JP4753754B2 - Method for producing toner for electrostatic charge development - Google Patents

Description

The present invention relates to a method for producing an electrostatic charge developing toner.

The image quality of copiers and printers has been improved, and recently, the reproducibility of fine dots has become very important. The dot reproducibility is greatly influenced by fluidity in addition to the charge amount of toner and developer, and it is necessary to stably supply a uniform toner layer or developer layer to a fine latent image portion. Is coming. Furthermore, the speed of copying machines and printers has increased, and the stable supply of toner and developer to the development area has become more essential than ever.
Further, as the image quality is improved, the toner used in the toner is becoming smaller in particle size and higher in function. For this reason, the structure of the toner has become complicated, and finer control at the time of production has become necessary. In particular, the fluidity of toner is considered to be a very important technique because it affects various image quality in addition to dot reproducibility.
In addition, when the toner production method changes from the pulverization method to another method such as a polymerization method, the change in the flow characteristics with respect to the manufacturing conditions is large. Evaluation is required.

In Patent Document 1, the surface roughness of the latent image carrier is measured with an atomic force microscope (AFM), and the surface roughness and the wear rate of the latent image carrier are defined. However, this technique is not related to the interparticle force between toner base particles. Patent Document 2 discloses a technique in which the electrical characteristics of an electrophotographic endless belt are measured using SPM, and the value of the total surface current amount of 25 μm × 25 μm when 100 V is applied is disclosed. However, this technique is not related to the interparticle force between the toner base particles. Non-Patent Document 1 reports that the SiO ₂ and PMMA true spherical particles are attached to the tip of the AFM cantilever and the adhesion between the glass substrate and the organic polymer flat plate is measured. And the adhesion force between a flat plate made of a material different from this, and not the inter-particle force between particles of the same composition. Thus, a technique for evaluating the interparticle force between toner base particles is not known.
JP 2004-109492 A JP 2004-94178 A Konica Minolta Technology Report, Vol.1 (2004), p.19-22

The present invention, by appropriately controlling the inter-particle force between toner base particles, method for producing a can Ru toner for developing an electrostatic image of the good quality dot reproducibility can be stably the toner for electrostatic charge development obtained The purpose is to provide.

The present inventor has found that the interparticle force can be indirectly defined by obtaining the relationship between the interparticle force between the toner base particles and the particle size of the toner base particle and defining the particle size.
In the present invention, the toner base particles attached to the tip of the AFM probe are brought into contact with a single toner particle in the compacted toner powder phase, and the force change when the toner particles are separated is measured. The inter-particle force is obtained, and it is found that the inter-particle force is very important for the fluidity, and this is defined by the relationship with the particle size of the toner base particles. Furthermore, in the present invention, the optimum interparticle force is managed by the particle size using the relational expression between the particle size and the interparticle force. Thereby, the fluidity of the toner in the development area can be improved, a uniform toner brush can be realized, and a high image quality with excellent dot reproducibility can be obtained.

The present invention is as follows.
1) Toner base particles having an average circularity of at least 0.97 to 0.99 containing at least a resin and a pigment before adhering or fixing the additive to the surface are used, and one toner base particle is attached to the tip of the probe. Alternatively, the operation of attaching the probe to its periphery, pressing the probe once onto one particle on the surface of the compacted toner powder phase composed of the same toner base particles by AFM, and then pulling the probe apart is repeated 10 to 50 times. The average value Fa of the interparticle force between the toner base particles obtained by the difference in force acting on the probe when the probe is brought close to and separated from the toner base particle diameter D satisfies the following formula (1). In addition, the average value Fa was calculated using the value of the toner base particle diameter D in the toner evaluation method for electrostatic charge development for evaluating whether the average value Fa satisfies 20 to 80 nN. The average value Fa Concrete manage the quality of the toner base particles in step manufacturing method of the electrostatic image developing toner, wherein the toner is produced.
Fa = A × D ^2x (1)
(A: Coefficient)
(x: 1.0 to 1.4 )

According to the present invention, by appropriately controlling the inter-particle force between toner base particles, the can Ru toner for developing an electrostatic image of the good quality dot reproducibility can be stably the toner for electrostatic charge development obtained A manufacturing method can be provided.

