JP4832265B2 - Toner manufacturing method, toner, two-component developer, process cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to a toner manufacturing method, a toner, a two-component developer, a process cartridge, and an image forming apparatus.

  The image quality of copiers, printers, and the like has been improved, and recently, the reproducibility of fine dots has become very important. The dot reproducibility is greatly influenced by the fluidity of the toner in addition to the charge amount of the toner, and it is necessary to stably supply a uniform toner layer to the fine latent image portion.

  In addition, as the image quality increases, the toner used has a smaller particle size and higher functionality. As a result, the structure of the toner has become complicated, and finer control and evaluation at the time of toner production has become necessary as compared with the conventional structure. In particular, the fluidity of the toner has a great influence on various image quality in addition to the dot reproducibility. Therefore, this improvement in fluidity is regarded as a very important technique in toner production.

  In recent years, the toner production method has shifted mainly from the pulverization method to the polymerization method. However, the change in the flow characteristics of the toner with respect to the production conditions of the polymerization method is large, and it has been a problem that the control and evaluation at the time of production must be performed more accurately than in the case of production by the pulverization method.

  In addition, it is necessary to stably output high image quality, and it is also important to stably maintain the fluidity of the toner. That is, even if the toner repeatedly receives a force such as stirring in the developing portion, it is necessary to have a structure in which the change in the toner particle surface is small.

  For this reason, in a toner manufactured by a polymerization method, a method of providing appropriate unevenness on the surface of the resin separation structure has been proposed (see, for example, Patent Document 1).

In the method of developing by applying an oscillating electric field between the electrostatic latent image carrier and the developer carrier, the surface shape of the toner is D / d50 (D is assumed that the toner shape is a sphere). A method is also proposed in which the converted particle diameter from the BET specific surface area at the time, and d50 is defined as a numerical value equivalent to 50% of the relative weight distribution by particle diameter (see, for example, Patent Document 2). ). This method aims to improve toner mobility in the development area.
Japanese Patent No. 2961465 Japanese Patent Laid-Open No. 11-295989

  However, the toner having appropriate irregularities on the surface of the resin separation structure disclosed in Patent Document 1 has a problem in durability and stability because the characteristic that the irregularities are easily deteriorated by wear.

  In addition, the method disclosed in Patent Document 2 for defining the surface shape of the toner to a predetermined value does not take into account the periodicity of the surface property, so that variations occur between the toners, thereby realizing high image quality. There was a problem that it was difficult.

  The present invention has been made in view of the above points, and a method for producing a toner excellent in toner transportability during image formation, a toner produced by the method, a two-component developer containing the toner, and the toner It is an object to provide a process cartridge using the process cartridge and an image forming apparatus using the process cartridge.

  In order to achieve the above object, the present invention is characterized by the following means.

The toner production method of the present invention includes a surface treatment step in which, in the toner production method, the toner is vibrated and the surface of the toner is treated with fine particles containing silicon nitride and having an average particle diameter of 10 nm to 100 nm.

  The toner of the present invention is manufactured by the toner manufacturing method.

The two-component developer of the present invention includes the toner and a magnetic carrier. The process cartridge of the present invention forms an image using the toner.

  The image forming apparatus of the present invention uses the process cartridge.

  According to the present invention, a method for producing a toner excellent in toner transportability during image formation, a toner produced by the method, a two-component developer containing the toner, a process cartridge using the toner, and the process cartridge It is possible to provide an image forming apparatus using the.

  Next, the best embodiment of the present invention will be described with reference to the drawings.

(Method of supplying fine particles to the toner surface)
In the toner of this embodiment, attention is paid to the periodicity and uniformity of the surface shape of the toner, and a surface treatment method suitable for it is studied. This surface treatment method is realized by attaching silicon nitride fine particles to the surface of the toner particles and controlling the force between the toner particles. Specifically, fine particles containing at least silicon nitride having an average particle size of 10 nm or more and 100 nm or less are produced in the same tank, and after the fine particles are produced, they are adhered to the surface of toner particles containing at least a resin and a pigment, and surface treatment is performed. Do. Examples of such surface treatment methods include vapor deposition, sputtering, and CVD, but laser ablation is adopted as a treatment method for temperature-sensitive particles such as toner particles. It is preferable.

  FIG. 1 is a schematic view of a toner surface treatment apparatus using a laser ablation method in an embodiment of the present invention.

  Referring to FIG. 1, the toner surface treatment apparatus 10 generally includes a gas laser light source 11, a lens 12, a target 13, and a vibration device 17.

  The surface of the target 14 is heated by irradiating the surface of the target 14 having a composition to be adhered to the toner particle surface with the laser 13 formed by the gas laser light source 11 and the lens 12. In this method, molecules and clusters on the surface of the target 14 are ejected by this heating, and fine particles 15 composed of the molecules and clusters are attached to the surface of the toner particles 16 at a position away from the surface of the target 14.

  The fine particles produced by such a production method exhibit physical and chemical characteristics different from bulk fine particles due to the quantum size effect and the effects of the surface and the interface. The toner preparation method by this laser ablation method has the characteristics listed below.

  (1) Composition deviation hardly occurs. (2) Since light having a very high power density is used, any material that absorbs light can be easily deposited even with a material having a high melting point. (3) Since the influence of the vapor pressure is small, the atmospheric gas pressure can be increased. (4) Since no filament or the like is used in the resistance heating method, there is little contamination. (5) Since no plasma or the like is used, low temperature deposition is possible.

  Compared to the conventional method in which toner and silica are mixed and the fine particles adhere to the toner surface, the laser ablation method ionizes the produced fine particles, and the fine particles adhere to the toner particle surface in a clean state. Therefore, uniform and reliable adhesion of fine particles to the toner particle surface can be realized.

  However, if the surface of the toner particle 16 is always oriented in the same direction, the fine particles adhere only to the surface in that direction. Therefore, the toner particles 16 are vibrated together with the container using the vibration device 17 so that the toner particles are directed in different directions at a certain period. The vibration frequency is suitably 1 Hz or more and 60 Hz or less, and if the vibration frequency is less than 1 Hz, uneven distribution of fine particles on the toner particle surface occurs, and if the vibration frequency is higher than 60 Hz, the difference in the adhesion state between the toner particles. Tends to increase.

Since the laser 13 is preferably a high-power laser, a gas laser is suitable. A CO ₂ gas laser, a YAG laser, an Ar gas laser, a KrF excimer laser, an ArF excimer laser, or the like is preferably used. In the present embodiment, laser ablation is performed in an Ar gas atmosphere using an Nd: YAG laser (wavelength: 266 nm) to produce fine particles made of at least silicon nitride having an average particle size of 10 nm or more and 100 nm or less. Was directly attached to the particle surface of the toner containing at least a resin and a pigment.

  The size of the fine particles is a very important factor for making fine irregularities on the toner particle surface in order to control the interparticle force of the toner. Therefore, the average particle size of the fine particles is preferably 10 nm or more and 100 nm or less. When the average particle size of the fine particles is less than 10 nm, the unevenness is too small and the effective influence on the interparticle force is small, and when the average particle size is larger than 100 nm, the distribution of the fine particle size becomes wide, and the dispersion of the interparticle force is also large. It grows and causes problems.

  The fine particles serve to protect the toner particles from environmental influences such as temperature and humidity as well as controlling the interparticle force of the toner. Therefore, a stable material that is hardly affected by moisture or the like is suitable for the fine particles, and it is preferable to use silicon nitride. In the present embodiment, fine particles made of at least silicon nitride may contain silicon oxide. However, the more silicon nitride component is suitable in consideration of the protection function for the toner particles.

Laser ablation is performed in an inert gas atmosphere such as He, Ar, and Xe, but it is preferable to use Ar in terms of cost. The pressure of the inert gas is preferably 1 × 10 ⁻² Pa or more and 1 Pa or less. When the pressure of the inert gas is less than 1 × 10 ⁻² Pa, it is difficult to produce fine particles. When the pressure is higher than 1 Pa, fine particles having a large size are produced, and the surface treatment of toner particles is performed. Is no longer suitable.

  The laser output is preferably 10 mJ / pulse or more and 500 mJ / pulse or less. When surface treatment is performed with a laser output of less than 10 mJ / pulse, there is a problem that the surface treatment time is very long. When this laser output is larger than 500 mJ / pulse, many fine particles having a large particle diameter are produced, which is not suitable for the surface treatment conditions of the toner particles.

The target has a composition with a purity as high as possible, and a target having a size larger than the range that can be scanned by the laser is used. In the present embodiment, Si ₃ N ₄ is used as a target. The distance between the target and the toner sample is preferably 40 mm or more and 60 mm or less. If this distance is less than 40 mm, only a surface treatment can be performed on a narrow range of toner particles, and if it is greater than 60 mm, the surface adhesion efficiency of the fine particles to the toner particles decreases.

(Evaluation of fluidity of toner particles by AFM method)
The fluidity of the toner particles treated with the fine particles is evaluated by directly measuring the force acting between the toner particles by the atomic force microscope (AFM) method.

  The AFM method is a method in which a probe having a tip diameter of 10 nm is scanned, an atomic force acting between the probe and atoms on the sample surface is detected, and the surface shape of the sample is measured. The AFM method can measure with very high resolution, and can measure the uneven shape in the Z direction when the scanning direction of the probe is the X direction.

