of a cyclone, a decanter, a centrifugal machine or the like.
[000157] After completion of spraying and classification, the sprayed product is classified in an air stream by a centrifugal force or similar, thereby making it possible to produce toner base particles with a predetermined particle diameter.
[000158] The dissolution suspension method is a method for producing base particles of a toner, for example, by dispersing or emulsifying in an aqueous medium an oil phase composition for which a toner composition containing at least one resin binder or resin precursor, a coloring substance, and a release agent is dissolved or dispersed in an organic solvent.
[000159] The organic solvent to be used when dissolving or dispersing the toner composition is preferably a volatile solvent having a boiling point less than 100°C in consideration of ease in subsequent solvent removal.
[000160] Examples of the organic solvent include ester-based or ether-ether-based solvents such as ethyl acetate, butyl acetate, methoxy butyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; ether-based solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; alcohol-based solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethyl hexyl alcohol, and benzyl alcohol; and solvent mixtures of two or more of these.
[000161] In the dissolution suspension method, when dispersing or emulsifying an oil phase composition in an aqueous medium, an emulsifying agent or dispersing agent can be used as needed.
[000162] As the emulsifying agent or dispersing agent, a known surface active agent, water-soluble polymer, or the like can be used. The surface active agent is not particularly limited, and examples thereof include anionic surface active agents (alkyl benzene sulfonate, phosphorate ester, and the like), cationic surface active agents (quaternary ammonium salt types, amine salt types , and the like), ampholytic surface active agents (carboxylate types, sulfate types, sulfonate types, phosphate types and the like) and nonionic surface active agents (AO adduct types, polyalcohol types and the like). As a surface active agent, these surface active agents can be used individually or in combination of two or more.
[000163] Examples of water-soluble polymer include compounds based on cellulose (for example, methyl cellulose, ethyl cellulose, hydroxy ethyl cellulose, ethyl hydroxy ethyl cellulose, carboxy methyl cellulose, hydroxy propyl cellulose, and saponified products thereof), gelatins, starches, dextrins, arabic gums, chitins, chitosans, polyvinyl alcohols, polyvinyl pyrrolidones, polyethylene glycols, polyethylene imines, polyacrylamides, acrylate-containing polymers (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, polyacrylate partially neutralized with sodium hydroxide, acrylic acid-sodium acrylate ester copolymers), maleic anhydride-styrene copolymers (partially) neutralized with sodium hydroxide, and water-soluble polyurethanes (reaction products of polyethylene glycol, polycaprolactone diol and others with polyisocyanate and the like).
[000164] Furthermore, as an emulsification or dispersion aid, the organic solvent described above and a plasticizer can be used in combination.
[000165] It is preferable to obtain a toner according to the present invention by granulating base particles of a toner by a method (production method (I)) for which, in a suspension by dissolution method, a phase composition of oil including at least one binder resin, a binder resin precursor (reactive group-containing prepolymer) having a functional group reactive with an activated hydrogen group, a colorant, and a release agent is dispersed or emulsified in an aqueous medium including fine resin particles, and a compound containing active hydrogen group included in the oil phase composition and/or aqueous medium and the prepolymer containing reactive group are allowed to react.
[000166] The resin fine particles can be formed by using a known polymerization method, but are preferably obtained as an aqueous dispersion of resin fine particles. Examples of a method for preparing an aqueous dispersion of fine resin particles include the following (a) to (h). (a) A method in which vinyl monomer is used as a starting material, polymerization reaction is conducted by any method selected from suspension polymerization method, emulsion polymerization method, seed polymerization method, and disperse polymerization method to directly prepare an aqueous dispersion of fine resin particles. (b) A method in which a precursor (monomer, oligomer, or others) of a polyaddition or condensing resin such as a polyester resin, polyurethane resin, and epoxy resin or solvent solution thereof is dispersed in a medium aqueous in the presence of a suitable dispersing agent, and then cured by heating or adding a curing agent, thereby preparing an aqueous dispersion of fine resin particles. (c) a method in which an appropriate emulsifying agent is dissolved in a precursor (monomer, oligomer or others) of a polyaddition or condensing resin such as a polyester resin, polyurethane resin and epoxy resin or in a solvent solution of same (which is preferably in a liquid, or which can be liquefied by heating), and then water is added to effect the phase inversion emulsification, thereby preparing an aqueous dispersion of fine resin particles.
[000167] (d) A method in which a resin previously synthesized by polymerization reaction (for example, addition polymerization, ring opening polymerization, polyaddition, addition condensation, or condensation polymerization) is sprayed using a sprayer of the type mechanical rotation or a jet-type spray, and then classified to obtain fine resin particles, which are further dispersed in water in the presence of a suitable dispersing agent, thereby preparing an aqueous dispersion of fine resin particles.
[000168] (e) a method in which a resin previously synthesized by polymerization reaction (for example, addition polymerization, ring opening polymerization, polyaddition, addition condensation, or condensation polymerization) is dissolved in a solvent to provide a resin solution, which is sprayed in a mist form to obtain fine resin particles, thereafter, the fine resin particles are dispersed in water in the presence of a suitable dispersing agent, thereby preparing an aqueous dispersion of fine resin particles. resin.
[000169] (f) a method in which a resin previously synthesized by polymerization reaction (for example, polymerization reaction is acceptable as addition polymerization, ring opening polymerization, polyaddition, addition condensation, or condensation polymerization) is dissolved in a solvent to provide a resin resolution, to which a weak solvent is added, or a resin solution previously dissolved in a solvent by heating is cooled to prepare fine resin particles, the solvent is removed to obtain resin particles, and thereafter the resin particles are dispersed in water in the presence of a suitable dispersing agent, thereby preparing an aqueous dispersion of fine resin particles.
[000170] (g) a method in which a resin previously synthesized by polymerization reaction (for example, addition polymerization, ring opening polymerization, polyaddition, addition condensation or condensation polymerization) is dissolved in a solvent to provide a resin solution, and the resin solution is dispersed in an aqueous medium in the presence of a suitable dispersing agent, and thereafter the solvent is removed by heating or under reduced pressure, thereby preparing an aqueous dispersion of fine resin particles.
[000171] (h) A method in which a resin previously synthesized by polymerization reaction (for example, addition polymerization, ring opening polymerization, polyaddition, addition condensation, or condensation polymerization) is dissolved in a solvent to provide a resin solution, a suitable emulsifying agent is dissolved in the resin solution, and then water is added to effect phase inversion emulsification, thereby preparing an aqueous dispersion of fine resin particles.
[000172] The fine resin particles preferably have an average particle diameter: volume of 10 nm or more and 300 nm or less, and more preferably 30 nm or more and 120 nm or less. Where the average particle diameter: volume of resin fine particles is less than 10 nm and where it exceeds 300 nm, the toner may deteriorate in particle size distribution, which is therefore not preferable.
[000173] The oil phase preferably has a solid content concentration of 40% by mass to 80% by mass. When the concentration is too high, the oil phase is difficult to dissolve or disperse. Also, the oil phase is increased in viscosity and handling is difficult. Where concentration is excessively low, toner productivity decreases.
[000174] Toner compositions such as the coloring agent and release agent other than a resin binder as well as master batches thereof can be individually dissolved or dispersed in an organic solvent and then mixed with a resin binder solution or dispersion solution .
[000175] As the aqueous medium, water can be used individually, however a water miscible solvent can be used in combination. Examples of the miscible solvent include alcohols (methanol, isopropanol, ethylene glycol, and the like), dimethyl formamide, tetrahydrofuran, cellosolves (methyl cellosolve and the like) and lower ketones (acetone and methyl ethyl ketone and the like).
[000176] A method for dispersing or emulsifying in aqueous media is not particularly limited, and applicable is any known equipment selected from low speed shear, high speed shear, friction, high pressure jet and supersonic types. Of equipment, high speed shear equipment is preferable in terms of making particles with a small diameter. Where a high speed shear dispersion machine is used, there is no specific limitation on the number of revolutions, however this is normally 1,000 rpm to 30,000 rpm, and preferably 5,000 rpm to 20,000 rpm. The temperature in the dispersion is usually 0°C to 150°C (under pressure), and preferably 20°C to 80°C.
[000177] To remove organic solvent from an obtained emulsified dispersion product, any known technique can be used without specific limitation, and for example, a method can be adopted in which an entire system is gradually heated under normal or reduced pressure to remove fully evaporatively an organic solvent in droplets.
[000178] As a method for washing and drying base particles of a dispersed toner in an aqueous medium, known techniques are used. That is, after a centrifugal machine, a filter press, or the like is used to effect solid-liquid separation, the toner mass thus obtained is dispersed again in ion-exchanged water at normal temperature at approximately 40°C and acid or alkali is used to adjust the pH of the mass, if necessary, later performing the solid-liquid separation again. This step is repeated several times to remove impurities and a surface active agent, and thereafter drying is performed by using an instant dryer, a circulation dryer, a vacuum dryer, a vibration fluidized dryer, or the like to obtain toner powder . In that case, centrifugation or the like can be performed to remove fine particle components from the toner. Furthermore, any known classifier can be used to obtain desired particle-particle distribution after drying, if necessary.
[000179] The aggregation method is a method for producing toner base particles by mixing at least a resin fine particle dispersion made of a binder resin and a dyestuff particle dispersion and a release agent particle dispersion , if necessary, to perform aggregation. The resin fine particle dispersion is obtained by a known method, for example an emulsion polymerization method, a seed polymerization method, or a phase inversion emulsification method, and the dyestuff particle dispersion and The release agent particle dispersion are obtained by dispersing a coloring substance or a release agent in an aqueous medium by a known wet dispersion method or the like.
[000180] An aggregation state is preferably controlled by a method such as applying heat, adding a metal salt, or adjusting pH.
[000181] There is no specific restriction on metal salt. Examples of the metal salt include monovalent metals which constitute salts such as sodium or potassium; divalent metals that constitute salts such as calcium or magnesium; and trivalent metals that constitute salts such as aluminum.
[000182] Examples of anions that make up salts include chloride ions, bromide ions, iodide ions, carbonate ions and sulfate ions. Among these, magnesium chloride, aluminum chloride, a mesos complex, and a multimer thereof are preferable.
[000183] In addition, heating is done during aggregation or after completion of aggregation, whereby melting of the fine resin particles can be accelerated. This is preferable in terms of the uniformity of a toner. Still additionally, the shape of the toner can be controlled by heating. In most cases, more heat makes the toner closer to a spherical shape.
[000184] For a method for washing and drying base particles from a dispersed toner in an aqueous medium, the above method and similar may be used.
[000185] In addition, to improve the fluidity, storage stability, revealability, and transferability of the toner, the toner base particles thus manufactured, which is added and mixed with the coalescing particles, can be additionally added and mixed with inorganic particles such as fine hydrophobic silica powder.
[000186] A common powder mixer is used to mix an additive, however it is preferable to equip a jacket or similar to adjust the temperature inside. Here, to change the history of stress applied to the additive, the additive can be added in the middle or gradually. In this case, the number of revolutions, rolling speed, time, temperature and the like of the mixer can be changed. Alternatively, first a strong voltage and then a relatively weak voltage can be added and vice versa. Examples of mixing equipment available include a V-shape mixer, a Rocking mixer, a LOEDIGE mixer, a NAUTA mixer and a HENSCHEL mixer. Next, coarse particles and aggregation particles are removed by sieving with a 250 mesh sieve or more, and in this way a toner can be obtained.
[000187] The toner is not particularly limited in terms of its shape and size and can be appropriately selected according to the purpose, however it is preferable to have the following average roundness, average particle diameter to volume, particle diameter ratio volume-average and number-average particle diameter (volume-average particle diameter/numeric mean particle diameter) and similar.
[000188] The average roundness is a value obtained by dividing a perimeter of an equivalent circle equal in the area projected to the toner shape by a perimeter of an actual particle, and is preferably 0.950 to 0.980, and more preferably 0.960 to 0.975, for example . One containing particles having an average roundness less than 0.95 to 15% or less is preferable.
[000189] When the average roundness is less than 0.950, satisfactory transferability and a high quality image without dust may not be obtained, and when this is greater than 0.980, in an imaging system employing cleaning of dust. blade or the like, there is a possibility that a cleaning defect occurs in the photoconductor, transfer belt, and the like to cause image fouling for example, in the case of formation of an image with a high image area ratio such as a photographic image, background dirt as a result of toner that has formed an untransferred image due to a paper feed defect and the like being accumulated as residual untransferred toner in the photoconductor or contaminating the charge roller bearing the photoconductor in contact to disable the load roller to display original load capacity.