  The present invention uses toner base particles having an average circularity of 0.97 to 0.99 including at least a resin and a pigment before adhering or fixing the additive to the surface, and probe the toner base particles. The tip is attached to the tip or the periphery thereof, and the probe is pressed once against one particle on the surface of the compacted toner powder phase composed of the same toner base particles by AFM, and then the probe is separated 10 to 50 times. Repeatedly, the average value Fa of the interparticle force between the toner base particles obtained by the difference in force acting on the probe when the probe is brought close to and separated from the toner base particle diameter D is expressed by the following equation (1). When satisfied, the average value Fa is optimized by the particle size D of the toner base particles, whereby an electrostatic charge developing toner capable of obtaining high image quality with good dot reproducibility can be provided.

Fa = A × D ^2x (1)
(A: Coefficient)
(x: 1.0 to 1.4)

The AFM (Atomic Force Microscope) method is a method of measuring a sample surface shape and the like by scanning a probe having a tip of about 10 nmφ, detecting an atomic force acting between the probe and atoms on the sample surface. The resolution is very high, and the uneven shape in the Z direction with respect to the scanning direction (X direction) of the probe can be measured. In the present invention, one toner base particle is attached to the tip of the probe, and the toner base particle attached to the probe is once pressed against one particle on the surface of the compacted toner powder phase and then separated. The force change at that time was measured. As a result, the force characteristics shown in FIG. 1 were obtained, and the interparticle force between the toner base particles was obtained from the difference between the characteristics when the probe was brought close and the characteristics when the probe was pulled away. An outline of the AFM apparatus is shown in FIG. A compacted toner powder phase (12) is provided on a substrate stage (11), and a probe (14) with one toner base particle (13) on its surface is brought close by using a piezo scanner (15). Or pull apart. At that time, the change in force generated in the probe (14) is irradiated from the laser generator (16) to the back side of the probe (14) with the laser beam (17), and the change in the reflected light is applied to the mirror (18). And detected by the detection unit (19). At the time of measurement, since it is necessary to detect all the forces acting on one toner base particle attached to the tip or the periphery of the probe with high accuracy, the same toner base particle attached to the tip or the periphery of the probe is the same. The distance when approaching the surface of the toner powder phase composed of toner base particles is important. In the case of toner base particles, since they are easily affected by frictional charging and the like, measurement from a considerably distant position is required. From one toner base particle adhered to the tip or the periphery of the probe, 1 of the toner powder phase is required. The preferred distance when approaching the individual particles was 500 to 2000 nm. Measurement was performed by operating the probe having one toner base particle adhered from the distance of 500 to 2000 nm close to the toner powder phase, pressing the probe once on the surface, and then pulling the probe apart. If this distance is shorter than 500 nm, the probe cannot be separated from the surface of the toner powder phase, which is not suitable for measurement. In addition, when this distance is longer than 2000 nm, the measurement accuracy is deteriorated, and it is difficult to accurately measure the difference between the characteristics when the probe approaches and the characteristics when the probe is separated. The probe is made of Si ₃ N ₄ , Si single crystal, or the like.

The toner powder phase is a state compressed at a pressure of 100 to 900 kg / cm ² and is fixed so that it does not move even when a probe with one toner base particle attached contacts. However, when the compression pressure is less than 100 kg / cm ^2, toner base particles that are not sufficiently fixed partially exist and are not suitable for measurement. When the compression pressure is greater than 900 kg / cm ² , the toner base particles are deformed, and the surface of the toner base particles is broken, resulting in a surface state in which the particles are aligned. The particles are in a flat planar surface state due to pressing, which is different from the state of the toner base particles and the toner base particles, and is not suitable for the measurement of the interparticle force. The toner powder phase compressed at a pressure of 100 to 900 kg / cm ² is formed into a flat plate size of 10 mm × 10 mm × 5 mmt or less and used for measurement. In the measurement, the compressed toner powder phase is fixed to the substrate stage of the AFM apparatus. At that time, the compressed toner powder phase is brought into close contact with the surface of the substrate stage and fixed so as to be as horizontal as possible. Further, a toner powder phase in which one particle is randomly arranged and fixed on an adhesive layer on the surface of a flat substrate such as glass is used, and the toner base particle is adhered to the toner base particle. Measurement may be performed by contacting a needle. However, in this case, it is difficult to adjust the position so that the toner base particles at the tip of the probe are brought into contact with one toner base particle on the substrate side.