  In the present embodiment, first, one toner particle is attached to the tip of the probe. Then, one toner particle at the tip of the probe is pressed once against one toner particle on the surface of the compacted toner powder phase, and then scanned so as to be separated, and a change in force at that time is measured.

  FIG. 2 is a characteristic diagram showing a force change when the toner particles according to the present embodiment are pressed against the surface of the compacted toner powder phase and then scanned so as to be separated.

  Referring to FIG. 2, the vertical axis represents the interparticle force (nN), and the horizontal axis represents the amount of piezo displacement (nm). In addition, the solid line in the figure shows the characteristics of force change when the toner particles of the present embodiment on the probe are pressed against the surface of the compacted toner powder phase, and the dotted line in the figure shows the characteristic on the probe. FIG. 5 shows the characteristics of force change when the toner particles of the present embodiment are pressed against the surface of the compacted toner powder phase and then separated from the surface of the toner powder phase.

  As a result of this measurement, the force characteristics shown in the figure are obtained, and the interparticle force between the toner particles can be obtained from the difference between the characteristics when the probe is brought close and the characteristics when the probe is pulled apart.

  FIG. 3 is a configuration diagram of the AFM apparatus of this embodiment.

  Referring to FIG. 3, the AFM apparatus 30 roughly includes a substrate stage 31, a toner powder phase 32, toner particles 33, a probe 34, a piezo scanner 35, a laser light source 36, a mirror 38, and a laser detector 39. .

  A compacted toner powder phase 32 is provided on the substrate stage 31. A probe 34 with a single toner particle 33 is brought close to or separated from the surface of the toner powder phase 32 using a piezo scanner 35. At this time, the piezo scanner 35 moves up and down in the direction of arrow A in the drawing.

  The force change generated in the probe 34 by the above-described movement irradiates the back side of the probe 34 with the laser 37 emitted from the laser light source 36 and detects the change of the laser 37 reflected there. Specifically, the laser 37 reflected by the back side of the probe 34 is detected by the laser detection unit 39 via the mirror 38, and the above-described change is detected.

  At the time of measurement using the AFM apparatus 30, it is necessary to detect all forces acting on one toner particle 33 attached to the tip or the periphery of the probe 34 with high accuracy. Therefore, the distance at which one toner particle 33 attached to the tip or the periphery of the probe 34 is brought close to the surface of the toner powder phase 32 made of the same kind of toner particles is important. When toner particles are used as a measurement material, the toner particles have a property of being easily affected by frictional charging and the like, and therefore measurement from positions apart from each other is required. A preferable distance when the toner particles 33 attached to the tip or the periphery of the probe 34 are brought close to one toner particle in the toner particle powder phase 32 is preferably 0.5 μm or more and 2 μm or less. From this distance of 0.5 μm or more and 2 μm or less, the probe 34 to which one toner particle 33 is attached is brought close to the surface of the toner particle powder phase 32, and once pressed against this surface, the probe 34 is operated to be separated. Thus, the force acting between the toner particles is measured. If this distance is shorter than 0.5 μm, the probe 34 may not be able to be separated from the surface of the toner particle powder phase 32, which is not suitable for measurement. When this distance is longer than 2 μm, the measurement accuracy is deteriorated, and it is difficult to accurately measure the difference between the characteristics when the probe 34 approaches and the characteristics when the probe 34 is pulled apart.

Further, Si ₃ N ₄ and Si single crystal are used for the probe 34.

The toner particle powder phase 32 is in a state of being compressed at a pressure of 100 to 900 kg / cm ² , and the toner particle powder phase 32 even when the probe 34 to which one toner particle 33 is attached contacts. It is fixed so as not to collapse. However, when the compression pressure is less than 100 kg / cm ^2, there are toner particles that are not sufficiently fixed partially, and thus are not suitable for measurement. On the other hand, when the compression pressure is higher than 900 kg / cm ² , the toner particles are deformed and the structure of the toner particles is distorted. For this reason, it becomes a state different from normal toner particles, and is not suitable for the measurement of the force between particles.

The toner particle powder phase 32 compressed at a pressure of 100 kg / cm ² or more and 900 kg / cm ² or less is formed into a flat plate size of 10 mm (length) × 10 mm (width) × 5 mm (thickness) or less. After that, it was used for measurement. In measurement, the compressed toner particle powder phase 32 is fixed to the substrate stage 31 and measured. At that time, the compressed toner particle powder phase 32 adheres to the surface of the substrate stage 31 and is fixed so as to be as horizontal as possible. Further, a toner particle powder phase 32 in which one toner particle is randomly arranged and fixed on an adhesive layer on the surface of a substrate stage 31 such as glass is used, and one toner particle 33 is attached to the toner particle. The measurement may be performed by bringing the probe 34 in contact with each other.

  The scanning speed of the piezo when one toner particle 33 attached to the tip or the periphery of the probe 34 is brought close to the compressed toner particle powder phase 32 is preferably 0.16 Hz to 4.0 Hz. When the piezo scan speed is less than 0.16 Hz, the piezo operates slowly, so that it is strongly influenced by the adsorption state of the toner particle surface, resulting in a large variation and not suitable as a measurement condition. When the piezo scan speed is higher than 4.0 Hz, the piezo operates fast, and the operation of pressing and separating toner particles is not sufficient. For this reason, the interparticle force between the toner particles, which is obtained from the difference in force between when the probe 34 to which one toner particle 33 is adhered, is brought close to and separated from the toner particle powder phase 32 tends to be small. Not suitable as measurement conditions.

  The method of attaching one toner particle 33 to the tip of the probe 34 is to contact the wire coated with the adhesive with the probe 34 while viewing an enlarged image using an optical microscope, and to attach the adhesive to the tip of the probe 34. To attach. Next, the wire on which the toner particles are loosely attached is brought close to the probe 34 having an adhesive attached to the tip, and only one toner particle 33 is attached to the tip of the probe 34. Next, the probe 34 having one toner particle 33 attached is dried at room temperature for 24 hours or more. As the adhesive, a curable adhesive is suitable because the force between particles is accurately measured. Further, a two-component mixed type capable of adjusting the curing time is suitable. Examples of the two-component mixed cured resin adhesive include EP-330 (manufactured by Cemedine).

  The measurement of the force between the toner particles using the AFM apparatus 30 is repeated 10 to 50 times and evaluated using the average value. This repetition is not repeated at the same location on the toner particle powder phase 32, but is preferably measured while moving about 50 nm, for example. At that time, it is also important to evaluate the distribution of interparticle forces.

  The interparticle force of toner particles varies depending on the toner particle surface state and toner particle shape. The interparticle force when the toner particle surface has fine irregularities is, for example, 22 nN, and the toner particle force when the toner particle surface has a smooth surface without fine irregularities is, for example, 127 nN. From this result, it can be seen that when fine irregularities exist on the surface of the toner particles, the interparticle force becomes small. This is because the distance between the toner particles is increased due to the unevenness on the surface of the toner particles, or the contact area between the toner particles is reduced, and the interaction between the particles is reduced.

(Toner shape)
The shape of the toner particles also affects the interparticle force. The shape of the toner particles close to a sphere is suitable for measuring the force between particles because the measurement variation is small.

  The shape of the toner is evaluated by the circularity. A specific method for measuring the circularity is measured using a flow type particle image analyzer (FPIA-2000, manufactured by Sysmex Corporation). The average circularity is preferably in the range of 0.92 to 0.99. Toners within this range have good fluidity and can realize high image quality. Further, within this range, since one toner particle is attached to the tip of the probe, no matter which part of the toner particle is attached to the tip of the probe, the surface of the particle having substantially the same shape It comes into contact with the powder phase. Therefore, the measurement variation of the interparticle force can be reduced. When the average circularity is smaller than 0.92, the contact surface of the particles changes every time a probe having toner particles attached thereto is made, and the variation in the force between particles becomes large. Further, the addition process of the fine particles is affected by the shape of the powder (toner base) before adding the fine particles, but the average circularity of the powder (toner base) before adding the fine particles is 0.92 or more and 0. When it is close to a sphere of .99 or less, it is possible to achieve high image quality with excellent effect of adding fine particles and excellent dot reproducibility.

(Toner particle size)
The toner of the present exemplary embodiment has a weight average particle diameter of 4 μm or more and 8 μm or less, and more preferably 5 μm or more and 7 μm or less in order to realize a high quality image. If the weight average particle size is less than 4 μm, problems such as contamination in the apparatus due to toner scattering during long-term use, image density reduction in a low-humidity environment, and poor photoconductor cleaning are likely to occur. The impact is also a concern. When the weight average particle diameter exceeds 8 μm, the resolution of minute spots of 100 μm or less is not sufficient, and the image quality tends to be inferior due to many scattering to non-image areas.

  As an apparatus for measuring the particle size distribution of toner particles by the Coulter Counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). A measuring method using this measuring apparatus will be described.

  0.1 to 5 ml of a surfactant (preferably polyoxyethylene alkyl ether: trade name drywell) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles in the toner particles are measured with a measuring apparatus using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained volume distribution and number distribution, the weight average particle diameter of the toner can be obtained.