[000190] Average circularity was measured using a flow-type particle image analyzer ("FPIA-2100" manufactured by SYSMEX CORPORATION) and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00 -10). Specifically, in a 100 ml glass beaker, 0.1 ml to 0.5 ml of 10% by mass surface active agent (alkyl benzene sulfonate, NEOGEN SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. ) was placed, then 0.1 g to 0.5 g of each of the toners was added and stirred with a micro spatula, and then 80 ml of ion exchange water was added. The dispersion thus obtained was dispersed in an ultrasonic dispersion machine (manufactured by Honda Electronics Co., Ltd.) for 3 minutes. Toner shape and distribution of the dispersion were measured using the FPIA-2100 analyzer until a concentration of 5,000 to 15,000 particles/uL was obtained. In the present measurement method, control of the dispersion concentration at 5,000 to 15,000 particles/uL is important from the reproducibility point of average roundness measurement. To obtain the dispersion concentration, it is necessary to change the dispersion conditions, that is, the amount of surface active agent and the amount of toner to be added. Similar to the toner particle diameter measurement described above, the surface active agent requirement differs depending on the hydrophobicity of the toner, noise due to bubbles occurs when a large amount of the surface active agent is added, although it is impossible to sufficiently wet the toner when the quantity is small, and thus the dispersion is insufficient. Also, the toner addition amount differs depending on the particle diameter, the amount is small with a small particle diameter, although it is necessary to increase the amount with a large particle diameter, and when the toner particle diameter is 3 1 to 10 µm, it becomes possible to adjust the dispersion concentration from 5,000 to 15,000 particles/ul by adding the toner at 0.1 g to 0.5 g.
[000191] The volume-average particle diameter of the toner is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 3 µm to 10 µm, and more preferably 4 µm to 7 µm, for example. When the volume-average particle diameter is less than 3 µm with a two-component developer, toner can be melt bonded to the surface of a carrier as a result of long-term agitation in a developer device, which deteriorates the carrying capacity of the carrier, and when it is more than 10 µm, it becomes difficult to get a high resolution, high image quality, and the toner particle diameter can fluctuate a lot when the toner is consumed and replenished in the developer.
[000192] The ratio of volume-average particle diameter and number-average particle diameter (volume-average particle diameter/numeric mean particle diameter) in the toner is preferably 1.00 to 1.25, and more preferably 1 .10 to 1.15.
[000193] The volume-average particle diameter and the ratio of the volume-average particle diameter and the number-average particle diameter (volume-average particle diameter/numeric mean particle diameter) were measured at an aperture diameter of 100 µm by use of a particle size analyzer (“Multisizer III”, manufactured by Beckman Coulter, Inc.) and analyzed by analysis software 100 ml glass beaker 0.5 ml of a 10% surface active agent bulk (alkyl benzene sulfonate, NEOGEN SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was put in, then 0.5 g of each of the toners was added thereto and stirred with a micro spatula, then 80 mL of ion exchange water was added. The dispersion thus obtained was dispersed in an ultrasonic dispersion machine (W-113MK-II, manufactured by Honda Electronics Co., Ltd.) for 10 minutes. Using Isoton III (manufactured by Beckman Coulter, Inc.) as a measurement solution, the dispersion properties were measured using the Multisizer III. The measurement was carried out by dropping the toner sample dispersion in such a way that its concentration indicated by the analyzer reaches 8+2%. In the present measurement method, controlling the concentration of the toner sample dispersion by 8+2% is important from the point of reproducibility of measuring the particle diameter. In this concentration range, no error regarding the particle diameter occurs. developer
[000194] A developer in the present invention is a two-component developer containing toner and carrier. When used in a high-speed printer suitable for improvements in information processing speeds in recent years, two-component developer is preferred in terms of an extended service life.
[000195] In two-component developer in which toner is used, even after the toner is balanced for a long time, the diameter of toner particles in the developer changes less, and favorable and stable developing ability is also provided after prolonged stirring by the developer unit. Conveyor
[000196] A carrier of the present invention is not particularly limited as long as it meets formula (1) above, and can be appropriately selected according to the purpose, however one having a core particle and a resin layer (coating layer) coating the core particle is preferable. Furthermore, it is preferable to have a magnetic core particle and a coating layer that covers the core particle and has an SF-2 shape factor of 115 to 150 and a bulk density of 1.8 g/cm3 to 2, 4 g/cm3 and that the core particle has an SF-2 shape factor of 120 to 160, the core particle has an arithmetic mean surface roughness Ra of 0.5 µm to 1.0 µm, and the layer of coating contains a resin and inorganic fine particles, and contains the inorganic fine particles at a rate of 50 parts by weight to 500 parts by weight per 100 parts by weight of resin.
[000197] By combining with a carrier having the above-described specific shape, bulk density, etc., also in an imaging apparatus loaded with a toner excellent in low temperature fixing ability, the occurrence of a hysteresis can be similarly suppressed. core particle
[000198] The core particle is not particularly limited as long as it is a magnetic core particle, and can be appropriately selected according to the purpose. Examples thereof include resin particles for which magnetic materials such as ferromagnetic metals including iron and cobalt; iron oxides such as magnetite, hematite, and ferrite; and various alloys and compounds are dispersed in the resin. Among these, Mn-based ferrite, Mn-Mg-based ferrite, and Mn-Mg-Sr-based ferrite are preferable in terms of environmental considerations. Core Particle SF-1 Shape Factor
[000199] The core particle is regulated by an SF-1 format factor.
[000200] The SF-1 regulates the degree of roundness of the particle.
[000201] When SF-1 has a larger value, the particle shape deviates from a circle (spherical shape).
[000202] An SF-1 shape factor of the core particle is not particularly limited, and can be appropriately selected according to the purpose.
[000203] The determination of an SF-1 shape factor of the core particle is performed by randomly sampling 100 particle images of the core particles magnified at 300x using a scanning electron microscope (eg FE-SEM ( S-800), manufactured by Hitachi, Ltd.) and analyze image information obtained by an image analyzer (eg Luzex AP, manufactured by NIRECO CORPORATION, and calculate using the following formula (I)). SF-1 = (L2/A) x (π/4) x 100 ...
[000204] In the above formula (I), L indicates the absolute maximum length (length of circumscribed circle) of a particle, and A indicates a projected area of a particle. Core Particle SF-2 Shape Factor -
[000205] The core particle is regulated by an SF-2 format factor.
[000206] SF-2 regulates the degree of particle irregularity.
[000207] When the SF-2 has a higher value, the particle surface irregularity has more intense up and down movements.
[000208] The SF-2 core particle shape factor is not particularly limited as long as it is 120 to 160, and can be appropriately selected according to the purpose. Where the SF-2 form factor is less than 120, the projections on the core particle are easily coated so that local low strength may become difficult to form. On the other hand, where the SF-2 form factor exceeds 160, there is a large empty space in the core particle, not only does the core particle have a weak strength, but also when used in a developing device for a long period. over time, the core particle is greatly exposed to having a large change between an initial resistance value and a resistance value after use, so the amount of toner in an element that contains electrostatic imaging and the way in which a Toner image is formed in the same image density may vary.
[000209] The determination of an SF-2 shape factor of the core particle is performed by randomly sampling 100 particle images of core particles magnified at 300x using a scanning electron microscope (eg FE-SEM ( S-800), manufactured by Hitachi, Ltd.) and analyze image information obtained by an image analyzer (eg Luzex AP, manufactured by NIRECO CORPORATION) and calculate using the following formula (II). SF-2 = (P2/A) x (1/4π) x 100 ... (II)
[000210] In formula (II) above, R indicates a perimeter of a particle, and A indicates a projected area of a particle. - arithmetic mean surface roughness Ra of the core particle
[000211] An arithmetic mean surface roughness Ra of the core particle regulates the surface roughness of the core particle.
[000212] The arithmetic mean surface roughness Ra of the core particle is preferably 0.5 µm to 1.0 µm, and more preferably 0.6 µm to 0.9 µm. Where the arithmetic mean surface roughness Ra of the core particle is less than 0.5 µm, there is a case where a carrier has an excessively small arithmetic mean surface roughness after being formed with a coating layer, and as a result of a reduction in contacts between the carrier and toner, the adhesion force between the toner and carrier cannot act properly, so the toner remains adhered to the developer-containing element and a hysteresis easily occurs, which is not preferable. Where the arithmetic average surface roughness Ra of the core particle exceeds 1.0 µm, there is a case where a carrier has an excessively large arithmetic average surface roughness after being formed with a coating layer, and when used in a developing device by a Long period of time, the wear of the coating layer on projections is notable to have a large change between an initial resistance value and a resistance value after use, so that the amount of toner in an element that contains electrostatic imaging and the way a toner image is formed on it varies to vary the image density, which is not preferable.
[000213] The determination of an arithmetic mean surface roughness Ra of the core particle is performed, by using an optical microscope (eg OPTELICS C130, manufactured by Lasertec Corporation), by adjusting the objective lens magnification to 50x, scanning a image at a resolution of 0.20 µm, and then adjust an observation area of 10 µm x 10 µm around an apex part of the core particle, and determine an average value of the surface roughness Ra of the 100 core particles .
[000214] Weight mean particle diameter Dw of core particle
[000215] A core particle weight average particle diameter Dw means a particle diameter at an integrated value of 50% in a particle size distribution of the core particles determined by a laser diffraction or scanning method. The weight-average particle diameter Dw of the core particles is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 10 µm to 80 µm.
[000216] For determination of a weight-average particle diameter Dw of the core particle, a particle diameter distribution of particles measured on a number basis (the relationship between number frequency and particle diameter) is measured under the conditions to be described later using a Microtrac particle size analyzer (HRA9320-X100, manufactured by Honeywell, Inc.), and a weight-average particle diameter is calculated using the following formula (III). Each channel indicates a length to divide the particle diameter range into a particle diameter distribution graph in measurement width units, and the representative particle diameter adopts a lower bound particle diameter value that is stored in each channel.
[000217] Dw = {1/∑(nD3)} x {∑(nD4)} ... (III)
[000218]
[000219] In formula (III) above, D indicates a representative particle diameter (one) of core particles present in each channel, and n indicates a total number of core particles present in each channel. Measurement conditions [1] particle diameter range: 100 µm to 8 µm [2] channel length (channel width): 2 µm [3] number of channels: 46 [4] refractive index: 2.42 coating layer
[000220] The coating layer is formed of a resin and a coating layer-forming solution that contains a filler material, and inorganic particles are preferable as the filler material.
[000221] The coating layer is not particularly limited and can be appropriately selected according to the purpose as long as it is a coating layer containing the filler material at a rate of 50 parts by mass to 500 parts by mass to 100 parts by mass of resin, however a coating layer that contains the filler at a rate of 100 parts by mass to 300 parts by mass to 100 parts by mass of resin is preferable. Where the content of the filler material is less than 50 parts by mass, the coating layer can be scraped off, and where it exceeds 500 parts by mass, a relatively small ratio of resin appears on the carrier surface, and used toner can easily occur on the conveyor surface. On the other hand, where the content is in the preferable range, there is an advantage that a coating layer is difficult to scrape off when used for a long period of time in a developing device.
[000222] As the thickness of the coating layer, if it is excessively thin, the surface of the core particle is easily exposed due to agitation in a developing device, which can result in a large change in strength value, and if it is excessively thick, the projections on the core particle are not exposed, thus making it difficult to form a state of low local resistance. The thickness of the coating layer can be controlled by the resin content relative to the core particle. The resin content for the core particle is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 0.5% by mass to 3.0% by mass in consideration of allowing the formation of a state of local low resistance by coating layer thickness. Resin
[000223] The resin is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyesters, polycarbonates, polyethylenes, fluorides of polyvinyl, polyvinylidene fluorides, polytrifluoroethylenes, polyhexafluoropropylenes, vinylidene fluoride and vinyl fluoride copolymers, fluoroterpolymers such as tetrafluoroethylene terpolymers, vinylidene fluoride, and non-fluorinated monomers and silicone resins. These can be used individually or in combination of two or more. Among these, a silicone resin is particularly preferable in view of high efficiency.
[000224] The resin is not particularly limited and can be appropriately selected according to the purpose, however it is preferably a resin including a cured mixture containing a silane coupling agent and a silicone resin. silicone resin
[000225]

[000226] In the general formula (A) above, R1 indicates a hydrogen group and a methyl group, R2 indicates an alkyl group having 1 to 4 carbon atoms, m indicates an integer from 1 to 8, and X indicates a molar ratio in the copolymer, and indicates 10% by mol to 90% by mol.

[000227] In the general formula (B) above, R1 indicates a hydrogen group and a methyl group, R2 indicates an alkyl group having 1 to 4 carbon atoms, R3 indicates any of an alkyl group having 1 to 8 atoms of carbon or an alkoxy group having 1 to 4 carbon atoms, m indicates an integer from 1 to 8, and Y indicates a molar ratio in the copolymer and indicates 10% by mole to 90% by mole. silane coupling agent
[000228] The silane coupling agent allows to stably disperse the filling material.
[000229] The silane coupling agent is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include r-(2-aminoethyl)aminopropyltrimethoxysilane, r-(2-aminoethyl)aminopropylmethyldimethoxysilane, r-methacryloxypropyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-r-aminopropyltrimethoxysilane hydrochloride, r-glycidoxypropyltrimethoxysilane, r-mercaptopropyltrimethoxysilane , methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, r-chloropropyltrimethoxysilane, hexamethyldisilazane, r-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, r-chloropropylmethyldichlorotoxysilane, 3-methyltrimethoxysilane, trimethyldimethyoxysilane aminopropyltrimethoxysilane, dimethyldiethoxysilane, 1,3-divinyltetramethyldisilazane, and methacryloxyethyldimethyl(3-trimethoxysilylpropyl) ammonium chloride. These can be used individually or in combination of two or more.