  The optimum scanning speed of the piezo when one toner base particle attached to the tip or the periphery of the probe is brought close to the compressed toner powder phase is 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 on the surface of the toner base particles, 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, so that the operation of pressing and separating the toner base particles is not sufficient, and the probe with one toner base particle attached is used as the toner powder phase. The interparticle force between toner base particles, which is obtained by the difference in force between approaching and separating, tends to be small, and is not suitable as a measurement condition. The method of attaching one toner base particle to the tip of the AFM probe is as follows: (1) The probe is brought close to and brought into contact with the wire coated with an adhesive while viewing an enlarged image using an optical microscope. (2) A probe with adhesive attached to the tip is brought close to a sparsely attached wire or rod with one toner base particle, and only one toner particle is attached to the tip of the probe. (3) The probe with one toner particle attached is dried at room temperature for 24 hours or more. Since the adhesive accurately measures the force between the particles, a curable adhesive is suitable. 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 interparticle force between the toner base particles using AFM is repeated 10 to 50 times, and the average value is used for evaluation. The repetition is not repeated at the same place, but is preferably carried out while changing the place (for example, moving about 50 nm). At that time, it is also very important to evaluate the distribution of interparticle forces. Although it is better to have a large number of repetitions, if it is too large, measurement time and analysis time are required, so 10 to 50 times is suitable.

  The interparticle force between the toner base particles varies depending on the surface state of the toner base particles and the shape of the toner base particles. When the interparticle force between the toner base particles when the surface of the toner base particle has fine irregularities and the surface without a fine unevenness is obtained, the following values are obtained, and the fine unevenness on the surface of the toner base particles It can be seen that the interparticle force is reduced when the is present. This is because the distance between the toner base particles is increased due to the unevenness of the surface of the toner base particles, or the contact area between the toner base particles is reduced, and the interaction between the particles is reduced.

When the volume particle size is 4.3 μm: Interparticle force 28 nN
When the volume particle size is 6.5 μm: Interparticle force 91 nN

  The shape of the toner base particles also affects the force between the particles, and a shape close to a sphere is suitable for measurement with little variation in measurement. The shape of the toner was measured in terms of circularity. Specifically, measurement was performed using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). When the average circularity was 0.97 to 0.99, the interparticle force of the toner was small, and high image quality could be realized. Also, in this condition range, since toner base particles are attached to the tip of the probe, the toner powder in which the particle surface having the same shape is compressed no matter which part of the particle is attached to the tip of the probe. Since it comes in contact with the phase, the variation in interparticle force measurement is reduced, and high-precision measurement is possible. When the average circularity is less than 0.97, the interparticle force between the toner base particles is large, and the interparticle force is different every time when the contact surface of the particle makes a probe with the toner base particles attached. The variation became large. Further, the addition process of the fine particles is affected by the shape of the powder (matrix) before adding the fine particles, but the average circularity of the powder (matrix) before adding the fine particles is 0.97 to 0.99. In the case of a very nearly spherical shape, the effect of adding fine particles was excellent, and high image quality with excellent dot reproducibility could be realized. As a method for controlling the shape of the toner base particles, the toner base particles after the classification process are put into a rotating body and rotated at a high speed (Hybridizer, Nara Machinery Co., Ltd.), or heat is instantaneously applied to the particle surface. This process can be realized by passing the process (saffusion system, Nippon Pneumatic Industry Co., Ltd.).

  Therefore, using toner base particles having an average circularity of 0.97 to 0.99, the toner base particle size was changed, and the relationship between the particle size and the interparticle force was examined. As a result, as shown in FIG. 3, the value of the interparticle force increased in a quadratic function as the toner base particle diameter increased. That is, the relationship expressed by the following equation (1) is established, and the average value Fa of the interparticle force between the toner base particles can be managed by the toner base particle diameter D. In the formula (1), x is a constant that varies depending on the surface state of the toner base particles, the type of resin of the toner base particles, and the like, and a value of 1 to 1.4 is suitable. When the ratio is smaller than 1, the interparticle force between the toner base particles is small, so that the coverage of the additive is reduced, and the protection function against the environment (temperature, humidity) is lowered, which causes a problem. When the ratio is higher than 1.4, it is necessary to increase the coverage of the additive, and problems such as release, scattering, and filming of the additive are likely to occur.