  In the analysis regarding the particle diameter of these toners, toner particles having a particle diameter of 2.00 μm or more and less than 40.30 μm are targeted. The channel is 2.00 μm or more and less than 2.52 μm, 2.52 μm or more and less than 3.17 μm, 3.17 μm or more and less than 4.00 μm, 4.00 μm or more and less than 5.04 μm, 5.04 μm or more and less than 6.35 μm. 6.35 μm to less than 8.00 μm, 8.00 μm to less than 10.08 μm, 10.08 μm to less than 12.70 μm, 12.70 μm to less than 16.00 μm, 16.00 μm to less than 20.20 μm, 20.20 μm or more 13 channels of less than 25.40 μm, 25.40 μm or more and less than 32.00 μm, and 32.00 μm or more and less than 40.30 μm are used.

(resin)
As the toner resin of this embodiment, polystyrene resin, epoxy resin, polyester resin, polyamide resin, styrene acrylic resin, styrene methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene butadiene resin, phenol resin, polyethylene resin, silicone Resins, butyral resins, terpene resins, polyol resins, and the like can be used.

  Examples of the vinyl resin include styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, which are homopolymers of the substituted products. Styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Polymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene- Vinyl methyl ether copolymer, styrene Nyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, and styrene- Styrenic copolymers such as maleate ester copolymers, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, and polyvinyl acetate can be used.

  The polyester resin is composed of a dihydric alcohol as shown in the following group A and a dibasic acid salt as shown in the group B, and more than trivalent as shown in the group C. Alcohol or carboxylic acid may be added as a third component.

  Group A: ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4 butanediol, neopentyl glycol, 1,4 butenediol, 1,4-bis (hydroxymethyl) cyclohexane Bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylene (2,2) -2,2′-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3) -2, 2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, and polyoxypropylene (2,0) -2,2′-bis ( 4-hydroxyphenyl) propane and the like.

  Group B: maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid, linolenic acid, and These acid anhydrides or esters of lower alcohols.

  Group C: Trivalent or higher alcohols such as glycerin, trimethylolpropane, and pentaerythritol, and trivalent or higher carboxylic acids such as trimellitic acid and pyromellitic acid.

  As the polyol resin, an alkylene oxide adduct of an epoxy resin and a dihydric phenol, or a compound having one active hydrogen in the molecule that reacts with the glycidyl ether and the epoxy group, and an active hydrogen that reacts with the epoxy resin in the molecule Some of them are obtained by reacting two or more compounds.

  Further, crystalline polyester may be used as the resin of the toner of this embodiment. Preferred is an aliphatic polyester having crystallinity, having a sharp molecular weight distribution, and having the absolute amount of the low molecular weight increased as much as possible. This polyester resin undergoes a crystal transition at the glass transition point, and at the same time, its melt viscosity is drastically lowered from the solid state and exhibits a fixing function to paper. By using this crystalline polyester resin, low-temperature fixing can be achieved without excessively reducing the glass transition point and molecular weight of the resin. Therefore, there is no decrease in storage stability accompanying a decrease in glass transition point. In addition, excessive gloss and offset resistance deterioration due to low molecular weight does not occur. Therefore, the introduction of the crystalline polyester resin is very effective for improving the low-temperature fixability of the toner.

  In the toner according to the exemplary embodiment, in order to exhibit low-temperature fixability and ensure hot offset resistance, the crystalline polyester is used with respect to the total amount of the resin in the toner and the release agent described below. The content is preferably 1% by weight or more and 50% by weight or less, and the content of the release agent is preferably 2% by weight or more and 15% by weight or less. When the content of the crystalline polyester is less than 1% by weight, the low-temperature fixability is not effective, and when it exceeds 50% by weight, the hot offset property is deteriorated. When the release agent content is less than 2% by weight, there are cases where the offset resistance is not effective, and when it exceeds 20% by weight, the toner fluidity is lowered.

  Examples of the crystalline polyester resin include a polyester resin and / or a polyol resin conventionally used for color toners. Polyester resins and polyol resins are suitable because they have better low-temperature fixability and relatively better heat-resistant storage stability than styrene-acrylic resins that have been widely used. However, polyester resins and polyol resins have poor dispersibility of the release agent compared to styrene-acrylic resins. If the dispersibility is poor, the pulverization stress tends to concentrate at the interface between the resin and the wax during pulverization, so the pulverization is easy at the interface between the resin and the release agent, and the ratio of the added release agent to the surface of the pulverized toner As described above, the release agent is exposed, and the fluidity of the toner is deteriorated.

  Regarding the molecular structure of the crystalline polyester resin, from the viewpoint of the crystallinity of the polyester resin and the glass transition point, a diol compound having 2 to 6 carbon atoms, particularly 1,4-butanediol, 1,6-hexanediol, and An aliphatic polyester represented by the following general formula (1) synthesized using an alcohol component containing these derivatives, and maleic acid, fumaric acid, succinic acid, and an acid component containing these derivatives. Although it is preferable to contain, it is not limited to this.

ｍ及びｎは、繰り返し単位の数を示す。Ｒ１及びＲ２は、炭化水素基を示す。

m and n represent the number of repeating units. R1 and R2 represent a hydrocarbon group.

  In addition, from the viewpoint of the crystallinity of the polyester resin and the glass transition point, in order to synthesize a non-linear polyester, a trihydric or higher polyhydric alcohol such as glycerin is added to the alcohol component, and trimellitic anhydride is added to the acid component. The polycondensation may be performed by adding a trivalent or higher polyvalent carboxylic acid.

  The glass transition point of the crystalline polyester resin is desirably as low as possible within a range in which the heat resistant storage stability is not deteriorated, and is preferably 80 ° C. or higher and 130 ° C. or lower. When the glass transition point is 80 ° C. or lower, the heat resistant storage stability is deteriorated, and blocking tends to occur at the temperature inside the developing device. On the other hand, when the glass transition point is 130 ° C., the lower limit fixing temperature becomes high, so that the low temperature fixing property cannot be obtained.

(Measurement of glass transition point)
For the measurement of the glass transition point of the present embodiment, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used. First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, the sample was cooled to room temperature and allowed to stand for 10 minutes, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was carried out by heating at / min. The glass transition point of the crystalline polyester resin was calculated from the endothermic peak temperature at the second temperature increase using the analysis system in the TAS-100 system.

(Pigment)
As the pigment used in the present embodiment, the following pigments are used.

  Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.

  Examples of yellow pigments include cadmium yellow, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, and Tartrazine Lake. It is done.

  Examples of the orange pigment include molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK.

  Examples of red pigments include Bengala, Cadmium Red, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, and Brilliant Carmine 3B. .

  Examples of purple pigments include fast violet B and methyl violet lake.

  Examples of blue pigments include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, fast sky blue, and indanthrene blue BC.

  Examples of the green pigment include chrome green, chromium oxide, pigment green B, and malachite green lake.

  These pigments can be used alone or in combination of two or more.

  Particularly in color toners, uniform pigment dispersion is essential. For this reason, a method is used in which a master batch in which a pigment is once dispersed at a high concentration is prepared and then diluted in a diluted manner, instead of directly charging the pigment into a large amount of resin. In this case, a solvent is generally used to assist dispersibility, but the waste liquid is dispersed using water in the present embodiment in consideration of the environmental problem recently discussed.

(Charge control agent)
In the toner of this embodiment, a charge control agent is blended (internally added) inside the toner particles. Further, it may be used by mixing (external addition) with toner particles. The charge control agent makes it possible to control the optimum charge amount according to the development system. In particular, in this embodiment, the balance between the particle size distribution and the charge amount can be further stabilized.

  As the charge control agent for controlling the toner to be positively charged, nigrosine, a quaternary ammonium salt, a triphenylmethane dye, an imidazole metal complex and salts can be used alone or in combination of two or more.

  As the charge control agent for controlling the toner to be negatively charged, salicylic acid metal complexes and salts, organic boron salts, calixarene compounds, and the like are used.

(Release agent)
A release agent can be internally added to the toner in the present embodiment to prevent offset at the time of fixing.

  As release agents, natural waxes such as candelilla wax, carnauba wax and rice wax, montan wax and derivatives thereof, paraffin wax and derivatives thereof, polyolefin wax and derivatives thereof, and sazol There are waxes, low molecular weight polyethylene, low molecular weight polypropylene, and alkyl phosphates.

  The melting point of these release agents is preferably 65 ° C. or higher and 90 ° C. or lower. When the melting point is lower than 65 ° C., blocking during storage of the toner is likely to occur, and when the melting point is higher than 90 ° C., offset is likely to occur in a region where the fixing roller temperature is low. .

  A dispersant may be added for the purpose of improving the dispersibility of a release agent or the like.

  As the dispersant, styrene acrylic resin, polyethylene resin, polystyrene resin, epoxy resin, polyester resin, polyamide resin, styrene methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene butadiene resin, phenol resin, butyral resin, terpene resin, And a polyol resin, etc., and a mixture of two or more of each resin may be used.

  The addition amount of the dispersant is suitably 10 parts by mass or less with respect to 100 parts by mass of the resin. Even if the amount is more than 10 parts by mass, the acidic effect of the release agent is not observed, and conversely, the fixing property and the image reproducibility are deteriorated.