[000230] Examples of commercially available products of the silane coupling agent include AY43-059, SR6020, SZ6023, SH6020, SH6026, SZ6032, SZ6050, AY43-310M, SZ6030, SH6040, AY43-026, AY43-031, sh6062, Z-6911, sz6300, sz6075, sz6079, sz6083, sz6070, sz6072, Z-6721, AY43-004, Z-6187, AY43-021, AY43-043, AY43-040, AY43-047, Z-6265, AY43- 204M, AY43-048, Z-6403, AY43-206M, AY43-206E, Z6341, AY43-210MC, AY43-083, AY43-101, AY43-013, AY43-158E, Z-6920, and Z-6940 (all which are manufactured by Dow Corning Toray Co., Ltd.).
[000231] An addition amount of the silane coupling agent is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 0.1% by mass to 10% by mass. Where the amount of addition is less than 0.1% by mass, the core particle, filler material and resin decrease in adhesion, so that a coating layer may fall off over a long period of use, and where exceeds 10% by mass, toner film formation may occur over a long period of use. Filling material
[000232] The filler material is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include conductive filler materials and non-conductive filler materials. These can be used individually or in combination of two or more. Among these, it is preferable to make the coating layer contain a conductive filler material and a non-conductive filler material.
[000233] Conductive filler material means a filler material having a powder resistivity value of 100 Q-cm or less.
[000234] Non-conductive filler material means a filler material having a powder resistivity value greater than 100Q-cm.
[000235] The determination of a fill material resistivity value is performed by measuring under conditions of a 1.0 g sample, a 3 mm electrode spacing, a 10.0 mm sample radius, and a load 20 kN using a powder resistivity measurement system (MCP-PD51, Dia Instruments Co., Ltd.) and a resistivity meter (4-probe 4-terminal method, Loresta-GP, manufactured by Mitsubishi Chemical Analytic Co., Ltd.) Conductive Filling Material
[000236] The conductive filler material is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include conductive filler materials for which tin dioxide or indium oxide is formed as a layer on bases such as aluminum oxide, titanium oxide, zinc oxide, barium sulfate, silicon oxide, and zirconium oxide; and conductive fillers formed using carbon blacks. Among these, conductive fillers that contain aluminum oxide, titanium oxide, or barium sulfate are preferable. Non-conductive filling material
[000237] The non-conductive filler material is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include non-conductive filler materials formed using aluminum oxide, titanium oxide, barium sulfate, aluminum oxide zinc, silicon dioxide, zirconium oxide, and the like. Among these, conductive fillers containing aluminum oxide, titanium oxide or barium sulfate are preferable. Numerical mean particle diameter of filler material
[000238] A numerical average particle diameter of the filler material is not particularly limited and can be appropriately selected according to the purpose, however it is preferably 50 nm to 800 nm, and more preferably 200 nm to 700 nm in consideration that the Filler material easily projects from the surface of a resin contained in the coating layer to easily form a low partial strength and easily scrape a used component on the conveyor surface and being excellent in wear resistance. For determination of a numerical mean particle diameter of the filler material, 100 particle images of a filler material magnified by 10,000x using a scanning electron microscope (eg FE-SEM (S-800), manufactured by Hitachi, Ltd.) are sampled at random to measure particle diameters, and a numerical mean particle diameter thereof is used. Other components
[000239] The other components are not particularly limited and may be appropriately selected according to the purpose, however it is preferable to make the coating layer contain a catalyst, and a solvent, a curing agent, and others may be contained. Catalyst
[000240] The catalyst is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include titanium based catalysts, tin based catalysts, zirconium based catalysts, and aluminum based catalysts, and specifically include acetyl acetonate complexes, alkyl acetoacetate complexes, and salicylaldehyde complexes thereof. These can be used individually or in combination of two or more. Among these, titanium based catalysts are preferable on account of having a great effect to promote a condensation reaction of a silanol group and the catalyst being difficult to inactivate, and diisopropoxy bis(ethyl acetoacetate) titanium is more preferable. conveyor production method
[000241] A production method for the carrier is not particularly limited and can be appropriately selected according to the purpose, but is preferably a method for producing the same by applying a coating layer-forming solution containing the resin and material of filling to the surface of the core particle using a fluidized bed coater. Furthermore, condensation of a resin contained in the coating layer can proceed when applying the coating layer-forming solution, and condensation of a resin contained in the coating layer can proceed after applying the coating layer-forming solution. A condensing method for the resin is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include a method of applying heat, light, etc., to the coating layer-forming solution to condense resin. Conveyor toilet work function
[000242] The Wc work function of a carrier in formula (1) above can be controlled to a desired value, for example, by changing the type and amount of addition of the silane coupling agent, the type of a resin to form the coating layer, and amount of filler addition. Conveyor SF-2 Format Factor
[000243] The carrier is regulated by an SF-2 form factor.
[000244] The SF-2 regulates the degree of particle irregularity.
[000245] When the SF-2 has a higher value, the particle surface irregularity has more intense up and down movements.
[000246] The SF-2 carrier shape factor is not particularly limited as long as it is 115 to 150, and may be appropriately selected according to the purpose, but is preferably 120 to 145 in consideration of allowing coating with a particle irregularity of core that remains to some extent.
[000247] The determination of an SF-2 format factor of the carrier is performed by randomly sampling 100 images of a carrier particle magnified at 300x using a scanning electron microscope (eg FE-SEM (S- 800) manufactured by Hitachi, Ltd.) and analyze image information obtained by an image analyzer (eg Luzex AP, manufactured by NIRECO CORPORATION), and calculate using the following formula (IV). SF-2 = (P2/A) x (1/4π) x 100 ... (IV)
[000248] In formula (IV) above, R indicates a perimeter of a conveyor, and A indicates a projected area of a conveyor. Conveyor volume density
[000249] A bulk density of the carrier is not particularly limited as long as it is 1.80 g/cm3 to 2.40 g/cm3, and can be appropriately selected according to the purpose. Where the bulk density is less than 1.80 g/cm3, so-called carrier adhesion in which a carrier adheres to an element containing electrostatic imaging easily occurs, and where it exceeds 2.40 g/cm3, the voltage of agitation in the developing device is great, which can result in a large resistance change of a carrier.
[000250] The determination of a bulk carrier density is performed by dropping a funnel having an orifice diameter Φ of 3 mm at a height of 25 mm into a container of 25 cm3. Dw weight mean particle diameter of carrier
[000251] A weight average carrier particle diameter Dw means a particle diameter at an integrated value of 50% in a particle size distribution of the core particles determined by a laser diffraction/scanning method. The weight-average particle diameter Dw of the carrier is not particularly limited and may be appropriately selected according to the purpose, however it is preferably 10 µm to 80 µm.
[000252] For determination of a weight-average particle diameter Dw of the carrier by measuring a particle diameter distribution of particles measured on a number basis (the relationship between number frequency and particle diameter) is measured under the conditions to be described later using a Microtrac particle size analyzer (HRA9320-X100, manufactured by Honeywell, Inc.), and a weight-average particle diameter is calculated using the following formula (V).
[000253] In formula (V) above, D indicates a representative particle diameter (one) of carriers present in each channel, and n indicates a total number of carriers present in each channel. Measurement conditions [1] particle diameter range: 100 µm to 8 µm [2] channel length (channel width): 2 µm [3] number of channels: 46 [4] refractive index: 2.42
[000254] When the developer is a two-component developer, the mixing ratio of toner and carrier in the two-component developer is preferably 2.0 parts by mass to 12.0 parts by mass, and more preferably 2.5 parts by mass. mass to 10 parts by mass, in terms of the toner to carrier mass ratio. Imaging Method and Imaging Apparatus
[000255] An imaging method to be used in the present invention includes at least an electrostatic latent imaging step (charge step and exposure step), a development step, a transfer step, and a step of fixing, and further includes other steps, e.g., a discharge step, a cleaning step, a recycling step, a control step, and the like, appropriately selected as needed.
[000256] An imaging apparatus of the present invention includes: an element containing electrostatic latent imaging; a charging unit configured to charge a surface of the element that contains electrostatic latent imaging; an exposure unit configured to expose the element surface containing charged electrostatic latent image to form an electrostatic latent image; a developer unit configured to develop the electrostatic latent image with a toner to form a visible image; a transfer unit configured to transfer the visible image to a recording medium; and a fixing unit configured to fix a transfer image transferred to the recording medium; and further includes other units, for example, a discharge unit, a cleaning unit, a recycling unit, a control unit, and the like, appropriately selected according to need. The developing unit is a developing device of the present invention. Latent imaging step and latent imaging unit
[000257] The electrostatic imaging step is a step of forming an electrostatic imaging on the element that contains electrostatic imaging.
[000258] The element that contains electrostatic latent imaging (sometimes referred to as “electrophotographic photoconductor” or “photoconductor”) is not particularly limited in material, shape, structure, size and the like, and can be appropriately selected from those known. The format is suitably a drum shape, and examples of the material include amorphous silicon and selenium from inorganic photoconductors and polysilane and phthalopolymethine from organic photoconductors (OPCs). Among these, amorphous silicon or similar is preferable in consideration of a long lifetime.
[000259] Electrostatic imaging can be formed, for example, by uniformly charging the surface of the element that contains electrostatic latent imaging and then exposing the surface in the imaging direction, and this can be accomplished by the electrostatic imaging unit. The electrostatic imaging unit includes at least, for example, a charging unit (charger) that uniformly charges the surface of the element that contains electrostatic imaging and an exposure unit (display) that exposes the surface of the element that contains electrostatic imaging in the imaging sense.
[000260] The charge can be performed, for example, by applying voltage on the surface of the element that contains electrostatic latent image by using the charger.
[000261] Although the charger is not particularly limited and may be appropriately selected according to the purpose, examples thereof include a contact charger which is known per se endowed with a conductive or semiconductive roller, brush, film, rubber sheet , or similar, and a non-contact charger utilizing a corona discharge such as a corotron or scorotron.
[000262] As a charger, one that is arranged in contact or out of contact with the element that contains electrostatic latent imaging and charges the surface of the element that contains electrostatic imaging because it is superimposed with direct current voltages and alternating current.
[000263] Furthermore, the charger is preferably a charging roller which is disposed in proximity out of contact with the electrostatic imaging element through a slack tape and charges the surface of the electrostatic imaging containing element as a result of be superimposed with direct current and alternating current voltages to the load roller.
[000264] The exhibition can be carried out, for example, by exposing the surface of the element that contains electrostatic latent image in the image sense by using the exhibitor.
[000265] The exhibitor is not particularly limited as long as it is able to exhibit in a form of an image to be formed on the surface of the element that contains electrostatic latent image loaded by the charger and can be appropriately selected according to the purpose, but examples of even include various exhibitors like an optical copying system, a rod lens assembly system, a laser optical system, and a liquid crystal shutter optical system.
[000266] Here, in the present invention, a backlight system for exposing the electrostatic latent imaging element in the imaging direction from the back surface side can be employed. Development step and development unit
[000267] The development step is a step of developing the electrostatic latent image by using the developer to form a visible image.
[000268] The visible image can be formed for example, by developing the electrostatic latent image by using the developer, and this can be performed by the developing unit.
[000269] As the developing unit, for example, one that includes at least one developing device that contains the developer of the present invention and is capable of applying the developer to the electrostatic imaging in a contact or non-contact mode is appropriate, and a developing device with a developer container is more preferable.
[000270] The developing device may be a single color developing sports or a multi-color developing device, and suitable examples thereof include one that includes an agitator that frictionally agitates the developer so that it is loaded and a magnet roller. rotating (element that contains developer).
[000271] In the developing device, for example, the toner and the conveyor are mixed and stirred, the toner is friction-loaded at that moment and is retained in a state of elevation on the surface of the rotating magnet roller to form a magnetic brush. Since the magnet roller is disposed in the vicinity of the electrostatic latent image-containing (photoconductor) element, a portion of the toner retained in the magnetic brush formed on the surface of the magnet roller is moved to the surface of the electrostatic latent image-containing element ( photoconductor) by an electrical suction force. As a result, electrostatic latent image is developed with toner to form a visible image of the toner on the surface of the element that contains electrostatic latent image (photoconductor). Transfer step and transfer unit
[000272] The transfer step is a step of transferring the visible image to a recording medium. It is preferable to use an intermediate transfer element, mainly to transfer a visible image onto the intermediate transfer element, and then secondly transfer the visible image onto the recording medium, and it is more preferable that the transfer step includes a transfer step of transferring a visible image onto an intermediate transfer element to form a composite transfer image by using, as the toner, a two or more color toner, preferably a full color toner, and a secondary transfer step transferring the composite transfer image onto a recording medium.