Fa = A × D ^2x (1)
(A: Coefficient)
(x: 1.0 to 1.4)

  Using toner base particles having an average circularity of 0.97 to 0.99, the optimum region of interparticle force between toner base particles was determined from the relationship between toner fluidity and image quality. As a result, the force between the toner base particles was repeatedly measured by AFM 10 to 50 times, and when the average value Fa was 20 to 80 nN, the toner fluidity was good and the reproducibility of fine image quality was improved. If the average value Fa of the interparticle force is less than 20 nN, it is not suitable because a problem such as scattering occurs when the toner is conveyed. If the average value Fa of the interparticle force is greater than 80 nN, the toner fluidity is poor. Therefore, high image quality could not be realized and it was not suitable.

  Further, it was found that the volume average particle size of the toner base particles is preferably in the range of 4 to 6 μm in order to satisfy the above optimal base particle force Fa of the base using the formula (1). When the volume average particle size of the toner base particles is smaller than 4 μm, the interparticle force between the toner base particles before the addition of the additive is already small, so the coverage of the additive may be small. When the coverage was small, the protection function against the environment (temperature, humidity) was lowered, which became a problem. When the volume average particle diameter of the toner base particles is larger than 6 μm, the interparticle force between the toner base particles before the addition of the additive is large. Therefore, it is necessary to increase the coverage of the additive. Problems such as liberation and toner scattering occurred.

  The shape of the surface of the toner base particles can be controlled by the type of fine particles of the additive, the particle size, the mixing conditions at the time of addition, and the fixing injection conditions. The fine particles to be added are optimally inorganic fine powder, and the average particle size is optimally a small particle size of 10 to 200 nm. When the particle diameter is smaller than 10 nm, it is difficult to produce the unevenness effect, and when the particle diameter is larger than 200 nm, it is difficult to create appropriate unevenness. A combination of at least an inorganic fine powder having an average particle size of 10 to 100 nm and an inorganic fine powder having an average particle size of 100 to 200 nm may be adhered or fixed to the surface of toner base particles made of resin or pigment.

As the inorganic fine powder used in the present invention, Si, Ti, Al, Mg, Ca, Sr, Ba, In, Ga, Ni, Mn, W, Fe, Co, Zn, Cr, Mo, Cu, Ag, V , Oxides such as Zr, and composite oxides. Of these, fine particles of silicon dioxide (silica), titanium dioxide (titania), and alumina are preferably used. Furthermore, it is effective to perform a surface modification treatment with a hydrophobizing agent or the like. Typical examples of the hydrophobizing agent include the following.
Dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, Chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, hexaphenyldisilazane, hexatolyldisilazane, etc.
The added amount of the inorganic fine powder is preferably 0.1 to 5% by weight based on the toner. If it is less than 0.1% by weight, the effect of improving the toner fluidity is poor, and if it exceeds 5% by weight, problems such as toner scattering between fine wires, contamination in the machine, scratches and abrasion of the photoreceptor tend to occur. There is.

The mixing or fixing injection conditions when the additive is added are mainly controlled by the mixing rotation speed. That is, the mixing rotation speed can control the force for attaching the fine powder to the toner surface. The mixing rotation speed is optimally 1000 rpm to 6000 rpm. When the mixing rotation speed is lower than 1000 rpm, the fine powder adheres to the surface of the toner base particles with a very weak force, and the surface shape is stable. Lost, and toner scattering, in-machine contamination, etc. are likely to occur. When the mixing rotational speed is higher than 6000 rpm, the fine powder added will bite into the surface of the toner base particles before being added, and the unevenness of the surface will be smoothed to reduce the unevenness, resulting in poor fluidity. Become.
These mixing conditions vary depending on the type of mixer. In the mixer, powder is mixed by rotating the container, etc., mixed by stirring blades, kneaded through a gap, etc., rotated at high speed to collide with the wall, charged into high-speed air current and collided with particles, etc. In the present invention, the fine powder adhering to the toner surface is finely dispersed and uniformly adhered, so that the gap between the walls is passed to give shear energy between the particles, or a stirring blade is used. A method of giving collision energy to particles by rotating at high speed or throwing it into a high-speed air stream is suitable. In the case of such a mixer, since the shear energy acting on the particles and the collision energy between the particles are large, the energy acting between the toner base particles and the fine powder before being added tends to be large. It is necessary to finely adjust the optimum conditions. That is, it is necessary to carry out the mixing under the optimum mixing condition of 1000 rpm to 6000 rpm. The mixing time is preferably short so that the temperature of the toner does not increase.

Details of the toner and developer are shown below.
As resins, 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, silicon resin, butyral resin, terpene There are resins, polyol resins and the like.
Examples of vinyl resins include styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and homopolymers thereof: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer. Polymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacrylic copolymer Acid methyl copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Coalescence, styrene-vinyl ethyl acetate Copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers: polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate and the like.