(Toner production method)
Examples of methods for producing the toner of the present embodiment include so-called pulverization methods and polymerization methods (methods using suspension polymerization, emulsion polymerization dispersion polymerization, emulsion aggregation, and emulsion association). It is not limited to.

  As an example of the pulverization method, first, the above-described resin, a pigment or dye as a colorant, a charge control agent, a release agent, an additive, and the like are sufficiently mixed by, for example, a mixer such as a Henschel mixer. After mixing, the components are thoroughly kneaded using a thermal kneader such as a batch-type two roll, Banbury mixer, continuous twin-screw extruder, and continuous single-screw kneader. Do. The toner kneaded product after cutting is coarsely pulverized using a hammer mill or the like, and further finely pulverized by a fine pulverizer and a mechanical pulverizer using a jet stream, and a classifier using a swirling air stream and the Coanda effect are used. Classification to a predetermined particle size by a classifier. Thereafter, fine particles made of at least silicon nitride having an average particle diameter of 10 nm or more and 100 nm or less are produced by the laser ablation treatment in the Ar gas atmosphere described above. Then, the fine particles are directly attached to the particle surface of the toner composed of at least a resin and a pigment. After this surface treatment, in order to evaluate whether or not a predetermined interparticle force is obtained, one toner particle is attached to the periphery of the tip of the probe of the above-mentioned AFM apparatus, and the compressed toner particle powder phase is It is manufactured and evaluated by the method of this embodiment described above.

  As a result of the evaluation, when the numerical value is within the predetermined setting range described above, the sample is passed to the wind sieving step, passed through a sieve of 250 mesh or more to remove coarse particles and agglomerated particles, and then the sample is sent to the filling step. The toner of this embodiment is obtained.

  The characteristics of the present evaluation method using the AFM method are as follows, and the sample can be used as it is, and the measurement can be performed with high accuracy without individual differences. Moreover, the measurement in a manufacturing line is also possible, and it can install between each process in a manufacturing process, and can perform quality evaluation in the middle of a process.

  FIG. 4 is a configuration diagram of the toner evaluation apparatus of the present embodiment.

  Referring to FIG. 4, the toner evaluation apparatus roughly includes a toner extraction means 51, an extraction valve 52, a container 53, and an AFM apparatus 54.

  For example, after passing through the mixing step, the toner extracting means 51 is provided in the middle of the path (arrow B in FIG. 4) for conveying the powder toner sample to the next step. By opening and closing the extraction valve 52 at a certain timing, a certain amount of toner sample is conveyed to the measuring unit. The tip of the measurement part is a container made of SUS or the like, and can be directly measured by this evaluation method. Alternatively, as shown in FIG. 4, the container 53 containing the extracted toner can be taken to an AFM apparatus 54 in another nearby location and measured by this evaluation method.

  As a result of the evaluation by the AFM apparatus, when the numerical value is out of the predetermined setting range, the sample is not transported to the path for transporting to the next process (arrow C in FIG. 4), but is transported to the toner reprocessing process. Turn to the route (arrow X in FIG. 4). These mechanisms can be applied to the inspection after the pulverization / classification process, which is the process before the surface treatment process, the inspection after the air sieving process after the surface treatment process, the inspection before filling, and the like.

  A method other than the pulverization method can be considered as a method for producing the toner of the present embodiment. As an example of the polymerization method, a monomer composition in which a colorant, a charge control agent, and the like are added to a monomer is suspended in an aqueous medium. Toner particles are obtained by turbidity and polymerization. The granulation method is not particularly limited.

  For example, the toner according to the exemplary embodiment includes an oil dispersion in which at least a polyester-based prepolymer containing an isocyanate group is dissolved in an organic solvent, a pigment-based colorant is dispersed, and a release agent is dissolved or dispersed. A urea-modified polyester having a urea group which is dispersed in an aqueous medium in the presence of inorganic fine particles and / or fine polymer particles, and in which the prepolymer is reacted with a polyamine and / or a monoamine having an active hydrogen-containing group. It is obtained by forming a resin and removing the liquid medium contained in the dispersion containing the urea-modified polyester resin.

  In the urea-modified polyester resin, the glass transition point is 40 ° C. or more and 65 ° C. or less, preferably 45 ° C. or more and 60 ° C. or less. The number average molecular weight (Mn) is 2500 or more and 50,000 or less, preferably 2500 or more and 30,000 or less. The weight average molecular weight (Mw) is 10,000 to 500,000, preferably 30,000 to 100,000.

  This toner contains, as a binder resin, a urea-modified polyester resin having a urea bond that has been polymerized by the reaction of the prepolymer and the amine. The colorant is highly dispersed in the binder resin.

  The obtained toner powder after drying is air-classified, and fine particles made of at least silicon nitride having an average particle size of 10 nm to 100 nm are prepared by laser ablation in an Ar gas atmosphere. It adheres to the particle surface of the toner consisting of at least resin and pigment.

  After this surface treatment step, evaluation is performed using the interparticle force of the toner particles in order to evaluate whether or not a predetermined particle structure is obtained.

  As a result of the evaluation, when the numerical value is within a predetermined setting range, it is turned to the wind sieving step, passed through a sieve of 250 mesh or more, and after removing coarse particles and agglomerated particles, the sample is turned to the filling step, The toner of this embodiment is obtained.

  In addition, this evaluation using the AFM method is the same as the toner manufactured by the pulverization method, after the granulation inspection, the inspection after the air classification, the inspection after the surface treatment process, and after the wind sieving process after the surface treatment process. It can be applied to inspections before and after filling.

(Single component developer)
The toner of this embodiment is used as a one-component developer used in a contact or non-contact development method. Various known development methods are used as the contact or non-contact development method. For example, a contact development method using an aluminum sleeve, a contact development method using a conductive rubber belt, and a non-contact development method using a development sleeve in which a conductive resin layer containing carbon black or the like is formed on the surface of an aluminum base tube. is there.

  Further, since the toner of the present embodiment has excellent fluidity when developing using an AC bias voltage component during development, the toner vibrates faithfully in accordance with an electric field and can faithfully develop fine latent images. Development with good dot reproducibility is possible. A method of developing using an AC bias voltage component during development will be described below.

  FIG. 5 is a diagram for explaining a developing system using a one-component developer in the present embodiment.

  Referring to FIG. 5, the toner supplied from the toner supply hopper 71 is supplied to the entire surface of the supply roller 73 through the diffusion blade 72. The supply roller 73 is in contact with the developing roller 74, and the toner on the supply roller 73 is supplied to the developing roller 74. Since the developing roller 74 rotates in the direction of the arrow E in the figure, the region on the developing roller 74 to which the toner is supplied comes into contact with the doctor roller 75. The doctor roller 75 is a roller blade that shapes the toner supplied onto the developing roller 74 so as to form a uniform layer. The toner layer that has become uniform on the developing roller 74 then comes into contact with the photoreceptor 76 rotating in the direction of arrow F, and toner develops the electronic latent image on the photoreceptor 76.

  The toner of this embodiment can be used in a developing system having the doctor roller 75 shown in FIG.

  Further, the toner of the present embodiment may be employed in a developing method using a supply roller 73 in addition to the doctor roller 75 shown in FIG. However, in general, in such a system, not only filming on the photosensitive member 76 but also filming on the doctor roller 75 and the supply roller 73 occurs. For this reason, not only the toner layer cannot be formed uniformly, but also the toner charge becomes non-uniform and the toner charge amount becomes small, resulting in poor development. When the toner of this embodiment is used, filming to the doctor roller 75 and the supply roller 73 does not occur, a stable development is performed, and a development system with excellent durability characteristics can be obtained.

  Further, when the magnetic toner is used, magnetic particles may be internally added to the toner particles. Examples of the magnetic material include ferromagnetic materials such as ferrite, magnetite, iron, nickel, cobalt, and alloys thereof. The average particle size of the magnetic material is preferably 0.1 μm or more and 1 μm or less. The content of the magnetic material is preferably 10 to 70 parts by weight with respect to 100 parts by weight of the toner.

(Two-component developer)
Further, when used as a two-component developer, toner particles and a magnetic carrier described below are mixed at a predetermined mixing ratio to obtain a two-component developer.

  As the carrier used for the two-component developer, known ones can be used. For example, magnetic particles such as iron powder, ferrite powder, nickel powder, and magnetite powder, and the surface of these magnetic particles are fluorine-based. Examples thereof include those treated with resin, vinyl resin, silicone resin, and the like, and magnetic particle-dispersed resin particles in which magnetic particles are dispersed in the resin. The average particle size of these magnetic carriers is preferably 20 μm or more and 70 μm or less. More preferably, they are 25 micrometers or more and 65 micrometers or less. When the average particle diameter of the carrier is in the range of 20 μm or more and 70 μm or less, the charge amount of the toner can be made more uniform when the toner concentration in the developing machine is in the range of 2 wt% or more and 10 wt% or less. When the average particle diameter of the carrier is smaller than 20 μm, the carrier particles are likely to adhere to the photoreceptor, and the stirring efficiency with the toner is deteriorated, so that it is difficult to obtain a uniform charge amount of the toner. On the other hand, when the average particle diameter of the carrier exceeds 70 μm, fine image reproducibility deteriorates and a high-quality image cannot be obtained.