[000273] The transfer is performed for example by loading the visible image on the element that contains electrostatic latent image (photoconductor) by using a transfer charger, and this can be performed by the transfer unit. The transfer unit preferably includes a primary transfer unit which transfers a visible image onto an intermediate transfer element to form a composite transfer image and a secondary transfer unit which transfers the composite transfer image onto a recording medium.
[000274] Here, the intermediate transfer element is not particularly limited and may be appropriately selected from known transfer elements according to the purpose, and suitable examples include a transfer belt.
[000275] The transfer unit (the primary transfer unit and the secondary transfer unit) preferably includes at least one transfer device that releases and carries the visible image formed in the electrostatic latent image containing element (photoconductor) on the side of the recording medium. One or a plurality of transfer units can be provided.
[000276] Transfer device examples include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesion transfer device.
[000277] Here, the recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper). Clamping step and clamping unit
[000278] The fixation step is a step of fixing a visible image transferred onto a recording medium by the use of a fixation device, and this can be performed for respective color developers every time these are transferred to the recording medium or it can be simultaneously performed for respective color developers in a laminated state at a time.
[000279] Although the clamping device is not particularly limited and can be appropriately selected according to the purpose, a known heating pressure unit is suitable. Examples of the heat pressure unit include a combination of a heat roller and a pressure roller and a combination of a heat roller, a pressure roller, and an endless belt.
[000280] The sport fastener is preferably a unit that includes a heater with a heating element, a film that contacts the heater, and a pressure element that pressure contacts the heater through the film and makes a recording medium with an unfixed image formed is passed through between the film and the pressure element for heat setting. Typically, heating by the pressure heating unit is preferably at 80°C to 200°C.
[000281] Here, in the present invention, for example, a known optical fixation device can be used in combination with the fixation step and fixation unit or in place of these.
[000282] The discharge step is a discharge step by applying a discharge bias in the element that contains electrostatic latent image, and this can be properly performed by a discharge unit.
[000283] The discharge unit is not particularly limited, it is satisfactory as long as it is able to apply a discharge bias to the element containing electrostatic imaging, and can be appropriately selected from known dischargers. Appropriate examples include a discharge lamp.
[000284] The cleaning step is a step of removing the toner remaining in the electrostatic latent imaging element, and this can be properly performed by a cleaning unit.
[000285] The cleaning unit is not particularly limited, and is satisfactory as long as it is able to remove the toner remaining in the element containing electrostatic latent image, and can be properly selected from known cleaning means. Appropriate examples include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a paddle cleaner, a brush cleaner, and a weft cleaner.
[000286] The recycling step is a step of having the developer unit recycle the toner removed by the cleaning step, which can be properly performed by a recycling unit. The recycling unit is not particularly limited, and this may be a known transfer unit, or similar.
[000287] The control step is a step of controlling the respective steps, and the respective steps can be properly controlled by a control unit.
[000288] The control unit is not particularly limited as long as it is capable of controlling operations of the respective units, and can be appropriately selected according to the purpose. Examples of it include devices such as a sequencer and a computer.
[000289] Figure 6 shows a first example of the imaging apparatus of the present invention. Imaging apparatus 100A includes a photoconductive drum 10, a loading roller 20, an exposure device (not shown), a developing device 40, an intermediate transfer belt 50, a cleaning sport 60 having a paddle. cleaning ode, and a discharge lamp 70.
[000290] The intermediate transfer belt 50 is an endless belt stretched by three rollers 51 arranged inside, and is movable in the arrow direction in the figure. A portion of the three rollers 51 also functions as a transfer bias roller which is capable of applying a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Furthermore, in the vicinity of the intermediate transfer belt 50, a cleaning device 90 having a cleaning paddle is arranged. In addition, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) to transfer a toner image onto a transfer sheet 95 is disposed opposite the intermediate transfer belt 50. Furthermore, around the belt of intermediate transfer belt 50, a corona charging device 58 is arranged to transmit a charge to the toner image on the intermediate transfer core 50, with respect to a direction of rotation of the intermediate transfer belt 50, between a contact portion between the intermediate transfer belt 50. photoconductive drum 10 and intermediate transfer belt 50 and a contact portion between intermediate transfer belt 50 and transfer sheet 95.
[000291] The developer device 40 is composed of a development core 51 and a 45K black developer cartridge, a 45Y yellow developer cartridge, a 45M magenta developer cartridge, and a 45C cyan developer cartridge provided side by side around the developer belt 41. Here, the developer unit 45 for each color includes a developer-containing portion 42, a developer feed roller 43, and a developer roller (developer-containing element) 44. Furthermore, the developing belt 41 is an endless belt stretched by a plurality of belt rollers, and is movable in the direction of the arrow in the figure. Furthermore, a part of the developing belt 41 is in contact with the photoconductive drum 10.
[000292] In the following, a method for forming an image by using the image forming apparatus 100A will be described. First, the surface of the photoconductive drum is uniformly charged using the charge roller 20, and then an exposure light L is exposed to the photoconductive drum using an exposure device (not shown) to form an electrostatic latent image. Next, the electrostatic latent image formed on the photoconductive drum 10 is developed by a toner fed from the developing device 40 to form a toner image. Furthermore, the toner image formed on the photoconductive drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by a transfer bias applied from the rollers 51 and is then transferred (secondary transfer) onto the sheet. transfer 95 by a transfer bias applied from transfer roller 80. On the other hand, the photoconductive drum 10 from which the toner image was transferred to the intermediate transfer belt 50 is discharged by the discharge lamp 70 after a toner remaining on the surface is removed by the cleaner 60.
[000293] Figure 7 shows a second example of the imaging apparatus to be used in the present invention. Imaging apparatus 100B has the same configuration as that of imaging apparatus 100A except that no developing belt 41 is provided, and a 45K black developer unit, a 45Y yellow developer unit, a unit 45M magenta developer unit, and a 45C cyan developer unit are arranged in a directly opposite mode around the photoconductive drum 10.
[000294] Figure 8 shows a third example of the imaging apparatus to be used in the present invention. Imaging apparatus 100C is a tandem-type color imaging apparatus, and includes a copier body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400 .
[000295] An intermediate transfer belt 50 provided in the central portion of the copier body 150 is an endless belt stretched around three rollers 14, 15 and 16, and is rotatable in the direction of the arrow in the figure. In the vicinity of the roller 15, a cleaning device 17 is arranged having a cleaning paddle for removing a toner remaining on the intermediate transfer belt 50 from which the toner image was transferred to the recording paper. Yellow, cyan, magenta, and black 120Y, 120C, 120M, and 120K imaging units are juxtaposed in an opposite way to the intermediate transfer belt 50 stretched by rollers 14 and 15 along a transfer direction. Furthermore, in the vicinity of the image forming units 120, an exhibition sport 21 is arranged. Furthermore, on the side of the intermediate transfer belt 50 opposite the side where the imaging units 120 are disposed, a secondary transfer belt 24 is disposed. Here, the secondary transfer belt 24 is an endless belt stretched through a pair of rollers 23 and the embossing sheet which is transferred onto the secondary transfer belt 24 and the intermediate transfer belt 50 can contact between the rollers 16 and 23 In the vicinity of the secondary transfer belt 24, a fastening device 25 is arranged which includes a fastening belt 26 serving as an endless belt stretched through a pair of rollers and a pressure roller 27 disposed while being pressed against the belt Here, in the vicinity of the secondary transfer belt 24 and the securing device 25, a sheet invert device 28 is arranged to invert the recording paper by forming images on the two surfaces of the recording paper.
[000296] In the following, a method for forming a full color image by using the image forming apparatus 100C will be described. First a color document is placed on a document table 130 of the automatic document feeder (ADF) 400 or the automatic document feeder 400 is opened to place a color document on a contact glass 32 of the scanner 300, and then the automatic document feeder document 400 is closed. When a start switch (not shown) is pressed, scanner 300 is activated, when the document has been placed in automatic document feeder 400, after the document is transferred and moved onto contact glass 32; on the other hand, when the document was placed immediately on the contact glass 32, and a first shifter 33 including a light source and a second shifter 34 including a mirror shift. At that time, by reflecting by the second shifter 34 a light reflected from the surface of the document from light radiated from the first shifter 33 and then receiving the reflected light by a read sensor 36 through an imaging lens 35, the document is read, and thus black, yellow, magenta, and cyan image information is obtained.
[000297] Respective color image information is transmitted to respective color imaging units 120, and respective color toner images are formed. Respective color imaging units 120 include, as shown in Fig. 9, photoconductor drums 10, charge rollers 160 uniformly charging photoconductor drums 10, display devices that expose an exposure light L to the drums. photoconductor 10 based on respective color image information and thereby form respective color electrostatic latent images, developing devices 61 developing the electrostatic latent images with respective color developers to form respective color toner images, transfer roller 62 for transferring the toner images onto the intermediate transfer belt 50, cleaning devices 63 having cleaning paddles, and discharge lamps 64, respectively. The respective color toner images formed by the respective color imaging unit 120 are transferred (primary transfer) in sequence onto the intermediate transfer belt 50 which are supported by rollers 14, 15 and 16 to move, and overlaid to form a composite toner image.
[000298] On the other hand, at the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to let recording paper out of one of the paper feed cassettes 144 provided in multiple series in a paper group 143, and the paper is separated sheet by sheet by a separation roller 145 and separately sent out to a paper feed path 146, transferred by a transfer roller 147 and guided to a paper feed path 148 in the body of copier 150, is struck against a resist roller 49 and stopped. Alternatively, the paper feed roller is rotated to leave recording paper in a manual feed tray 54, and the paper is separated sheet by sheet by the separation roller 52 and separately guided to a manual paper feed path 53, and hit against resist roller 49 and stopped. Here, the resist roller 49 is generally used grounded, but it can be used in a state where a bias is applied to remove dust from the recording sheets. Next, by rotating the resist roller 49 in adjustment with the composite toner image formed on the intermediate transfer belt 50, the recording paper is sent out between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is transferred (secondary transfer) onto the recording paper, a color image is transferred and formed on the recording paper. Here, a remaining toner on the intermediate transfer belt 50 from which the composite toner image was transferred is cleaned by the cleaning device 17.
[000299] The recording paper onto which a composite image has been transferred is conveyed by the secondary transfer belt 24, and then fixed with the composite toner image by the fixing sport 25. Next, the recording paper is switched to transfer path by a switching jaw 55, and is discharged onto a unloaded paper tray 57 by a discharge roller 56. Alternatively, the recording paper is switched in the transfer path by switching jaw 55, it is inverted by the device of invert sheet 28, is similarly formed with an image on the rear surface as well, and then is discharged onto the discharged paper tray 57 by discharge roller 56.
[000300] The imaging apparatus of the present invention can provide high quality images over a long period. Examples
[000301] Hereinafter, the examples of the present invention will be described, however, the present invention is by no means limited to these embodiments. Examples
production 1 to 12 Production of external additives 1 to 12
[000302] For production of external additives 1 to 10, by mixing primary silica particles having various average particle diameters and a treating agent by a spray dryer and burning the mixtures under conditions described in table 1, the primary particles were coalesced to produce coalescent particles, and then classification was performed by a classification device to obtain a sharp particle size distribution. Furthermore, external additives 11 to 12 were produced only by applying hydrophobization treatment to primary silica particles having various average particle diameters without performing treatment with the treating agent.
[000303] Here, the treating agent was prepared by adding 0.1 parts by mass of a treatment aid (water or a 1% aqueous solution by mass of acetic acid) to 1 part of methyl methoxy silane. The average particle diameters, shapes, etc., of secondary particles produced by coalescing the primary particles are shown in table 1. Multiple measurements
[000304] For Db5o in coalescing particles (secondary particles), particle diameters of coalescing particles were measured to determine a particle diameter where the accumulated value of a cumulative distribution when plotted from the smaller particle side reaches 50% in number . For Db10, coalescent particle particle diameters were measured to determine a particle diameter where the accumulated value of a cumulative distribution when plotted from the smaller particle side reaches 10% in number.
[000305] For a numerical mean particle diameter (Dba) of the coalescing particles (secondary particles), the maximum lengths (length of arrow shown in figure 2) of aggregated particles were measured (number of measured particles: 150). For the average diameter (Da) of primary particles of the coalescent particles, whose images are estimated from the outer frames of coalescing silica, and an average value of the maximum lengths (lengths of all arrows shown in figure 1) of the entire images was measured (the number of measured particles: 150).