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 further a trihydric or higher alcohol as shown in the group C 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, 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, or 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. There are those obtained by reacting two or more compounds.

As the resin, crystalline polyester may be used. It is an aliphatic polyester having crystallinity, having a sharp molecular weight distribution, and increasing the absolute amount of its low molecular weight as much as possible. This resin undergoes a crystal transition at the glass transition temperature (Tg), and at the same time, the melt viscosity suddenly decreases 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 Tg and molecular weight of the resin. Therefore, there is no decrease in storage stability associated with a decrease in Tg. Further, there is no excessively high gloss and offset resistance deterioration due to the low molecular weight. Therefore, the introduction of the crystalline polyester resin is very effective for improving the low-temperature fixability of the toner.
In the toner of the present invention, the content of the crystalline polyester is 1 to 50 weights with respect to the total amount of the resin and the release agent in the toner in order to exhibit low-temperature fixability and ensure hot offset resistance. It is preferable that the content of the release agent is 2 to 15% by weight. When the content of the crystalline polyester is less than 1% by weight, there is no effect on the low-temperature fixability, and when it exceeds 50% by weight, the hot offset property is deteriorated. When the release agent content is less than 2% by weight, the offset resistance may not be effective, and when it exceeds 15% by weight, the toner fluidity decreases.

The molecular structure of the crystalline polyester resin is not limited, but from the viewpoint of the crystallinity and softening point of the polyester resin, a diol compound having 2 to 6 carbon atoms, particularly 1,4-butanediol and 1,6-hexanediol. And an aliphatic polyester represented by the following general formula (2) synthesized using an alcohol component containing these derivatives and maleic acid, fumaric acid, succinic acid, and an acid component containing these derivatives It is preferable to contain.
General formula (2) [-0-CO-CR ₁ = CR ₂ -CO-O- (CH ₂ ) _n- ] _m
(Here, n and m are the number of repeating units. R ₁ and R ₂ are hydrocarbon groups.)
From the viewpoint of the crystallinity and softening point of the polyester resin, a trihydric or higher polyhydric alcohol such as glycerin is added to the alcohol component to synthesize a non-linear polyester, and trimellitic anhydride or the like is added to the acid component. Polycondensation may be performed by adding a trivalent or higher polyvalent carboxylic acid.
The glass transition temperature (Tg) of the crystalline polyester resin is desirably low so long as the heat resistant storage stability does not deteriorate, and is preferably in the range of 80 to 130 ° C. When the glass transition temperature (Tg) is less than 80 ° C., the heat-resistant storage stability deteriorates, and blocking tends to occur at the temperature inside the developing device. Cannot be obtained. The glass transition temperature (Tg) of the crystalline polyester resin is the endothermic peak temperature at the time of 2nd temperature increase by DSC.

The following are used as the pigment used in the present invention.
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. .
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, 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, first sky blue, and indanthrene blue BC.
Examples of green pigments include chrome green, chromium oxide, pigment green B, and malachite green lake.
These can use 1 type (s) or 2 or more types.
Especially for color toners, uniform dispersion of good pigments is essential. Instead of putting pigments directly into a large amount of resin, a master batch in which pigments are once dispersed at a high concentration is prepared and diluted. The method of throwing in is used. In this case, a solvent is generally used to help dispersibility. However, there is a problem of environment and the like, and in the present invention, water can be used for dispersion. When water is used, temperature control is important so that residual moisture in the masterbatch does not become a problem.

In the toner of the present invention, a charge control agent is blended (internally added) inside the toner base particles. However, it may be used by mixing (external addition) with toner base particles. The charge control agent makes it possible to control the optimum charge amount according to the development system. In particular, in the present invention, the balance between the particle size distribution and the charge amount can be further stabilized.
For controlling the toner to be positively charged, nigrosine and quaternary ammonium salts, triphenylmethane dyes, imidazole metal complexes and salts can be used alone or in combination of two or more. Further, salicylic acid metal complexes, salts, organic boron salts, calixarene compounds, and the like are used for controlling the toner to be negatively charged.