  Examples of the coating material on the carrier surface include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polystyrenes such as polyvinyl resins and polyvinylidene resins (for example, acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, and polystyrene resins), styrene acrylic copolymer resins, etc. Resin, halogenated olefin resin such as polyvinyl chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, Polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene Fluoro terpolymers such as terpolymer of Ren and the vinylidene fluoride and non-fluorinated monomer, and silicone resin or the like can be used.

  Moreover, you may contain conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide and the like can be used. These conductive fine particles preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, there arises a problem that it becomes difficult to control electric resistance.

  Further, the developer of the present embodiment includes other additives, lubricant powders such as Teflon (registered trademark) powder, zinc stearate powder, and polyvinylidene fluoride powder within a range that does not adversely affect the output image, and A small amount of a polishing agent such as cerium oxide powder, silicon carbide powder, and strontium titanate powder, and a conductivity imparting agent such as carbon black powder, zinc oxide powder, and tin oxide powder may be used as a developability improver. .

(Process cartridge)
The process cartridge of the present embodiment develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer containing toner. And at least developing means for forming a visible image, and further, other means appropriately selected as necessary.

  FIG. 6 is a configuration diagram of the process cartridge in the present embodiment.

  Referring to FIG. 6, the process cartridge 99 is roughly divided into a photosensitive member 110 which is an electrostatic latent image carrier, a charger 121 which is an electrostatic latent image forming unit, and an exposure apparatus which is also an electrostatic latent image forming unit. 130, a developing device 140 as a developing means, a cleaning device 160 as a cleaning means, a static elimination lamp 170 as a static elimination means, and a transfer roller 180 as a transfer means.

  Each component of the process cartridge 99 described above will be described in detail in the section of the image forming apparatus described below.

  The process cartridge according to this embodiment can be freely provided in various electrophotographic apparatuses and the like, and is preferably provided detachably in the image forming apparatus according to this embodiment described below. Further, being detachable enables maintenance of the image forming apparatus described below.

(Image forming device)
The image forming apparatus according to the present embodiment includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and other units appropriately selected as necessary. For example, it comprises a static elimination means, a cleaning means, a recycling means, and a control means.

  The material, shape, structure, size, etc. of the electrostatic latent image carrier, also referred to as a photoreceptor, are not particularly limited, and can be appropriately selected from known ones. A preferable example of the shape of the electrostatic latent image carrier is a drum shape. Examples of the material of the electrostatic latent image bearing member include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable because of its long life. The photoconductor made of amorphous silicon will be described in detail below.

  The formation of the electrostatic latent image can be performed by uniformly charging the surface of the above-described electrostatic latent image carrier and then performing imagewise exposure by the above-described electrostatic latent image forming unit.

  The electrostatic latent image forming means includes, for example, at least charging means for uniformly charging the surface of the above-described electrostatic latent image carrier and exposure means for exposing the surface of the electrostatic latent image carrier imagewise. .

  Charging can be performed by applying a voltage to the surface of the electrostatic latent image carrier using a charger.

  The charging means is not particularly limited and may be appropriately selected according to the purpose. For example, a known contact charging provided with a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotron and scorotron.

  In the present embodiment, it is preferable to use a charging unit that directly contacts the surface of the electrostatic latent image carrier and applies a voltage to uniformly charge the surface of the electrostatic latent image carrier. Use of such a charging means is preferable in that generation of ozone in the apparatus can be suppressed.

  The exposure can be performed by exposing the surface of the electrostatic latent image carrier imagewise using the above-described exposure device.

  The exposure device means is not particularly limited as long as the surface of the electrostatic latent image carrier charged by the above-described charger can be exposed like an image to be formed, and is appropriately selected according to the purpose. Examples thereof include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.

  In the present embodiment, an optical backside system that performs imagewise exposure from the backside of the electrostatic latent image carrier may be employed.

  Next, the developing unit will be described.

  The developing means develops the above-described electrostatic latent image using the developer containing the toner of the present embodiment to form a visible image.

  The visible image can be formed by developing the electrostatic latent image using a developer containing the toner of the present embodiment by a developing unit.

  The developing means is not particularly limited as long as it can be developed using the developer containing the toner of the present embodiment, and can be appropriately selected from known ones. For example, a developer that contains at least a developer that contains the toner of the present embodiment and that can apply the developer to the electrostatic latent image in a contact or non-contact manner is preferably used. A developing device provided with the toner container of the present embodiment is more preferable.

  The developing means may be a single color developer or a multicolor developer. For example, it is preferable to use a stirrer for charging a developer containing toner by frictional stirring and a rotatable magnet roller.

  In the developing means, the toner and the carrier are mixed and agitated, and the toner is charged by the friction at that time, and is held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. Since the magnet roller is disposed in the vicinity of the above-described electrostatic latent image carrier (photosensitive member), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is statically absorbed by an electric attractive force. It moves to the surface of the electrostatic latent image carrier (photoconductor). As a result, the electrostatic latent image is developed with toner, and a visible image is formed with toner on the surface of the electrostatic latent image carrier (photoconductor).

  In the present embodiment, it is particularly preferable to perform the developing process using a developing method that applies an alternating electric field. The developing method for applying the alternating electric field will be described in detail below.

  The developer accommodated in the developing device is a developer containing the toner of the present embodiment, but the developer may be a one-component developer or a two-component developer. The toner contained in these developers is the toner of the present embodiment.

  Next, the transfer unit will be described.

  The transfer unit is a unit that transfers a visible image to a recording medium. The transfer unit preferably uses an intermediate transfer member, and after the primary transfer of the visible image onto the intermediate transfer member, the visible image is secondarily transferred onto the recording medium. Further, the transfer means uses a primary transfer means for forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as toner, and the composite transfer image as a recording medium. More preferable is a mode including a secondary transfer means for transferring the image on the top.

  The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt is preferably used.

  The primary transfer unit and the secondary transfer unit preferably include at least a transfer unit that peels and charges the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. There may be one transfer means, or two or more transfer means.

  Examples of the transfer means include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

  In addition, there is no restriction | limiting in particular as a recording medium, It can select suitably from well-known recording media (recording paper).

  The fixing means is means for fixing the visible image transferred to the recording medium by the fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or the toners of each color are laminated. May be performed simultaneously at the same time.

  The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. However, a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller, and an endless belt.

  The heating in the heating and pressing means is usually preferably 80 ° C. or higher and 200 ° C. or lower.

  In this embodiment, for example, a known optical fixing device may be used together with or instead of the fixing step and the fixing unit depending on the purpose.

  In this embodiment, it is particularly preferable to use a surf fixing device as the fixing device. The surf fixing device will be described in detail below.

  The neutralizing unit is a unit that performs neutralization by applying a neutralizing bias to the electrostatic latent image carrier (photoconductor). The neutralizing means is not particularly limited as long as it can apply a neutralizing bias to the electrostatic latent image carrier, and can be appropriately selected from known neutralizers. For example, a static elimination lamp etc. are mentioned suitably.

  The cleaning means is means for removing the electrophotographic toner remaining on the electrostatic latent image carrier.

  The cleaning means is not particularly limited as long as it can remove the toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. For example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, a web cleaner, and the like are preferable.

  The recycling means is means for recycling the color toner for electrophotography removed by the above-described cleaning means to the developing means.

  There is no restriction | limiting in particular as a recycle means, A well-known conveyance means etc. are mentioned.

  The control means is a process for controlling the above-described steps, and can be suitably performed by the control means.

  The control means is not particularly limited as long as it can control the movement of each means described above, and can be appropriately selected according to the purpose. For example, devices such as a sequencer and a computer can be mentioned.

  One aspect of the image forming apparatus of this embodiment will be described.

  FIG. 7 is a configuration diagram of the image forming apparatus in the present embodiment.

  Referring to FIG. 7, an image forming apparatus 100 includes a photosensitive member 110 as an electrostatic latent image carrier, a charging roller 120 as a charging unit, an exposure unit 130 as an exposure unit, a developing unit 140 as a developing unit, an intermediate unit. The image forming apparatus includes a transfer member 150, a cleaning device 160 as a cleaning unit having a cleaning blade, and a static elimination lamp 170 as a static elimination unit.

  The intermediate transfer member 150 is an endless belt, and is designed to be movable in the direction of the arrow by three rollers 151 that are arranged inside and stretched. Some of the three rollers 151 also function as transfer bias rollers that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 150. The intermediate transfer body 150 is provided with a cleaning device 190 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 195 as a final transfer material. A transfer roller 180 as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 180. Around the intermediate transfer member 150, a corona charger 158 for applying a charge to the toner image on the intermediate transfer member 150 is in contact with the photosensitive member 110 and the intermediate transfer member 150 in the rotation direction of the intermediate transfer member 50. And the contact portion between the intermediate transfer member 150 and the transfer paper 195.

  The developing device 140 includes a developing belt 141 as a developer carrier, and a black developing unit 145K, a yellow developing unit 145Y, a magenta developing unit 145M, and a cyan developing unit 145C provided around the developing belt 141. The black developing unit 145K includes a developer accommodating portion 142K, a developer supplying roller 143K, and a developing roller 144K. The yellow developing unit 145Y includes a developer accommodating portion 142Y, a developer supplying roller 143Y, and a developing roller 144Y. The magenta developing unit 145M includes a developer accommodating portion 142M, a developer supplying roller 143M, and a developing roller 144M. The cyan developing unit 145C includes a developer accommodating portion 142C and a developer supplying roller 143C. And a developing roller 144C. The developing belt 141 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoreceptor 110.