[000306] The determination of the particle diameters of these respective particles was carried out, with a sample for which the coalescing particles were dispersed in an appropriate solvent (THF or similar) and then the solvent was removed for drying and hardening on a substrate, by measure particle diameters in a field of view using a field-emission scanning electron microscope (FE-SEM, accelerating voltage: 5 kV to 8 kV, observation magnification: 8000x 10,000x). Conveyor production A
[000307] The following carrier raw materials were dispersed for 10 minutes by a homomixer to obtain a coating layer forming solution of an acryl resin and a silicone resin including alumina particles. The above-described coating layer forming solution was coated onto the surface of fired ferrite powder [(MgO)1.8(MnO)49.5(Fe2O3)48.0: 35 µm mean particle diameter] used as a core material in order to provide a thickness of 0.15 µm using SPIRA COTA (manufactured by Okada Seiko Co., Ltd.) and dried to obtain coated ferrite powder. The obtained coated ferrite powder was fired by being left to stand at 150°C for 1 hour in an electric oven. After cooling, the ferrite powder volume was disintegrated by using a sieve with an opening of 106 µm to obtain a carrier. For a film thickness measurement, a coating layer covering the carrier surface can be observed by looking at a carrier section through a transmission electron microscope, an average value of its thickness is considered to be the thickness of a layer. of coating. Thereby, a carrier A with a weight-average particle diameter of 35 µm was obtained. Carrier A raw material
[000308] Acrylic resin solution (solid content: 50% by mass) 21.0 parts by mass
[000309] Guanamine resin solution (solid content: 70% by mass) 6.4 parts by mass
[000310] Alumina particles (0.3 µm, specific resistance 1014 Q-cm) 7.6 parts by mass
[000311] Silicone resin solution (solid content: 23% by mass) 65.0 parts by mass
[000312] [SR2410, manufactured by Dow Corning Toray Co., Ltd.]
[000313] Aminosilane coupling agent (solid content: 100% by mass) 1 part by mass
[000314] [SR6020, manufactured by Dow Corning Toray Co., Ltd.]
[000315] Toluene 60.0 parts by mass
[000316] Butyl cellosolve 60.0 parts by mass Assessment of breakage or collapse of an external additive
[000317] A total of 50 g placed in a 50 mL bottle (manufactured by NICHIDEN-RIKA GLASS CO., LTD.) consisting of 0.5 g each of external additives 1 to 12 and 49.5 g of carrier A above described was agitated by using an oscillating mill (manufactured by Seiwa Giken Co., Ltd.) under the conditions of 67 Hz and for 10 minutes. The agitator developer was diluted and dispersed in tetrahydrofuran (THF), the external additive was separated to the supernatant fluid side, and then scanning electron microscope-field emission observation (FE-SEM) was performed. By FE-SEM observation, a rate (%) of the number of broken or bent particles in 1000 particles of the external additive was determined. Figure 4 shows a photograph of a measurement result where the rate of the number of broken or bent particles is 30% or less, and Figure 5 shows a photograph of a measurement result where the rate of the number of broken or bent particles exceeds 30%. In the measurement case, particles such as a particle that existed by itself as shown by reference sign 2 of figure 3 and particles that existed by itself as shown in the blackboards of figure 4 to figure 5 were counted as “broken or bent particles ” to determine the rate. Table 1

[000318] Production example 13
[000319] Production of crystalline polyester resin 1
[000320] 202 parts by mass (1.0 mol) of sebacic acid, 154 parts by mass of 1,6-hexane diol (1.30 mol), 0.5 parts by mass of tetrabutoxy titanate as a condensation catalyst were placed in a reaction tank equipped with a cooling tube, an agitator, and a nitrogen introducing tube and allowed to react for 8 hours while distilling water to be produced, at 180°C under a stream of nitrogen. Thereafter, the result was gradually heated to 220°C while being allowed to react for 4 hours under a stream of nitrogen while distilling water to be produced and 1,6-hexane diol, and the result was further allowed to react under a reduced pressure of 5 mmHg to 20 mmHg until the weight-average molecular weight Mw reached approximately 15,000 to obtain a [crystalline polyester resin 1]. The [crystalline polyester resin 1] obtained had a Mw of 14,000 and a melting point of 66°C. Production example 14 Production of non-crystalline polyester resin 1 (unmodified polyester resin)
[000321] 222 parts by mass of 2 mol EO bisphenol A adduct, 129 parts by mass of 2 mol PO bisphenol A adduct, 150 parts by mass of terephthalic acid, 15 parts by mass of adipic acid, and 0.5 parts batches of tetrabutoxy titanate were placed in a reaction tank equipped with a cooling tube, an agitator, and a nitrogen introducing tube and allowed to react for 8 hours while distilling water to be produced, under normal pressure, at 230°C under a stream of nitrogen. Thereafter, the result was allowed to react under a reduced pressure of 5 mmHg to 20 mmHgm, and cooled to 180°C at the point in time where the acid value had reached 2 mgKOH/g and 35 parts by mass of trimellitic anhydride were added to the same and allowed to react for 3 hours under normal pressure to obtain a [non-crystalline polyester resin 1]. The [non-crystalline polyester resin 1] obtained had a Mw of 6,000 and a Tg of 54°C. Production example 15 Production of non-crystalline polyester resin 2 (unmodified polyester resin)
[000322] 212 parts by mass of 2 moles EO bisphenol A adduct, 116 parts by mass of 2 moles PO bisphenol A adduct, 166 parts by mass of terephthalic acid, and 0.5 parts by mass of tetrabutoxy titanate were placed in a reaction tank equipped with a cooling tube, an agitator, and a tube to introduce nitrogen and allowed to react for 8 hours while distilling water to be produced, under normal pressure, at 230°C under a stream of nitrogen. Thereafter, the result was allowed to react under a reduced pressure of 5 mmHg to 20 mmHgm, and allowed to react until Mw reached approximately 15,000 to obtain a [non-crystalline polyester resin 2]. The [non-crystalline polyester resin 2] obtained had a Mw of 14,000 and a Tg of 60°C. Production example 16 Production of non-crystalline polyester resin 3 (unmodified polyester resin)
[000323] 204 parts by mass of 2 mol EO bisphenol A adduct, 106 parts by mass of 2 mol PO bisphenol A adduct, 166 parts by mass of terephthalic acid, and 0.5 parts by mass of tetrabutoxy titanate were placed in a reaction tank equipped with a cooling tube, an agitator, and a tube to introduce nitrogen and allowed to react for 8 hours while distilling water to be produced, under normal pressure, at 230°C under a stream of nitrogen. Thereafter, the result was allowed to react under a reduced pressure of 5 mmHg to 20 mmHgm, and allowed to react until Mw reached approximately 40,000 to obtain a [non-crystalline polyester resin 3]. The [non-crystalline polyester resin 3] obtained had a Mw of 38,000 and a Tg of 62°C. Production example 17 Polyester Prepolymer Production
[000324] 720 parts by mass of adduct of 2 moles EO of bisphenol A, 90 parts by mass of adduct of 2 moles PO of bisphenol A, 290 parts by mass of terephthalic acid, and 1 part by mass of tetrabutoxy titanate were placed in a reaction tank equipped with a cooling tube, an agitator, and a tube to introduce nitrogen and allowed to react for 8 hours while distilling water to be produced, under normal pressure at 230°C under a stream of nitrogen. Then, the result was allowed to react for 7 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain [olyester intermediate 1]. The [olyester intermediate 1] obtained had Mn of 3200 and Mw of 9,300.
[000325] Next, 400 parts by mass of the obtained [olyester intermediate 1], 95 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate were placed in a reaction tank equipped with a cooling tube, a stirrer, and a tube introducing nitrogen and allowed to react at 80°C for 8 hours under a stream of nitrogen to obtain a 50% by weight ethyl acetate solution of [olyester prepolymer 1] having an isocyanate group free of [olyester prepolymer 1] was 1.47%. Production example 18 Graft Polymer Production
[000326] 480 parts by mass of xylene and 100 parts by mass of low molecular weight polyethylene (SANWAX LEL-400, manufactured by Sanyo Chemical Industries, Ltd.: softening point 128°C) were placed in an equipped reaction vessel with a stirring rod and a thermometer and sufficiently dissolved, and after nitrogen replacement, a mixed solution of 740 parts by mass of styrene, 100 parts by mass of acrylonitrile, 60 parts by mass of butyl acrylate, 36 parts by mass of di-t-butyl peroxy hexahydroterephthalate, and 100 parts by mass of xylene was dropped at 170°C for 3 hours for polymerization, and additionally the result was left to stand at this temperature for 30 minutes. Next, desolventization was performed to synthesize a [graft polymer]. The [graft polymer] obtained had a Mw of 24,000 and a Tg of 67°C. Production example 19 Toner base production 1 (ester elongation method) Preparation of release agent dispersion 1
[000327] 50 parts by mass of paraffin wax (HNP-9, manufactured by Nippon Seiro Co., Ltd., melting point 75°C), 30 parts by mass of [graft polymer] and 420 parts by mass of Ethyl acetate were placed in a container equipped with a stirring rod and a thermometer, heated to 80°C under agitation, and allowed to stand for 5 hours at 80°C, and then cooled to 30°C in 1 hour, and the result was dispersed by the use of a bead mill (ULTRAVISCOMILL manufactured by Aimex Co., Ltd.) under the conditions of a feed speed of 1 kg/h, a circumferential disk speed of 6 m/second 0.5 mm of zirconia beads filled to 80% by volume and 3 passes to obtain a [dispersion of release agent 1]. Master batch preparation 1 Non-crystalline polyester resin 1 100 parts by mass
[000328] Carbon black (Printex 35, manufactured by Degussa AG) 100 parts by mass (amount of DBP oil absorption: 42 mL/100 g, pH: 9.5).
[000329] Ion exchanged water - 50 parts by mass
[000330] The above raw materials were mixed by a Henschel mixer (manufactured by Nippon Coke & Engineering Co., Ltd.). the obtained mixture was kneaded by a two-roll mill. Kneading was started from a kneading temperature of 90°C, which was then gradually cooled to 50°C. the obtained kneaded product was pulverized by a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a [master batch 1]. Oil Phase 1 Preparation
[000331] 107 parts by mass of [non-crystalline polyester resin 1], 75 parts by mass of [release agent dispersion 1], 18 parts by mass of [master batch 1], and 73 parts by mass of acetate acetate. Ethyl were placed in a container equipped with a thermometer and a stirrer, pre-dispersed by the stirrer, and then stirred at a rotation speed of 5,000 rpm with a TK type homomixer (manufactured by Primix Corporation) to be uniformly dissolved and dispersed to get a [oil stage 1]. Production of aqueous dispersion of fine resin particles
[000332] 600 parts by weight of water, 120 parts by weight of styrene, 100 parts by weight of methacrylic acid, 45 parts by weight of butyl acrylate, 10 parts by weight of allyl alkyl sodium sulfosuccinate (ELEMINOL JS-2 , manufactured by Sanyo Chemical Industries, Ltd.) and 1 part by mass of ammonium persulfate were charged into a reaction vessel equipped with a stirring rod and a thermometer and stirred at 400 rpm for 20 minutes, and as a result, an emulsion white was obtained. The emulsion was heated to a system temperature of 75°C and allowed to react for 6 hours. In addition, 30 parts by mass of 1% aqueous ammonium persulfate solution was added thereto, and the result was aged at 75°C for 6 hours to obtain an [aqueous dispersion of fine resin particles]. Particles included in this [aqueous dispersion of fine resin particles] had a volume-average particle diameter of 60 nm, the resin component had a weight-average molecular weight of 140,000 and Tg was 73°C. Preparation of aqueous phase 1
[000333] 990 parts by mass of water, 83 parts by mass of [aqueous dispersion of fine resin particles], 37 parts by mass of an aqueous solution of 48.5% by mass of sodium dodecyl diphenyl ether disulfonate (ELEMINOL MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts by mass of ethyl acetate were mixed and stirred to obtain an [aqueous phase 1]. Emulsification or dispersion
[000334] 45 parts by mass of an ethyl acetate solution of [olyester prepolymer 1] and 3 parts by mass of an ethyl acetate solution of 50% by mass of isophorone diamine were added to 273 parts by mass of [Oil stage 1] and stirred at a rotation speed of 5,000 rpm by a TK type homomixer (manufactured by Primix Corporation) to be uniformly dissolved and dispersed to obtain an [oil stage 1']. Next, 400 parts by mass of [aqueous phase 1] were placed in another container equipped with a stirrer and a thermometer, and stirred at 13,000 rpm with a TK type homomixer (manufactured by Primix Corporation) while being added with [hase of oil 1'], and the result was emulsified for 1 minute to obtain an [emulsified paste 1]. Desolventization for washing to drying:
[000335] The [emulsified paste 1] was loaded into a container equipped with a stirrer and a thermometer, and desolventized at 30°C for 8 hours to obtain a [aste 1]. The [aste 1] obtained was filtered under reduced pressure, and then subjected to the following washing treatment. (1) 100 parts by mass of ion-exchanged water were added to a filter cake and mixed by a TK-type homomixer (for 5 minutes at a rotation speed of 6,000 rpm), and then the result was filtered. (2) 100 parts by mass of a 10% by mass aqueous sodium hydroxide solution were added to the filter cake prepared in (1) and mixed by the TK type homomixer (for 10 minutes at a rotation speed of 6,000 rpm ), and then the result was filtered under reduced pressure. (3) 100 parts by mass of hydrochloric acid at 10% by mass were added to the filter mass prepared in (2) and mixed by the type TK homomixer (for 5 minutes at a rotation speed of 6,000 rpm) and then the result was filtered. (4) 300 parts by mass of ion-exchanged water were added to the filter cake prepared in (3) and mixed by the type TK homomixer (for 5 minutes at 6,000 rpm), and then the result was filtered. The above procedure was conducted twice to obtain a [filter mass 1].