  Further, a release agent can be internally added to the toner in the present invention to prevent offset at the time of fixing. Release agents include natural waxes such as candelilla wax, carnauba wax, rice wax, montan wax and derivatives thereof, paraffin wax and derivatives thereof, polyolefin wax and derivatives thereof, sazol wax, low molecular weight polyethylene, and low molecular weight polypropylene. And alkyl phosphate esters. The melting point of these release agents is preferably 65 to 90 ° C. When the temperature is lower than this range, blocking during storage of the toner tends to occur, and when the temperature is higher than this range, an 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, There is a polyol resin or the like, and a mixture of two or more of these resins may be used. The addition amount of the dispersant is suitably 10 parts by weight or less with respect to 100 parts by weight of the resin. Even if the amount is more than 10 parts by weight, the effect of acidity of WAX is not observed, and conversely, the fixing property and the image reproducibility are deteriorated.

  Examples of the method for producing the toner according to the present invention include a pulverization method and a polymerization method (suspension polymerization, emulsion polymerization dispersion polymerization, emulsion aggregation, emulsion association, etc.), but are not limited to these production methods.

  As an example of the pulverization method, first, the above-mentioned resin, pigment or dye as a colorant, charge control agent, release agent, other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer, and then batch type. The constituent materials are well kneaded using a two-roll, Banbury mixer, continuous twin-screw extruder, continuous single-screw kneader, or the like, and cut after rolling and cooling. The toner kneaded product after cutting is crushed, coarsely pulverized using a hammer mill, etc., and further pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, and a classifier or Coanda effect using a swirling airflow Is classified to a predetermined particle size by a classifier using After this classification step, the particle size of the toner base particles is evaluated in order to evaluate whether or not a predetermined interparticle force is obtained. The volume average particle size is evaluated using a Coulter Counter TA-II or Coulter Multisizer (manufactured by Coulter). Thereafter, an additive composed of inorganic fine particles or the like is adhered or fixed to the particle surface by a mixer under the optimum mixing conditions.

  In the present invention, the interparticle force between the toner base particles in the production process is controlled by the particle size D of the toner base particles using the equation (1). For that purpose, it is necessary to obtain the values of A and x in equation (1) in advance. For both A and x, a preliminary experiment is performed to determine the relationship between the interparticle force between the toner base particles and the particle diameter D between the toner base particles under the condition that the average circularity is constant, and the respective values are determined. Since it is considered that it is difficult in terms of time to obtain the interparticle force between the toner base particles every time the quality check of the manufacturing process is performed, there is a problem in the evaluation during the manufacturing process. However, in the present invention, the interparticle force can be determined by determining the particle size of the toner base particles, which is suitable as an evaluation method in the manufacturing process. Also, by evaluating the quality of the matrix after the classification process more accurately than before using this evaluation method, the quality variation after the subsequent mixing process can be made low and stable, and finally high. Toners that can achieve high image quality can be manufactured and supplied stably.

  As a result of the evaluation, when the numerical value is within the predetermined setting range, the sample is turned to the mixing step and the air sieving step, passed through a sieve of 250 mesh or more to remove coarse particles and agglomerated particles, and then the sample filling step The toner of the present invention is obtained.

  As a method for producing the toner according to the present invention, methods other than the pulverization method are conceivable. 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, in the toner of the present invention, an oily 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 in an aqueous medium. A urea-modified polyester resin having a urea group by dispersing in the presence of inorganic fine particles and / or fine polymer particles and reacting the prepolymer with a polyamine and / or a monoamine having an active hydrogen-containing group in the dispersion. And a liquid medium contained in the dispersion containing the urea-modified polyester resin is removed.
In the urea-modified polyester resin, the Tg is 40 to 65 ° C, preferably 45 to 60 ° C. The number average molecular weight Mn is 2500 to 50000, preferably 2500 to 30000. 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 increased in molecular weight by the reaction between the prepolymer and the amine. The colorant is highly dispersed in the binder resin.
The obtained toner powder after drying is air-classified, the particle size of the toner base particles is measured, and the interparticle force is evaluated. The volume average particle size is evaluated using a Coulter Counter TA-II or Coulter Multisizer (manufactured by Coulter). As a result of the evaluation, when the numerical value falls within a predetermined setting range, an additive composed of inorganic fine particles or the like is adhered or fixed to the particle surface by a mixer under optimum mixing conditions. Alternatively, the charge control agent may be applied to the surface of the toner powder after drying and fixedly injected. Further, thereafter, an additive made from inorganic fine particles or the like may be adhered or fixed to the particle surface. By placing the charge control agent on the surface, the charge amount of the toner can be easily controlled.
Specific means for mixing and fixing and injecting are as follows: a method of applying an impact force to the powder mixture with blades rotating at high speed; For example, there is a method of causing the particles to collide with an appropriate collision plate. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc. Thereafter, the sample is passed to the air sieving step, passed through a sieve of 250 mesh or more to remove coarse particles and aggregated particles, and then the sample is passed to the filling step to obtain the toner of the present invention.