  The surface layer material and the surface layer of the developing belt 141 prevent contamination of the photosensitive member by an elastic material, reduce surface friction resistance to the transfer belt surface, reduce toner adhesion, and provide cleaning and secondary transfer properties. What is needed is to be enhanced. For example, one type or two or more types such as polyurethane, polyester, and epoxy resin are used. In addition, a material that reduces surface energy and increases lubricity, for example, one or more powders or particles of fluororesin, fluorine compound, fluorocarbon, titanium dioxide, and silicon carbide, or a particle size Different types can be dispersed and used. In addition, a material that has a surface-energy reduced by forming a fluorine-rich layer on the surface by heat treatment, such as a fluorine-based rubber material, can be used.

  In the image forming apparatus 100, for example, the charging roller 120 charges the photoreceptor 110 uniformly. The exposure device 130 performs imagewise exposure on the photoconductor 110 to form an electrostatic latent image. The electrostatic latent image formed on the photoreceptor 110 is developed by supplying toner from the developing device 140 to form a visible image (toner image). This visible image (toner image) is transferred (primary transfer) onto the intermediate transfer body 150 by the voltage applied from the roller 151, and further transferred (secondary transfer) onto the transfer paper 195 by the transfer roller 180. As a result, a transfer image is formed on the transfer paper 195. The residual toner on the photoconductor 110 is removed by the cleaning device 160, and the charge on the photoconductor 110 is removed by the static elimination lamp 170. Similarly, the residual toner on the intermediate transfer member 150 is removed by the cleaning device 190.

(Development method applying an alternating electric field)
FIG. 8 is a schematic diagram illustrating a developing method for applying an alternating electric field according to the present embodiment.

  Referring to FIG. 8, in the developing device 702 for the photosensitive member 701 of the present embodiment, during development, an AC voltage is superimposed on a DC voltage as a developing bias by a power source 704 including an AC power source and a DC power source. The applied vibration bias voltage is applied. The background portion potential and the image portion potential are located between the maximum value and the minimum value of the vibration bias potential. As a result, an alternating electric field whose direction changes alternately is formed in the developing unit 705. In this alternating electric field, the developer toner and the carrier vibrate vigorously, and the toner flies off the electrostatic roller 703 and the carrier in the developer to fly to the photoconductor 701, and the latent image on the photoconductor 701. It adheres corresponding to.

  The difference (peak-to-peak voltage) between the maximum value and the minimum value of the vibration bias voltage is preferably 0.5 KV to 5 KV, and the frequency is preferably 1 KHz to 10 KHz. As the waveform of the vibration bias voltage, a rectangular wave, a sine wave, a triangular wave, or the like can be used. As described above, the DC voltage component of the vibration bias is a value between the background part potential and the image part potential, but the value closer to the background part potential than the image part potential is more likely to cover the background part potential region. This is preferable for preventing toner adhesion.

  When the vibration bias voltage waveform is a rectangular wave, the duty ratio is preferably 50% or less. Here, the duty ratio is a ratio of time during which the toner is directed to the photosensitive member during one period of the vibration bias. By doing so, the difference between the peak value at which the toner is directed to the photoreceptor and the time average value of the bias can be increased, so that the movement of the toner is further activated and the potential of the latent image surface is increased. It can adhere to the distribution and improve the roughness and resolution. In addition, since the difference between the peak value of the carrier having a charge opposite to that of the toner and the time average value of the bias toward the photosensitive member can be reduced, the movement of the carrier is reduced, and the background portion of the latent image is reduced. The probability of carriers adhering to the substrate can be greatly reduced.

(Surf fixing device)
FIG. 9 is a configuration diagram of the surf fixing device of the present embodiment.

  Referring to FIG. 9, a fixing device 800 is a so-called surf fixing device that fixes a fixing film 801 by rotating it in the direction of the arrow in the drawing. More specifically, the fixing film 801 is an endless belt-like heat-resistant film. A driving roller 802 which is a support rotating body of the film, a driven roller 803, and a heating body 804 provided below the two rollers in the figure. Suspended.

  The driven roller 802 also serves as a tension roller for the fixing film 801. The fixing film 801 is rotationally driven in the direction of the arrow in the drawing by the rotational driving of the driving roller 802 in the direction of the arrow in the drawing. The rotational driving speed is adjusted to a speed at which the speeds of the transfer material 806 and the fixing film 801 are equal in the fixing nip region L where the pressure roller 805 and the fixing film 801 are in contact with each other.

  Here, the pressure roller 805 is a roller having a rubber elastic layer having good releasability such as silicon rubber, and the total pressure is 4 kg or more and 10 kg or less with respect to the fixing nip region L while rotating in the arrow direction in the figure. The contact is made with contact pressure.

  The fixing film 801 is preferably a film having excellent heat resistance, releasability, and durability, and a thin film having a total thickness of 100 μm or less, preferably 40 μm or less. For example, a single layer film of heat-resistant resin such as polyimide, polyetherimide, PES (polyether sulfide), and PFA (tetrafluoroethylene bar fluoroalkyl vinyl ether copolymer resin), and a composite layer film, for example, 20 μm thick At least the image contact surface side of the film is provided with a 10 μm thick release coat layer in which a conductive material is added to a fluororesin such as PTFE (tetrafluoroethylene resin) and PFA, An elastic layer is applied.

  The heating body 804 is composed of a flat substrate 807 and a fixing heater 808. The flat substrate 807 is made of a material having high thermal conductivity and high electrical resistivity such as alumina and has a surface in contact with the fixing film 801. Is provided with a fixing heater 808 made of a resistance heating element in the longitudinal direction. The fixing heater 808 is formed by applying an electric resistance material such as Ag / Pd or Ta2N in a linear or belt shape by screen printing or the like. In addition, electrodes (not shown) are formed at both ends of the fixing heater 808, and the resistance heating element generates heat when energized between the electrodes. Further, a fixing temperature sensor 809 constituted by a thermistor is provided on the surface opposite to the surface provided with the fixing heater 808 of the substrate.

  The substrate temperature information detected by the fixing temperature sensor 809 is sent to a control unit (not shown), and the amount of electric power supplied to the fixing heater is controlled by the control unit, so that the heating body 804 is controlled to a predetermined temperature.

  Hereinafter, embodiments will be described in more detail with reference to examples. In addition, all the parts shown in the following Examples and Comparative Examples show parts by weight.

In this example, a toner was produced in which the toner composition and the surface treatment conditions on the toner particle surface were changed. The interparticle force of the toner particles is a toner powder in which one toner particle is attached to the tip or the periphery of the probe to produce a compressed toner particle powder phase and the toner particles attached to the probe are consolidated. After pressing once on one particle on the surface of the body phase and then scanning to separate, evaluation was performed by the AEM method described above, which was measured from the force change at that time. The toner particle powder phase was prepared at a compression pressure of 320 kg / cm ² .

[Example 1]
(Production of toner)
100 parts of a polyester resin (polyester synthesized from a bisphenol A propylene oxide adduct terephthalic acid and a succinic acid derivative) as a resin, and a copper phthalocyanine blue pigment (CI Pigment Blue 15: 3, Lionol Blue FG-) as a colorant 7351 (manufactured by Toyo Ink Co., Ltd.) 3.5 parts, 5 parts of salicylic acid zinc salt (Bontron E84, Orient Chemical) as a charge control agent, and 5 parts of low molecular weight polyethylene as a release agent were mixed thoroughly with a mixer. . This mixture was melt-kneaded with a twin-screw extruder at a barrel temperature of 110 ° C. and a kneader rotation speed of 120 revolutions / minute. The kneaded product is cooled and rolled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then classified into a particle size distribution having an average particle size of 6.0 μm using a swirling air classifier. Colored particles were obtained. Further, a fine particle made of at least silicon nitride was prepared on 100 parts of the base coloring particles under the following surface treatment conditions, and was adhered to the surface of the toner particle to prepare a toner. The toner produced in Example 1 is referred to as Toner 1.

(Surface treatment conditions)
A laser ablation method was used as the surface treatment method. The target was Si ₃ N ₄ . As the laser, an Nd: YAG laser having a wavelength of 266 nm was used. The laser output was 100 mJ / pulse. The atmosphere gas was Ar. The gas pressure was 5 × 10 ⁻² Pa. The target-sample distance was 50 mm. The powder vibration condition was a frequency of 30 Hz.

[Example 2]
(Production of toner)
Kneading and pulverization were carried out using the same raw materials and production method as in Example 1, and classified into a particle size distribution having an average particle size of 6.0 μm to obtain base colored particles. With respect to 100 parts of the base colored particles, fine particles made of at least silicon nitride were prepared under the following surface treatment conditions, and fixed on the surface of the toner particles to prepare a toner. The toner prepared in Example 2 is referred to as Toner 2.

(Surface treatment conditions)
A laser ablation method was used as the surface treatment method. The target was Si ₃ N ₄ . As the laser, an Nd: YAG laser having a wavelength of 266 nm was used. The laser output was 200 mJ / pulse. The atmosphere gas was Ar. The gas pressure was 5 × 10 ⁻² Pa. The target-sample distance was 50 mm. The powder vibration condition was a frequency of 30 Hz.