[000336] The [filter mass 1] thus obtained was dried at 45°C for 48 hours by using a circulation dryer. Subsequently, the mass was sieved through a mesh having a 75 µm opening to prepare a [toner base body 1]. Production example 20 Toner base production 2 (ester elongation method) Preparation of crystalline polyester resin dispersion 1
[000337] 100 parts by mass of [crystalline polyester resin 1] and 400 parts by mass of ethyl acetate were placed in a container equipped with a stirring rod and a thermometer, heated and dissolved at 75°C under stirring, and then cooled to 10°C or less in 1 hour, and the result was dispersed for 5 hours by using a bead mill (ULTRAVISCOMILL, manufactured by Aimex Co. Ltd.) under the conditions of a feed speed of 1 kg/ h, a circumferential disk speed of 6 m/sec, and 0.5 mm of zirconia cones filled at 80% by volume to obtain a [crystalline polyester resin dispersion 1]. Oil phase 2 preparation
[000338] 93 parts by mass of [non-crystalline polyester resin 1], 68 parts by mass of [crystalline polyester resin dispersion 1], 75 parts by mass of [release agent dispersion 1], 18 parts by mass of [master batch 1] and 19 parts by mass of ethyl acetate were placed in a container equipped with a thermometer and a stirrer, pre-dispersed by the stirrer, and then stirred at a rotation speed of 5,000 rpm with a homomixer of the type TK (manufactured by Primix Corporation) to be uniformly dissolved and dispersed to obtain an [oil phase 2]. Emulsification or dispersion
[000339] 45 parts by mass of an ethyl acetate solution of [olyester prepolymer 1] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophorone diamine were added to 273 parts by mass of [oil phase 2] and stirred at a rotation speed of 5,000 rpm with a TK type homomixer (manufactured by Primix Corporation) to be uniformly dissolved and dispersed to obtain a [oil phase 2']. Next, 400 parts by mass of [aqueous phase 1] were colored in another vessel equipped with a stirrer and a thermometer, and stirred at 13,000 rpm with a TK-type homomixer (manufactured by Primix Corporation) while being added with [hase of oil 2'], and the result was emulsified for 1 minute to obtain an [emulsified paste 2]. Desolventization for washing to drying
[000340] The [emulsified paste 2] was desolventized, washed, dried and sieved under the same conditions as those for [emulsified paste Production example 21 Toner base production 3 (dissolution suspension method) Oil Phase 3 Preparation
[000341] 107 parts by mass of [non-crystalline polyester resin 1], 23 parts by mass of [non-crystalline polyester resin 3], 75 parts by mass of [dispersion of release agent 1], 18 parts by mass of [master batch 1] and 97 parts by mass of ethyl acetate were placed in a container equipped with a thermometer and stirrer, pre-dispersed by the stirrer, and then stirred at a rotation speed of 5,000 rpm with a TK type homomixer ( manufactured by Primix Corporation) to be uniformly dissolved and dispersed to obtain an [oil stage 3]. Emulsification or dispersion
[000342] 400 parts by mass of [aqueous phase 1] were placed in another container equipped with a stirrer and a thermometer, and stirred at 13,000 rpm with a TK-type homomixer (manufactured by Primix Corporation) while being added with the [hase of oil 3], and the result was emulsified for 1 minute to obtain an [emulsified paste 3]. Desolventization for washing to drying
[000343] [Emulsified paste 3] was desolventized, washed, dried and sieved under the same conditions as those for [emulsified paste 1] to prepare a toner base 3. Production example 22 Toner base 4 production (dissolution suspension method) Oil Phase 4 Preparation
[000344] 93 parts by mass of [non-crystalline polyester resin 1], 23 parts by mass of [non-crystalline polyester resin 3], 68 parts by mass of [crystalline polyester resin dispersion 1], 75 parts by mass of [dispersion of release agent 1], 18 parts by mass of [master batch 1] and 43 parts by mass of ethyl acetate were placed in a container equipped with a thermometer and stirrer, pre-dispersed by the stirrer, and then stirred at a rotation speed of 5,000 rpm with a TK type homomixer (manufactured by Primix Corporation) to be uniformly dissolved and dispersed to obtain an [oil stage 4]. Emulsification or dispersion
[000345] 400 parts by mass of [aqueous phase 1] were placed in another container equipped with a stirrer and a thermometer, and stirred at 13,000 rpm with a TK type homomixer (manufactured by Primix Corporation) while being added with the [hase of oil 4], and the result was emulsified for 1 minute to obtain an [emulsified paste 4]. Desolventization for washing to drying
[000346] [Emulsified paste 4] was desolventized, washed, dried and sieved under the same conditions as those for [emulsified paste 1] to prepare a toner base 4. Production example 23 Production of toner base 5 (method of emulsion aggregation) Preparation of non-crystalline polyester resin dispersion 2
[000347] 60 parts by mass of ethyl acetate were added and dissolved in 60 parts by mass of [non-crystalline polyester resin 2]. Then 120 parts by mass of the resin solution was added to an [aqueous phase] to which 120 parts by mass of water, 2 parts by mass of an anionic surface active agent (NEOGEN R, manufactured by Daiichi KogyoSeiyaku Co., Ltd.), and 2.4 parts by mass of a 2% by mass aqueous sodium hydroxide solution were mixed, and the result was emulsified by using a homogenizer (Ultra Turrax T50, manufactured by IKA GmbH) and then subjected to to emulsification by a Manton Gaulin high pressure homogenizer (manufactured by Gaulin Corp.) to obtain an [emulsified paste].
[000348] Next, the [emulsified slurry] was loaded into a container equipped with a stirrer and a thermometer, and desolventized at 30°C for 4 hours to obtain a [non-crystalline polyester resin dispersion 2]. The mean particle-volume diameter of particles in the [non-crystalline polyester resin dispersion 2] obtained was 0.15 µm when measured by a particle size distribution analyzer (LA-920, manufactured by HORIBA, LTD.) Preparation of non-crystalline polyester resin dispersion 3
[000349] A [non-crystalline polyester resin dispersion 3] was obtained in the same manner as the preparation of [non-crystalline polyester resin dispersion 2] described above, except that [non-crystalline polyester resin 2] was replaced by a [non-crystalline polyester resin 3]. The mean particle-volume diameter of particles in the [non-crystalline polyester resin dispersion 3] obtained was 0.16 µm when measured by a particle size distribution analyzer (LA-920, manufactured by HORIBA, Ltd.) . Release agent dispersion preparation 2
[000350] 25 parts by mass of paraffin wax (HNP-9, manufactured by Nippon Seiro Co., Ltd., melting point 75°C), 1 part by mass of an anionic surface active agent (NEOGEN R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 200 parts by mass of water were mixed, and melted at 90°C. then, this fusion was emulsified by a homogenizer (Ultra Turrax T50, manufactured by IKA GmbH), and then subjected to emulsification by a Manton Gaulin high pressure homogenizer (manufactured by Gaulin Corp.) to obtain a [release agent dispersion] two]. Preparation of dyestuff dispersion 1
[000351] 20 parts by mass of carbon black (Printex 35, manufactured by Degussa AG), 0.5 parts by mass of an anionic surface active agent (NEOGEN R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 80 parts by mass of water were mixed, and dispersed by a TK type homomixer (manufactured by Primix Corporation) to obtain a [dying substance dispersion 1]. Aggregation
[000352] 235 parts by mass of [non-crystalline polyester resin dispersion 2], 57 parts by mass of [non-crystalline polyester resin dispersion 3], 45 parts by mass of [release agent dispersion 2], 26 parts by mass of [dying substance dispersion 1], and 600 parts by mass of water were placed in a container equipped with a thermometer and an agitator, and stirred at 30°C for 30 minutes. This dispersion was added with a 2% by mass aqueous sodium hydroxide solution to be adjusted to pH 10. This dispersion was then stirred at 5,000 rpm by a homogenizer (Ultra Turrax T50, manufactured by IKA (GmbH) while it is heated to 45°C, while a 5% by mass aqueous magnesium chloride solution was gradually dripped in. The result was held at 45°C until aggregated particles had grown to a volume-average particle diameter of 5.3 µm. This was added with a 2% by weight aqueous sodium hydroxide solution to be maintained at pH 9 while being heated to 90°C, and held for 2 hours in that state and then cooled to 20°C at 1°C/ minute to get a [folder 5]. Desolventization for washing to drying
[000353] [Folder 5] was washed, dried and sieved under the same conditions as those for [Folder 1] to prepare a toner base 5. Production example 24 Toner base production 6 (emulsion aggregation method) Preparation of crystalline polyester resin dispersion 2
[000354] 60 parts by mass of ethyl acetate were added and dissolved in 60 parts by mass of [crystalline polyester resin 1] by mixing and stirring at 60°C. then 120 parts by mass of the resin solution was added to an [aqueous phase] to which 120 parts by mass of water, 2 parts by mass of an anionic surface active agent (NEOGEN R, manufactured by Daiichi Kogyo Seiyaku Co. , Ltd.) and 2.4 parts by mass of a 2% by mass aqueous sodium hydroxide solution were mixed, and the result was emulsified by using a homogenizer (Ultra Turrax T50, manufactured by IKA GmbH), and then subjected to emulsification by a Manton-Gaulin high pressure homogenizer (manufactured by Gaulin Corp.) to obtain an [emulsified paste].