The toner of the present invention can be used as a one-component developer used in a contact or non-contact development system. As the contact or non-contact development method, various known methods are used. For example, there are 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. .
In addition, this toner is excellent in fluidity when developing using an AC bias voltage component during development, so that it vibrates faithfully according to the electric field, and can faithfully develop fine latent images, and dot reproducibility. Development is possible.

Further, in the one-component development method, the present toner is used in a development method in which a roller-shaped blade or a supply roller for making a toner layer uniform is provided at the outlet of the toner supply unit. FIG. 5 is a diagram for explaining an example of a developing device to which the toner of the present invention can be preferably applied. The developing device includes a toner supply hopper 31, a stirring blade 32 that stirs the toner inside, a doctor roller 33, a supply roller 34, and a developing roller 36 that supplies toner to an image holding member (photosensitive member) 35. In such a system, the fluidity of the toner greatly affects the uniformity of the toner layer on the developing roller and also affects the durability characteristics. When the durability characteristics are poor, not only filming on the photosensitive member but also filming on the doctor roller and the supply roller occurs. For this reason, the toner layer cannot be formed uniformly, the toner charge becomes non-uniform, and the toner charge amount becomes small. For this reason, poor development occurs.
However, when the toner produced by the production method of the present invention is used, since the toner fluidity is excellent, it is possible to easily achieve a uniform thinning of the toner layer on the developing roller via the supply roller and the doctor roller, The toner can be stably conveyed onto the developing roller at all times. Further, filming on the doctor roller and the supply roller does not occur, stable development is performed, and the system has excellent durability characteristics.

  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 to 1 μm. The content of the magnetic material is preferably 10 to 70 parts by weight with respect to 100 parts by weight of the toner.

  Further, when used as a two-component developer, a two-component developer is obtained by mixing with a magnetic carrier described later at a predetermined mixing ratio.

  As the carrier used in the two-component developer, known carriers can be used. For example, magnetic particles such as iron powder, ferrite powder, nickel powder, magnetite powder, or the surface of these magnetic particles are made of fluorine resin or vinyl resin. And those treated with a silicone-based resin or the like, or magnetic particle-dispersed resin particles in which magnetic particles are dispersed in the resin. The average particle diameter of these magnetic carriers is preferably 20 to 70 μm in order to realize a high quality image. When the average particle size of the carrier is in the range of 20 to 70 μm, the charge amount of the toner can be made more uniform when the toner concentration in the developing device is in the range of 2 to 10% by weight. When it is smaller than 20 μm, 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 high image quality 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. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive fine particles preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  In addition, the developer containing the toner of the present invention may further contain other additives such as Teflon (registered trademark) powder, zinc stearate powder, and polyvinylidene fluoride powder within a range that does not substantially adversely affect the developer. Or a polishing agent such as cerium oxide powder, silicon carbide powder or strontium titanate powder; or a conductivity-imparting agent such as carbon black powder, zinc oxide powder or tin oxide powder may be used in a small amount as a developability improver.

Since the present toner has excellent fluidity, it can be stored in a cartridge container and is suitable for an apparatus configured to convey toner from the cartridge container to the developing unit.
Examples of the cartridge container include a toner cartridge that fills toner, and a process cartridge that includes at least a photosensitive member and a developing unit, and that fills a toner storage portion of the developing unit. An image is formed by attaching the cartridge to the image forming apparatus.

FIG. 6 is a schematic view showing the configuration of the process cartridge of the present invention.
Examples of the process cartridge 90 include a toner cartridge that fills toner, and a toner cartridge 56 that includes at least the photoreceptor 60 and the developing device 50 and fills toner in a toner storage portion of the developing device. The toner cartridge 56 or the process cartridge 90 is mounted on the image forming apparatus, and image formation is performed. Reference numeral 80 denotes a cleaning member, and 70 denotes a charging member.