[Example 3]
(Production of toner)
Kneading and pulverization were carried out by the same raw materials and production method as in Example 1, and classified into a particle size distribution having an average particle size of 6.1 μm to obtain base colored particles. With respect to 100 parts of the base colored particles, fine particles made of at least silicon nitride were prepared under the following surface treatment conditions, and fixed on the surface of the toner particles to prepare a toner. The toner produced in Example 3 is referred to as Toner 3.

(Surface treatment conditions)
A laser ablation method was used as the surface treatment method. The target was Si ₃ N ₄ . As the laser, an Nd: YAG laser having a wavelength of 266 nm was used. The laser output was 300 mJ / pulse. The atmosphere gas was Ar. The gas pressure was 5 × 10 ⁻² Pa. The target-sample distance was 50 mm. The powder vibration condition was a frequency of 30 Hz.

[Example 4]
(Production of toner)
Kneading and pulverization were carried out using the same raw materials and production method as in Example 1, and classified into a particle size distribution having an average particle size of 6.0 μm to obtain base colored particles. With respect to 100 parts of the base colored particles, fine particles made of at least silicon nitride were prepared under the following surface treatment conditions, and fixed on the surface of the toner particles to prepare a toner. The toner produced in Example 4 is referred to as Toner 4.

(Surface treatment conditions)
A laser ablation method was used as the surface treatment method. The target was Si ₃ N ₄ . As the laser, an Nd: YAG laser having a wavelength of 266 nm was used. The laser output was 100 mJ / pulse. The atmosphere gas was Ar. The gas pressure was 0.1 Pa. The target-sample distance was 50 mm. The powder vibration condition was a frequency of 30 Hz.

[Example 5]
(Production of toner)
Kneading and pulverization were carried out using the same raw materials and production method as in Example 1, and classified into a particle size distribution having an average particle size of 6.0 μm to obtain base colored particles. With respect to 100 parts of the base colored particles, fine particles made of at least silicon nitride were prepared under the following surface treatment conditions, and fixed on the surface of the toner particles to prepare a toner. The toner prepared in Example 5 is referred to as Toner 5.

(Surface treatment conditions)
A laser ablation method was used as the surface treatment method. The target was Si ₃ N ₄ . As the laser, an Nd: YAG laser having a wavelength of 266 nm was used. The laser output was 100 mJ / pulse. The atmosphere gas was Ar. The gas pressure was 1 × 10 ⁻² Pa. The target-sample distance was 50 mm. The powder vibration condition was a frequency of 30 Hz.

[Example 6]
(Synthesis of binder resin)
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid, and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. These were reacted at normal pressure at 230 ° C. for 8 hours, further reacted at a reduced pressure of 1.3 × 10 ^{3 to} 2.0 × 10 ³ Pa for 5 hours, cooled to 160 ° C., and 32 parts thereof. Phthalic anhydride was added and reacted for 2 hours. Next, the mixture was further cooled to 80 ° C., and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate-containing prepolymer I.

  Prepolymer I 267 parts and isophoronediamine 14 parts were reacted at 50 ° C. for 2 hours to obtain urea-modified polyester I having a weight average molecular weight of 64,000.

In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 724 parts of bisphenol A ethylene oxide 2-mol adduct and 276 parts of terephthalic acid were subjected to polycondensation at 230 ° C. for 8 hours under normal pressure, and then 1.3 × 10 ³ to 2.0 × ¹⁰ 3 Pa vacuum 5 hours to at the, to obtain a polyester a unmodified peak molecular weight of 5,000. 200 parts of urea-modified polyester I and 800 parts of unmodified polyester A were dissolved and mixed in 2000 parts of an ethyl acetate / MEK (1/1) mixed solvent to obtain an ethyl acetate / MEK solution of toner binder I. The ethyl acetate / MEK solution of toner binder I was dried under reduced pressure to isolate toner binder I. The glass transition point of the toner binder I was 62 ° C. The glass transition point was measured by the method described above.

(Production of toner)
240 parts of an ethyl acetate / MEK solution of toner binder I, 20 parts of pentaerythritol tetrabehenate (melt viscosity 25 cps), and copper phthalocyanine blue pigment (CI Pigment Blue 15: 3, Lionol Blue FG-7351, Toyo Ink Co., Ltd.) 4 parts as a raw material was stirred in a TK homomixer at 12,000 rpm in a beaker at 60 ° C., and uniformly dissolved and dispersed to prepare a toner material solution.

  Separately from the toner material solution, 706 parts of ion-exchanged water, 294 parts of 10% hydroxyapatite suspension (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.2 part of sodium dodecylbenzenesulfonate were used as raw materials. The toner material solution described above was added and stirred for 10 minutes at 60 ° C. while stirring at 12,000 rpm with a TK homomixer. The mixture is then transferred to a stirring bar and a flask equipped with a thermometer, heated to 30 ° C., the solvent is removed under reduced pressure, filtered, washed, and dried, and then air classified to remove toner particles. Obtained. The volume average particle diameter was 6.3 μm. The volume average particle size was measured by the method described above. Further, a toner was prepared by preparing fine particles composed of at least silicon nitride under the following surface treatment conditions with respect to 100 parts of the base coloring particles and fixing them to the surface of the toner particles. The toner produced in Example 6 is referred to as Toner 6.

(Surface treatment conditions)
A laser ablation method was used as the surface treatment method. The target was Si ₃ N ₄ . As the laser, an Nd: YAG laser having a wavelength of 266 nm was used. The laser output was 100 mJ / pulse. The atmosphere gas was Ar. The gas pressure was 5 × 10 ⁻² Pa. The target-sample distance was 50 mm. The powder vibration condition was a frequency of 30 Hz.

[Example 7]
(Production of toner)
Powders were produced and classified using the same raw materials and production method as in Example 6, and classified into a particle size distribution with an average particle size of 6.3 μm to obtain matrix colored particles. With respect to 100 parts of the base colored particles, fine particles made of at least silicon nitride were prepared under the following surface treatment conditions, and fixed on the surface of the toner particles to prepare a toner. The toner produced in Example 7 is referred to as Toner 7.

(Surface treatment conditions)
A laser ablation method was used as the surface treatment method. The target was Si ₃ N ₄ . As the laser, an Nd: YAG laser having a wavelength of 266 nm was used. The laser output was 200 mJ / pulse. The atmosphere gas was Ar. The gas pressure was 5 × 10 ⁻² Pa. The target-sample distance was 50 mm. The powder vibration condition was a frequency of 30 Hz.

[Example 8]
(Production of toner)
Powders were produced and classified using the same raw materials and production method as in Example 6, and classified into a particle size distribution with an average particle size of 6.3 μm to obtain matrix colored particles. With respect to 100 parts of the base colored particles, fine particles made of at least silicon nitride were prepared under the following surface treatment conditions, and fixed on the surface of the toner particles to prepare a toner. The toner produced in Example 8 is referred to as Toner 8.

(Surface treatment conditions)
A laser ablation method was used as the surface treatment method. The target was Si ₃ N ₄ . As the laser, an Nd: YAG laser having a wavelength of 266 nm was used. The laser output was 300 mJ / pulse. The atmosphere gas was Ar. The gas pressure was 5 × 10 ⁻² Pa. The target-sample distance was 50 mm. The powder vibration condition was a frequency of 30 Hz.

[Example 9]
(Production of toner)
100 parts of a polyester resin (polyester synthesized from a propylene oxide adduct of bisphenol A and a succinic acid derivative) as a resin, and a magenta pigment (CI Pigment Blue 122, HostaperPink E; manufactured by Clariant) as a colorant 3 .5 parts and 5 parts of salicylic acid zinc salt (Bontron E84, Orient Chemical) as a charge control agent were mixed thoroughly with a mixer. This mixture was melt-kneaded with a twin-screw extruder at a barrel temperature of 100 ° C. and a kneader rotation speed of 110 revolutions / minute. This kneaded product is cooled and rolled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then classified into a particle size distribution having an average particle size of 6.7 μm using a swirling air classifier. Colored particles were obtained. Further, a fine particle made of at least silicon nitride was prepared on 100 parts of the base coloring particles under the following surface treatment conditions, and was adhered to the surface of the toner particle to prepare a toner. The toner produced in Example 9 is referred to as Toner 9.

(Surface treatment conditions)
A laser ablation method was used as the surface treatment method. The target was Si ₃ N ₄ . As the laser, an Nd: YAG laser having a wavelength of 266 nm was used. The laser output was 100 mJ / pulse. The atmosphere gas was Ar. The gas pressure was 5 × 10 ⁻² Pa. The target-sample distance was 50 mm. The powder vibration condition was a frequency of 30 Hz.

[Example 10]
(Production of toner)
Powders were produced and classified by the same raw materials and production method as in Example 9, and classified into a particle size distribution having an average particle diameter of 6.7 μm, to obtain base colored particles. With respect to 100 parts of the base colored particles, fine particles made of at least silicon nitride were prepared under the following surface treatment conditions, and fixed on the surface of the toner particles to prepare a toner. The toner produced in Example 10 is referred to as Toner 10.