[000355] Next, the [emulsified slurry] was loaded into a container equipped with a stirrer and a thermometer, and desolventized at 60°C for 4 hours to obtain a [crystalline polyester resin dispersion 2]. The mean particle diameter-particle volume in the [crystalline polyester resin dispersion 2] obtained was 0.17 µm when measured by a particle size distribution analyzer (LA-920, manufactured by HORIBA, Ltd.). Aggregation
[000356] 207 parts by mass of [non-crystalline polyester resin dispersion 2], 57 parts by mass of [non-crystalline polyester resin dispersion 3], 28 parts by mass of [crystalline polyester resin dispersion 2], 45 parts by mass of [dispersion of release agent 2], 26 parts by mass of [dispersion of dyestuff 1] and 600 parts by mass of water were placed in a container equipped with a thermometer and an agitator, and stirred at 30 °C for 30 minutes. This dispersion was added with a 2% by mass aqueous sodium hydroxide solution to be adjusted to pH 10. This dispersion was then stirred at 5,000 rpm by a homogenizer (Ultra Turrax T50, manufactured by IKA GmbH) while heating up to 45°C, while a 5% by mass aqueous magnesium chloride solution was gradually dropped. The result was held at 45°C until aggregated particles had grown to a volume-average particle diameter of 5.3 µm. This was cooled to 20°C to obtain a [folder 6]. Desolventization for washing to drying
[000357] The [aste 6] was washed, dried, and sieved under the same conditions as those for [emulsified paste 1] to prepare a toner base 6. Production example 25 Toner base 7 production (spray method) Master Batch Preparation 2
[000358] Non-crystalline polyester resin 2 - 100 parts by mass
[000359] Carbon black (Printex 35, manufactured by Degussa AG) 100 parts by mass
[000360] (Amount of DBP oil absorption: 42 mL/100 g, pH 9.5)
[000361] Ion exchanged water - 50 parts by mass
[000362] The above raw materials were mixed by a Henschel mixer (Henschel 20B, manufactured by Nippon Coke & Engineering Co., Ltd.). the obtained mixture was kneaded by a two-roll mill. Kneading was started from a kneading temperature of 90°C, which was then gradually cooled to 50°C. the obtained kneaded product was pulverized by a pulverizer (manufactured by Hosowaka Micron Corporation) to prepare a [master batch 2]. Kneading by melting/spraying/classifying
[000363] 49 parts by weight of [non-crystalline polyester resin 2], 40 parts by weight of [non-crystalline polyester resin 3], 6 parts by weight of paraffin (HNP-9, manufactured by Nippon Seiro Co., Ltd. ., melting point 75°C), and 12 parts by mass of the [master batch] were preliminarily mixed for 3 minutes at 1500 rpm by the use of a Henschel mixer (Henschel 20B, manufactured by Nippon Coke & Engineering Co., Ltd. ) and then melt kneaded by a single screw kneader (small size Buss co-kneader, manufactured by Buss AG) under the conditions of a preset temperature (inlet part: 90°C), one outlet part ( 60°C) and a feed amount (10 kg/Hr). the obtained kneaded product was rolled up and cooled, and coarsely pulverized by a sprayer (manufactured by Hosokawa Micron Corporation). Then, the result was finely pulverized, by a type I mill (manufactured by Nippon Pneumatic Mfg. Co. Ltd.), under the conditions of an air pressure (6.0 atm/cm2) and a feed quantity ( 0.5 kg/h) by using a flat collision plate, and further classified by a classifier (model IDS-2, manufactured by Alpine AG) to obtain a [toner base 7]. Production example 26 Toner base production 8 (spray method) Fusing kneading/spraying/sorting
[000364] 54 parts by mass of [non-crystalline polyester resin 2], 27 parts by mass of [non-crystalline polyester resin 3], 8 parts by mass of [crystalline polyester resin 1], 6 parts by mass of paraffin (HNP-9, manufactured by Nippon Seiro Co., Ltd., melting point 75°C), and 12 parts by mass of [master batch 2] were preliminarily mixed for 3 minutes at 1500 rpm using a Henschel mixer ( Henschel 20B, manufactured by Nippon Coke & Engineering Co., Ltd.) and then melt kneaded by a single screw kneader (small size Buss co-kneader, manufactured by Buss AG) under the conditions of a preset temperature ( input part: 90°C), an output part (60°C) and a feed amount (10 kg/Hr). the obtained kneaded product was rolled up and cooled, and coarsely pulverized by a sprayer (manufactured by Hosokawa Micron Corporation). Then, the result was finely pulverized, by a type I mill (model IDS-2, manufactured by Nippon Pneumatic Mfg. Co. Ltd.), under the conditions of an air pressure (6.0 atm/cm2) and a feed amount (0.5 kg/h) by using a flat collision plate, and further classified by a classifier (132MP, manufactured by Alpine AG) to obtain a [toner base 7]. Toner Preparation 1 to 26
[000365] toner 1 to toner 26 were obtained according to tables 3-1 to 3-3 by mixing, in 100 parts by mass each of [toner base 1] to [toner base 8] obtained, 2.0 parts by mass of any of external additive 1 to external additive 12, 2.0 parts by mass of silica (trade name “H1303VP”, manufactured by Clariant AG) having a mean-voltage particle diameter of 20 nm, and 0.6 parts by mass of titanium oxide (trade name "JMT-150IB", manufactured by Tayca Corporation) by a Henschel mixer (manufactured by Nippon Coke & Engineering Co., Ltd.) and pass the mixtures through a sieve having an opening of 500 mesh. Production of core particles 1
[000366] MnCO3, Mg(OH)2 and Fe2O3 powders were weighed, and mixed to obtain a mixed powder. This mixed powder was temporarily burnt at 900°C for 3 hours under one atmosphere by a heating oven, and the temporarily burnt product obtained was cooled, and then pulverized into a powder having a particle diameter of substantially 1 µm. That powder was added with 1% by mass of a dispersing agent together with water to prepare a slurry, and that slurry was fed to a spray drier for granulation to obtain a granulated product having an average particle diameter of approximately 40 µm. This granular product was loaded into a firing furnace and fired under a nitrogen atmosphere at 1180°C for 4 hours. The obtained burnt product was disintegrated by a disintegrator, and then particle size adjusted by sieving to obtain [core particles 1] which are spherical ferrite particles having an average-voltage particle diameter of approximately 35 µm. [Core particles 1] had SF-1 of 135, SF-2 of 122, and Ra of 0.63 µm. Production of core particles 2
[000367] MnCO3, Mg(OH)2 and Fe2O3 powders were weighed, and mixed to obtain a mixed powder. This mixed powder was temporarily burnt at 900°C for 3 hours under one atmosphere by a heating oven, and the temporarily burnt product obtained was cooled, and then pulverized into a powder having a particle diameter of substantially 1 µm. That powder was added with 1% by mass of a dispersing agent together with water to prepare a slurry, and that slurry was fed to a spray drier for granulation to obtain a granulated product having an average particle diameter of approximately 40 µm. This granular product was loaded into a firing furnace and fired under a nitrogen atmosphere at 1300°C for 5 hours. The obtained burnt product was disintegrated by a disintegrator, and then particle size adjusted by sieving to obtain [core particles 2] which are spherical ferrite particles having a voltage-mean particle diameter of approximately 35 µm. [Core particles 2] had SF-1 of 125, SF-2 of 119, and Ra of 0.45 µm. Production of core particles 3
[000368] MnCO3, Mg(OH)2 and Fe2O3 powders were weighed, and mixed to obtain a mixed powder. This mixed powder was temporarily burnt at 850°C for 1 hour under one atmosphere by a heating furnace, and the obtained calcined product was cooled, and then pulverized into a powder having a particle diameter of 3 µm or less. This powder was added with 1% by mass of a dispersing agent together with water to prepare a slurry, and this slurry was fed to a spray drier for granulation to obtain a granulated product having a volume-average particle diameter of approximately 40 a. This granular product was loaded into a firing furnace and fired under a nitrogen atmosphere at 1120°C for 4 hours. The obtained burnt product was disintegrated by a disintegrator, and then particle size adjusted by sieving to obtain [core particles 3] which are spherical ferrite particles having an average-voltage particle diameter of approximately 35 µm. [Core particles 3] had SF-1 of 145, SF-2 of 155, and Ra of 0.85 µm. Production of Conductive Inorganic Fine Particles 1
[000369] 100 g of aluminum oxide (AKP-30, manufactured by Sumitomo Chemical Co., Ltd.) was dispersed in 1 L of water to prepare a suspension, and this fluid was heated to 70°C. a solution in which 11.6 g of stannic chloride was dissolved in 1L of 2N hydrochloric acid and 12% by mass of ammonia water was dropped into this suspension in 40 minutes so that the suspension reached a pH of 7 to 8. Subsequently, a solution into which 36.7 g of indium chloride and 5.4 g of stannic chloride were dissolved in 450 ml of 2N hydrochloric acid and 12% by mass of ammonia water were dropped in 1 hour so that the suspension had pH 7 to 8. After dropping, a slurry obtained by filtering and washing the suspension was dried at 110°C. this dry powder was then treated at 500°C for 1 hour in a stream of nitrogen to obtain [conductive inorganic fine particles 1]. The [conductive inorganic fine particles 1] obtained had a numerical mean particle diameter of 300 nm and a specific voltage resistance of 4 Q-cm. Production of non-conductive inorganic fine particles 1
[000370] 100 g of aluminum oxide (AKP-30, manufactured by Sumitomo Chemical Co., Ltd.) was dispersed in 1 L of water to prepare a suspension, and this fluid was heated to 70°C. a solution in which 10 g of stannic chloride and 0.30 g of phosphorus pentoxide were dissolved in 100 ml of 2N hydrochloric acid and 12% by mass of ammonia water were dropped into this suspension in 12 minutes so that the suspension reached pH 7 to 8. After dropping, a slurry obtained by filtering and washing the suspension was dried at 110°C. this dry powder was then treated at 500°C for 1 hour in a stream of nitrogen to obtain [non-conductive inorganic fine particles 1]. The [non-conductive inorganic fine particles 1] obtained had a number-average particle diameter of 300 nm and a specific voltage resistance of 4 Q-cm. Coating resin production 1
[000371] 300 g of toluene was charged into a flask with a stir bar and heated to 90°C under a stream of nitrogen gas. Next, in that, a mixture of 84.4 g (200 mmol: Silaplane TM-0701T/manufactured by Chisso Corporation) of 3-methacryloxy propyl tris(trimethyl siloxy) silane expressed by CH2 = CMe-COO-C3H6-Si(OSiMe3 )3 (in the above formula Me indicates a methyl group), 37.2 g (150 millimols) of 3-methacryloxy propyl trimethoxy silane, 65.0 (650 mmol) of methyl methacrylate and 0.58 g (3 mmol) of 2,2'-azobis-2-methyl butyronitrile was dropped in 1 hour. After finishing the dripping, a solution to which 0.06 g (0.3 mmol) of 2,2'-azobis-2-methyl butyronitrile was dissolved in 15 g of toluene was further added (a total amount of 2.2 '-azobis-2-methyl butyronitrile 0.64 g = 3.3 mmol) and mixed at 90°C to 100°C for 3 hours to effect radical copolymerization to obtain a [coating resin 1].
[000372] The [coating resin 1] obtained had a Mw of 34,000. then that solution of [coating resin 1] was diluted with toluene so as to reach a non-volatile content of 25% by mass. The solution of [coating resin 1] thus obtained had a viscosity of 8.7 mm2/s and a specific gravity of 0.91. Conveyor Preparation 1
[000373] 26 parts by mass of a methyl silicone resin (Mw: 15,000, solid content: 25% by mass), 2.5 parts by mass of an acrylic resin (Hitaloid 3001, solid content: 50% by mass, manufactured by Hitachi Chemical Company, Ltd.), 5 parts by mass of a benzoguanamine-based resin (Mycoat 106, solids content: 77% by mass, manufactured by Mitsui Cytec Ltd.), 20 parts by mass of [Conductive Inorganic Fine Particles 1 ], 2 parts by mass of diisopropoxy bis(ethyl acetate acetate) titanium TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) as catalyst and 1.4 parts by mass of SH6020 (manufactured by Toray Silicone Co., Ltd. .) as a silane coupling agent prepared from di-functional or tri-functional monomers were diluted with toluene to obtain a resin solution with a solid content of 10% by mass. This resin solution was coated onto 1000 parts by mass of [core particles 1] by an immersion method using a multifunctional mixer. At that time, the carrier core temperature was set at 100°C, the resin solution was loaded into the mixer, and a mixing stirring paddle was rotated until the coating liquid evaporated to perform coating and stirring/drying treatment , and a carrier was removed. The conveyor obtained was burned at 180°C for 2 hours in an electric oven to obtain a conveyor 1. This conveyor 1 had a work function of 4.0 eV and SF-2 of 114, and the conveyor volume density was 2.42 g/cm3. Conveyor Preparation 2
[000374] 26 parts by mass of a methyl silicone resin (Mw: 15,000, solid content: 25% by mass), 2.5 parts by mass of an acrylic resin (Hitaloid 3001, solid content: 50% by mass, manufactured by Hitachi Chemical Company, Ltd.), 5 parts by mass of a benzoguanamine-based resin (Mycoat 106, solids content: 77% by mass, manufactured by Mitsui Cytec Ltd.), 16.4 parts by mass of [fine particles conductive inorganics 1], 2 parts by mass of diisopropoxy bis(ethyl acetate acetate) titanium TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) as catalyst and 0.7 parts by mass of SH6020 (manufactured by Toray Silicone Co. ., Ltd.) as a silane coupling agent prepared from di-functional or tri-functional monomers were diluted with toluene to obtain a resin solution with a solid content of 10% by mass. This resin solution was coated onto 1000 parts by mass of [core particles 2] by an immersion method using a multifunctional mixer. At that time, the carrier core temperature was set at 100°C, the resin solution was loaded into the mixer, and a mixing stirring paddle was rotated until the coating liquid evaporated to perform coating and stirring/drying treatment , and a carrier was removed. The conveyor obtained was burned at 180°C for 2 hours in an electric oven to obtain conveyor 2. This conveyor 2 had a work function of 4.3 eV and SF-2 of 111, and the conveyor volume density was 2.46 g/cm3. Conveyor Preparation 3
[000375] 26 parts by mass of a methyl silicone resin (Mw: 15,000, solid content: 25% by mass), 2.5 parts by mass of an acrylic resin (Hitaloid 3001, solid content: 50% by mass, manufactured by Hitachi Chemical Company, Ltd.), 5 parts by mass of a benzoguanamine-based resin (Mycoat 106, solids content: 77% by mass, manufactured by Mitsui Cytec Ltd.), 18 parts by mass of [Conductive Inorganic Fine Particles 1], 2 parts by mass of diisopropoxy bis(ethyl acetate acetate) titanium TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) as catalyst and 0.2 parts by mass of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent prepared from di-functional or tri-functional monomers were diluted with toluene to obtain a resin solution with a solid content of 10% by mass. This resin solution was coated onto 1000 parts by mass of [core particles 2] by an immersion method using a multifunctional mixer. At that time, the carrier core temperature was set at 100°C, the resin solution was loaded into the mixer, and a mixing stirring paddle was rotated until the coating liquid evaporated to perform coating and stirring/drying treatment until the coating liquid evaporated, and a carrier was removed. The conveyor obtained was burned at 180°C for 2 hours in an electric oven to obtain a conveyor 3. This conveyor 3 had a work function of 4.4 eV and SF-2 of 111, and the conveyor volume density was 2.44 g/cm3. Conveyor Preparation 4
[000376] 12 parts by mass of a methyl silicone resin (Mw: 15,000, solid content: 25% by mass), 48 parts by mass of [coating resin 1] (solid content: 25% by mass), 1 part by mass of diisopropoxy bis(ethyl acetate acetate) titanium TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) as catalyst and 1.8 parts by mass of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent prepared from di-functional or tri-functional monomers were diluted with toluene to obtain a resin solution with a solids content of 10% by mass. This resin solution was coated and dried, using a fluidized bed coater, on 1000 parts by mass of [core particles 3] while controlling the temperature in the fluidizing tank at 70°C each. The conveyor obtained was burned at 180°C for 2 hours in an electric oven to obtain a conveyor 4. This conveyor 4 had a work function of 4.0 eV and SF-2 of 139, and the conveyor volume density was 2.14 g/cm3. Conveyor Preparation 5
[000377] 64 parts by mass of a methyl silicone resin (Mw: 15,000, solids content: 25% by mass), 56 parts by mass of [conductive inorganic fine particles 1], 6 parts by mass of diisopropoxy bis(ethyl) acetate acetate) titanium TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) as a catalyst and 1.8 parts by mass of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent prepared from Di-functional or tri-functional monomers were diluted with toluene to obtain a resin solution with a solids content of 10% by mass. This resin solution was, using a fluidized bed coater, coated and dried on 1000 parts by mass of [core particles 1] while controlling the temperature in the fluidizing tank at 70°C each. The conveyor obtained was burned at 180°C for 2 hours in an electric oven to obtain a conveyor 5. This conveyor 5 had a work function of 4.0 eV and SF-2 of 114, and the conveyor volume density was 2.42 g/cm3. Conveyor work function measurement method
[000378] The work function of Wc conveyor was measured by using a work function measuring device (Surface Analyzer AC-2, manufactured by Riken Keiki Co., Ltd.) using a photoelectric effect. Specifically, a conveyor was filled into a recess portion of a sample measuring cell (having a shape with a recess portion with a diameter of 10 mm and a depth of 1 mm in the center of a disc made of stainless steel with a diameter of 13 mm and a height of 5 mm) and the surface was smoothed by the edge of a knife. After the sample measuring cell filled with a carrier was fixed in a defined position on a sample table, the amount of irradiation light was set to 500 nW, the irradiation area was given as 4 mm square, and a measurement was performed under a power sweep condition of 3.4 eV to 6.2 eV. Examples
1 to 22, comparative examples 1 to 4 Preparation of developers 1 to 26
[000379] Developers 1 to 26 of examples 1 to 22 and comparative examples 1 to 4 were prepared according to tables 3-1 to 3-3 by mixing 70 parts by mass each of toner 1 to toner 26 and 930 parts in mass each from conveyor 1 to conveyor 5 were mixed for 5 minutes at 81 rpm by a TURBULA mixer. In addition, as a refill developer for each developer, a refill developer has been manufactured by mixing so that the carrier concentration reaches 10% by mass.
[000380] In the following according to table 3-1 to 3-3, the obtained developers 1 to 26 were filled into developing devices including elements containing developer each made of a surface material of any of A1 (Ws: 3.7 eV), SUS (Ws: 4.4 eV) and TiB (4.7 eV), and evaluated for initial stability and stability over time against hysteresis, and low temperature fixation capacity (medium speed machine), the stability over time against a hysteresis to make comprehensive decisions as follows. Results are given in Tables 3-1 to 3-3.
[000381] Initial stability and stability over time against hysteresis (medium speed machine)
[000382] The respective prepared developers and refill developers were placed on commercially available digital full color printers (IMAGIO MPC6000, 50 sheets/minute of horizontal A4 size color images, manufactured by Ricoh Company, Ltd.) and 10kp graphics sheets of letter (the size of a letter: approximately 2mm x 2mm) with an image area ratio of 8% were printed, and then 200kp was printed additionally. In terms of hysteresis, vertical bar graphs shown in Figure 10 were printed after 10kp output sheets and after 200kp output sheets, and concentration differences between an image portion after a non-image portion (first sleeve stroke) ( a) and an image portion after a non-imaging portion (second glove stroke) (b) were respectively evaluated by X-Rite 938 (manufactured by X-Rite Inc.) using a mean concentration difference of measurements at three locations center, rear and front as ΔID, in the following criteria, with ΔID after 10kp output sheets considered as hysteresis (initial stability, medium speed machine) and ΔID after 200 kp output sheets, as hysteresis (stability over time, medium speed machine). Evaluation criteria A: very good, B: good, C: acceptable, D: impractical A, B, C: approved; D: fail A: 0.01 > ΔID B: 0.01 < ΔID < 0.03 C: 0.03 < ΔID < 0.06 D: 0.06 < ΔID Stability over time against hysteresis (high speed machine)
[000383] The respective prepared developers and refill developers were placed on commercially available digital full color printers (RICOH Pro C901, 90 sheets/minute horizontal A4-size color images, manufactured by Ricoh Company, Ltd.) and 200 kp of graphics (the size of a letter: approximately 2 mm x 2 mm) with an image area ratio of 8% were printed. In terms of hysteresis, vertical bar graphs shown in figure 10A and figure 10B were printed after 200kp of output sheets, and concentration differences between an image portion after a non-image portion (first glove stroke) (a) and an image portion after a non-image portion (second glove stroke) were respectively evaluated by X-Rite 938 (manufactured by X-Rite Inc.), using a mean concentration difference of measurements at three center, rear locations. and forward as ΔID, in the following criteria with ΔID after 10kp output sheets considered as a hysteresis (initial stability, average speed machine) and ΔID after 200kp output sheets, as a hysteresis (stability over time, average speed machine ). Evaluation criteria A: very good, B: good, C: acceptable, D: impractical A, B, C: approved; D: fail A: 0.01 > ΔID B: 0.01 < ΔID < 0.03 C: 0.03 < ΔID < 0.06 low temperature fixation capacity evaluation criteria
[000384] An apparatus for which an image forming apparatus (MF 2200, manufactured by Ricoh Company Ltd.) using a Teflon roller (trademark) as a fixation roller was modified in the fixation section was used to copy onto test on recording paper (6200 grade, manufactured by Ricoh Company, Ltd.). specifically, the fixation temperature was changed to determine a cold offset temperature (lower limit fixation temperature). As evaluation conditions for the lower limit setting temperature, the linear paper feed speed was set at 120 mm/second to 150 mm/second, the surface pressure at 1.2 kgf/cm2 and the pass width at 3 mm. Low temperature fixation capacity was evaluated on the following criteria. The lower the lower limit setting temperature, the more excellent the low temperature setting ability. Evaluation criteria A: very good, B: good, C: acceptable, D: impractical A, B, C: approved; D: fail A: lower limit setting temperature less than 120°C: lower limit setting temperature of 120°C or more and less than 130°C: lower limit setting temperature of 130°C or more and less than 140°CD: lower limit setting temperature of 140°C or more and less than 150°C Comprehensive judgments AA: extremely good, A: very good, B: good, C: acceptable, D: impractical AA, A, B, C: approved; D: fail AA: 3 or more As and no C or DA: 2 As and no C or DB: other C: 2 or more Cs and no A or DD: 1 or more D Table 2

Table 3-1
Table 3-2

Table 3-3


[000385] It can be understood from Tables 3-1 to 3-3 that as compared to the developers of comparative examples 1 to 4, the developers of examples 1 to 22 could obtain good results in terms of initial stability and relative stability in time against hysteresis and stability over time against hysteresis in a high speed machine.
[000386] Aspects of the present invention are, for example, as follows: 1. Development device, including: a developer-containing element, which is disposed opposite an electrostatic imaging-containing element and which contains over it a developer to develop an electrostatic latent image formed in the electrostatic latent image-containing element and transfers the developer to a developing region, wherein the developer comprises a toner and a carrier, the toner containing: a toner base containing a binder resin and a coloring substance; and an external additive, wherein the external additive comprises coalescing particles each composed of a plurality of primary coalescing particles, and wherein a carrier working function Wc and a developer containing element Ws working function meet a relationship of the following formula (1):
2. Developing device according to 1, wherein the working function Wc of the conveyor and the working function Ws of the developer-containing element meet a relationship of the following formula (1-1):
3. Developing device according to 1 or 2, wherein the coalescing particles have a particle size distribution index expressed by the following formula (2):
Where in formula (2), in a distribution diagram in which particle diameters (nm) of the coalesced particles are on the horizontal geometric axis and cumulative percentages (% by number) of the coalesced particles are on the vertical geometric axis and where the coalesced particles are accumulated from coalesced particles having smaller particle diameters to coalesced particles having larger particle diameters, Db50 indicates a particle diameter of the coalesced particle in which the cumulative percentage is 50% by number, and Db10 indicates a particle diameter of the coalesced particle in which the cumulative percentage is 10% by number. 4. Development device according to any one from 1 to 3, wherein the coalescing particles meet the following formula (3)
: Where in formula (3), Nx indicates the number of broken or bent particles in 1,000 of the coalescent particles, where the broken or bent particles are selected by agitating 10.5 g of the coalescent particles and 49.5 g of the carrier placed in a 50 mL flask by using an oscillating mill, which is manufactured by Seiwa Giken Co., Ltd., under conditions of 67 Hz and for 10 minutes, and then observing the stirred coalescent particles through a scanning electron microscope. 5. Development device, according to any one from 1 1 to 4, in which the coalescing particles meet the following formula (3-1) :
Where in formula (3-1) , Nx indicates the number of broken or bent particles in 1,000 of the coalescent particles, where the broken or bent particles are selected by stirring 10.5 g of the coalescent particles and 49.5 g of the carrier placed in a 50 mL vial by using an oscillating mill, which is manufactured by Seiwa Giken Co., Ltd., under 67 Hz conditions for 10 minutes, and then observing the stirred coalescent particles through a scanning electron microscope. 6. Developing device according to any one of 1 to 5, wherein the coalescing particles have a numerical mean particle diameter of 80 nm to 200 nm. 7. Developing device according to any one of 1 to 6, wherein the coalescing particles have a numerical mean particle diameter of 100 nm to 160 nm. 8. The developing device according to any one of 1 to 7, wherein the binder resin contains a crystalline polyester resin. 9. Developing device according to any one of 1 to 8, wherein the carrier contains a magnetic core particle and a coating layer that covers the core particle and has an SF-2 factor factor of 115 to 150 and a bulk density of 1.80 g/cm3 to 2.40 g/cm3, where the core particle has an SF-2 shape factor of 120 to 160 and has an arithmetic mean surface roughness Ra of 0.5 µm to 1.0 µm, and wherein the coating layer comprises a resin and inorganic fine particles, and comprises the inorganic fine particles at a rate of 50 parts by mass to 500 parts by mass to 100 parts by mass of the resin. 10. Imaging apparatus, including: an element that contains electrostatic latent imaging; a charging unit configured to charge a surface of the element that contains electrostatic latent imaging; an exposure unit configured to expose the charged surface of the electrostatic latent image-containing element to form an electrostatic latent image; a developer unit configured to develop the electrostatic latent image with a toner to form a visible image; a transfer unit configured to transfer the visible image to a recording medium; and a fixing unit configured to fix a transfer image transferred to the recording medium, wherein the developing unit is the developing device according to any one of 1 to 9.

权利要求:
Claims (10)
[0001]
1. A developing device characterized in that it comprises: a developer-containing element, which is disposed opposite an electrostatic latent image-containing element and which contains a developer thereon to reveal an electrostatic latent image formed in the image-bearing element electrostatic latent and transfers the developer to a developing region, wherein the developer comprises a toner and a carrier, the toner comprising: a toner base comprising a binder resin and a colorant; and an external additive, wherein the external additive comprises coalescing particles each composed of a plurality of primary coalescing particles, wherein a carrier working function Wc and a developer containing element Ws working function meet a relationship of the following formula (1):
[0002]
2. Development device according to claim 1, characterized in that the work function Wc of the conveyor and the work function Ws of the developer-containing element meet a relationship of the following formula (1-1):
[0003]
3. Development device according to claim 1, characterized in that the coalescing particles have a particle size distribution index expressed by the following formula (2):
[0004]
4. Development device according to claim 1, characterized in that the coalescing particles meet the following formula (3):
[0005]
5. Development device according to claim 1, characterized in that the coalescing particles meet the following formula (3-1):
[0006]
6. Development device according to claim 1, characterized in that the coalescing particles have a numerical mean particle diameter of 80 nm to 200 nm.
[0007]
7. Development device according to claim 1, characterized in that the coalescing particles have a numerical mean particle diameter of 100 nm to 160 nm.
[0008]
8. Development device according to claim 1, characterized in that the binder resin comprises a crystalline polyester resin.
[0009]
9. Development device characterized in that it comprises: a developer-containing element, which is disposed opposite an electrostatic latent image-containing element and which contains a developer thereon to reveal an electrostatic latent image formed in the image-bearing element electrostatic latent and transfers the developer to a developing region, wherein the developer comprises a toner and a carrier, the toner comprising: a toner base comprising a binder resin and a colorant; and an external additive, wherein the external additive comprises coalescing particles each composed of a plurality of primary coalescing particles, and wherein a carrier work function Wc and a developer containing element work function Ws meet a relationship of following formula (1):
[0010]
10. Imaging apparatus characterized by the fact that it comprises: an element that contains electrostatic latent image; a charging unit configured to charge a surface of the element that contains electrostatic latent imaging; an exposure unit configured to expose the charged surface of the electrostatic latent image-containing element to form an electrostatic latent image; a developing device configured to develop the electrostatic latent image with a toner to form a visible image; a transfer unit configured to transfer the visible image to a recording medium; and a fixing unit configured to fix a transfer image transferred to the recording medium, wherein the developing device is the developing device as defined in claim 1.

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法律状态:
2018-03-13| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|

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2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-09-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-06-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2012-200356|2012-09-12|

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JP2012200356A|JP5979593B2|2012-09-12|2012-09-12|Developing device and image forming apparatus|

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