(Surface treatment conditions)
A laser ablation method was used as the surface treatment method. The target was Si ₃ N ₄ . As the laser, an Nd: YAG laser having a wavelength of 266 nm was used. The laser output was 200 mJ / pulse. The atmosphere gas was Ar. The gas pressure was 5 × 10 ⁻² Pa. The target-sample distance was 50 mm. The powder vibration condition was a frequency of 30 Hz.

[Example 11]
(Production of toner)
Powders were produced and classified by the same raw materials and production method as in Example 9, and classified into a particle size distribution having an average particle diameter of 6.7 μm, to obtain base colored particles. With respect to 100 parts of the base colored particles, fine particles made of at least silicon nitride were prepared under the following surface treatment conditions, and fixed on the surface of the toner particles to prepare a toner. The toner produced in Example 11 is referred to as Toner 11.

(Surface treatment conditions)
A laser ablation method was used as the surface treatment method. The target was Si ₃ N ₄ . As the laser, an Nd: YAG laser having a wavelength of 266 nm was used. The laser output was 300 mJ / pulse. The atmosphere gas was Ar. The gas pressure was 5 × 10 ⁻² Pa. The target-sample distance was 50 mm. The powder vibration condition was a frequency of 30 Hz.

[Comparative Example 1]
(Production of toner)
Kneading and pulverization were carried out using the same raw materials and production method as in Example 1, and classified into a particle size distribution having an average particle size of 6.0 μm to obtain base colored particles. To 100 parts of the base colored particles, an additive was mixed under the following mixing conditions to prepare a toner. The toner produced in Comparative Example 1 is referred to as Toner 12.

(Mixing of additives)
100 parts of the matrix coloring particles and 1.5 parts of silica fine powder (R972, manufactured by Nippon Aerosil Co., Ltd.) as an additive were mixed with a super mixer mixer at a mixing rotation speed of 800 rpm and 120 seconds. .

[Comparative Example 2]
(Production of toner)
Using the same raw materials and production method as in Example 9, kneading and pulverization were carried out, and the particles were classified into a particle size distribution having an average particle size of 6.7 μm to obtain base colored particles. To 100 parts of the base colored particles, an additive was mixed under the following mixing conditions to prepare a toner. The toner produced in Comparative Example 2 is designated as Toner 13.

(Mixing of additives)
100 parts of the matrix colored particles, 1 part of silica fine powder (R972, manufactured by Nippon Aerosil Co., Ltd.) as an additive, and 0.5 part of titanium oxide fine powder (MT-150A; manufactured by Teika Co., Ltd.) were added using a super mixer mixer. The mixing was performed under the conditions of a mixing speed of 800 rpm and 150 seconds.

(Measurement by AFM)
The measurement with the AFM was performed under the conditions of a probe scanning distance of 1000 nm, a piezo scanning speed of 2.0 Hz, and a measurement count of 30 times, and the average value and variation of interparticle forces were obtained.

(Image evaluation)
The dot reproducibility of the output image when using the toner of the present embodiment was evaluated in five stages, with rank 1 being bad and rank 5 being good, as the roughness of the image.

  Furthermore, a running durability test by printing 20,000 sheets was performed with a copying machine using OPC. The toner transportability defects such as blocking in the developing unit were evaluated. The case where there was no defect was evaluated as ◯, and the case where there was a defect was evaluated as x.

  As for the fluidity of the toner, the space ratio was measured in a compacted state using a conical rotor evaluation apparatus, and then the torque value when the conical rotor entered 20 mm from the surface of the toner powder phase was measured. The evaluation conditions of the conical rotor were a toner phase space ratio of 0.53, an apex angle of the conical rotor of 60 degrees, a conical rotor rotational speed of 1 revolution / min, and a conical rotor penetration speed of 5 mm / min. In addition, fluidity | liquidity is so good that the value of torque is small.

(Measurement of circularity)
Further, the circularity of the powder (matrix) before being treated with the additive was measured as an average circularity by a flow type particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.).

  Table 1 shows the surface treatment conditions and powder characteristics of the toners 1 to 13 obtained in Examples 1 to 11 and Comparative Examples 1 and 2.

図１０は、本実施例及び比較例における粒子間力の変化を示す散布図である。

FIG. 10 is a scatter diagram showing changes in the interparticle force in the present example and the comparative example.

  Referring to FIG. 1, the average value (nN) of interparticle forces shown in Table 1 and σn-1 (nN) indicating variation are plotted on the horizontal and vertical axes, respectively. Circle marks indicate the results of the examples, and square marks indicate the results of the comparative examples.

  The toner of the example surface-treated with fine particles of silicon nitride is superior in toner transportability during running of 20,000 sheets as compared with the toner of the comparative example surface-treated with silica fine powder and / or titanium fine powder. It was.

  The toner fluidity was measured 10 to 50 times by AFM, and when the average value was 5 nN or more and 70 nN or less, the toner fluidity showed a good value. These toners showing good values have good dot reproducibility of the output image and fine image quality reproducibility.

  According to the above-described embodiments and examples, a toner manufacturing method that is excellent in toner transportability at the time of image formation, has good dot reproducibility, and can obtain a high-quality output image, and manufactured by the method. It is possible to provide toner.

  The preferred embodiments and examples of the present invention have been described in detail above, but the present invention is not limited to the specific embodiments, and within the scope of the gist of the present invention described in the claims, Various modifications and changes are possible.

It is a block diagram of the surface treatment apparatus using the laser ablation method in embodiment of this invention. FIG. 6 is a characteristic diagram illustrating a force change when the toner particles of the present embodiment are once pressed against the surface of the compacted toner powder phase and then scanned so as to be separated. It is a block diagram of the AFM apparatus of this embodiment. 1 is a configuration diagram of a toner manufacturing apparatus according to an exemplary embodiment. It is a figure explaining the developing system using the 1-component developer in this embodiment. It is a block diagram of the process cartridge of this embodiment. 1 is a configuration diagram of an image forming apparatus according to an exemplary embodiment. It is a schematic diagram explaining the developing method which applies the alternating electric field of this embodiment. It is a block diagram of the surf fixing device of this embodiment. It is a scatter diagram which shows the change of the force between particles in a present Example and a comparative example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Toner surface treatment apparatus 11 Gas laser light source 12 Lens 13, 37 Laser 14 Target 15 Fine particle 16, 33 Toner particle 17 Excitation apparatus 30, 54 AFM apparatus 31 Substrate stage 32 Toner powder phase 34 Probe 35 Piezo scanner 36 Laser light source 38 Mirror 39 Laser detector 51 Toner extraction means 52 Extraction valve 53 Container 71 Toner replenishment hopper 72 Diffusion blade 73 Supply roller 74 Development roller 75 Doctor roller 76 Photoconductor 99 Process cartridge 100 Image forming apparatus 110 Photoconductor 110K Black photoconductor, 110Y yellow photoconductor 110M magenta photoconductor, 110C cyan photoconductor 114, 115, 116 support roller 117 intermediate transfer cleaning device 118 image forming means 120 charging roller 121 charger 122 second Transfer device 123 Roller 124 Secondary transfer belt 125 Fixing device 126 Fixing belt 127 Pressure roller 128 Sheet reversing device 130 Exposure device 132 Contact glass 133 First traveling member 134 Second traveling member 135 Imaging lens 136 Reading sensor 140 Developer 141 Developing belts 142K, 142Y, 142M, 142C Developer accommodating portions 143K, 143Y, 143M, 143C Developer supply rollers 144K, 144Y, 144M, 144C Developing rollers 145K Black developer, 145Y Yellow developer 145M Magenta developer, 145C Cyan developer 149 Registration roller 150 Intermediate transfer member 151 Roller 152 Separation roller 153 Manual feed path 155 Switching claw 156 Discharge roller 157 Discharge tray 158 Corona charger 160, 190 Leaning device 161 Development device 162 Transfer charger 163 Photoconductor cleaning device 164 Static elimination device 170 Static elimination lamp 180 Transfer roller 195 Transfer paper 701 Photoconductor 702 Development device 703 Development roller 704 Power supply 705 Development unit 800 Fixing device 801 Fixing film 802 Driving roller 803 Follower roller 804 Heating body 805 Pressure roller 806 Transfer material 807 Flat substrate 808 Fixing heater 809 Fixing temperature sensor

Claims (9)

In the toner manufacturing method,
A method for producing a toner, comprising: a surface treatment step of vibrating the toner and treating the surface of the toner with fine particles containing silicon nitride and having an average particle diameter of 10 nm to 100 nm.   The method for producing a toner according to claim 1, further comprising a fine particle production step of producing the fine particles by laser ablation. 3. The toner manufacturing method according to claim 1, wherein the toner is vibrated together with a sample container using a vibration device. 4. The toner manufacturing method according to claim 1, wherein a vibration frequency when the toner is vibrated is 1 Hz or more and 60 Hz or less . A toner manufactured by the toner manufacturing method according to claim 1 . The toner according to claim 5 , wherein an interparticle force of the toner is 21.0 nN or more and 65.0 nN or less . A two-component developer comprising the toner according to claim 5 and a carrier having magnetism. A process cartridge using the toner according to claim 5 . An image forming apparatus that forms an image using the toner according to claim 5 .

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