Hereinafter, although an Example is described, this does not limit this invention at all. In this example, toners having different toner base particle compositions and toner base particle preparation methods were prepared, and the interparticle force between the toner base particles and the toner base particle size D were evaluated. The interparticle force between the toner base particles is evaluated by the method of the present invention, in which one toner base particle is attached to the tip or the periphery of the probe to produce a compressed toner powder phase of the same particles as the toner base particles. did. The toner powder phase was prepared at a compression pressure of 320 kg / cm ² , and the measurement with AFM was performed under the following conditions to determine the average value Fa of the interparticle force. Further, the evaluation of the toner base particle size D at that time was performed using FE-SEM (manufactured by Hitachi, Ltd.). Similarly, Fa was evaluated by changing the toner base particle diameter D, and the value of x was obtained from the relationship between D and Fa.

-Probe scanning distance: 1000 nm
-Piezo scan speed: 2.0Hz
・ Number of measurements: 32 times

  Further, the fluidity of the toner was evaluated using a conical rotor device, and the dot reproducibility was evaluated on a five-point scale (rank 1: bad → rank 5: good). The running characteristics were evaluated by the toner transportability of the developing unit. The evaluation conditions of the conical rotor device were as follows, and the torque value when the conical rotor entered 20 mm into the toner phase was measured. Further, the circularity of the toner (base material) 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.).

-Space ratio of toner phase: 0.53
・ Vertical angle of conical rotor: 60 °
・ Rotation speed of conical rotor: 1rpm
・ Invasion speed of conical rotor: 5 mm / min

  In addition, all the parts in the following mixing | blending are a weight part.

—Example 1—
Resin Polyester resin 100 parts
(Polyester synthesized from terephthalic acid and succinic acid derivative of propylene oxide adduct of bisphenol A)
Colorant Magenta pigment (CI Pigment Red 122) 3.5 parts
(Hostaperm Pink E; manufactured by Clariant)
Charge control agent Zinc salicylate 5 parts
(Bontron E84, Orient Chemistry)

After sufficiently mixing the raw materials with a mixer, the raw materials were melt kneaded with a twin screw extruder at a barrel temperature of 100 ° C. and a kneader rotation speed of 110 rpm. The kneaded product was rolled and cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then classified into a particle size distribution having a volume average particle size of 5.5 μm using a swirling air classifier. Thereafter, particles were spheroidized using a hybridization system (manufactured by Nara Machinery Co., Ltd.) to obtain matrix colored particles. The interparticle force Fa was measured using particles having different particle diameters D of the base colored particles, and the value of x in the equation (1) was determined from the relationship between the particle diameter D and the interparticle force Fa. Moreover, the average circularity was calculated | required. This time, the interparticle force was measured using base particles having a particle diameter D of 4.3 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

—Example 2—
Kneading, pulverization, classification, and spheronization were carried out using the same raw materials and production methods as in Example 1, and the interparticle force was measured using base particles having a particle diameter D of 5.2 μm.
Further, in the same manner as in Example 1, 100 parts of the base colored particles were mixed with an additive under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

—Example 3—
Kneading, pulverization, classification, and spheronization were performed using the same raw materials and production methods as in Example 1, and the interparticle force was measured using base particles having a particle diameter D of 5.8 μm.
Further, in the same manner as in Example 1, 100 parts of the base colored particles were mixed with an additive under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

—Example 4—
Kneading, pulverization, classification, and spheronization were performed using the same raw materials and production method as in Example 1, and the interparticle force was measured using base particles having a particle diameter D of 6.0 μm.
Further, in the same manner as in Example 1, 100 parts of the base colored particles were mixed with an additive under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

-Example 5-
(Synthesis of toner binder)
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, and reacted at 230 ° C. under normal pressure for 8 hours. The reaction was further carried out at a reduced pressure of 10 to 15 mmHg for 5 hours, followed by cooling to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Subsequently, it cooled to 80 degreeC and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the isocyanate containing prepolymer (1) was obtained. Next, 267 parts of the prepolymer (1) and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a urea-modified polyester (1) having a weight average molecular weight of 64,000. In the same manner as above, 724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Polyester A was obtained. 200 parts of urea-modified polyester (1) 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 (1). . Part of the mixture was dried under reduced pressure to isolate toner binder (1). As a result of analysis, Tg was 62 ° C.

[Production of toner]
Toner binder (1) in ethyl acetate / MEK solution 240 parts Pentaerythritol tetrabehenate (melt viscosity 25 cps) 20 parts Carbon black (# 44; manufactured by Mitsubishi Chemical Corp.) 10 parts The above raw materials in a beaker at 60 ° C The mixture was stirred at 12000 rpm with a TK homomixer and uniformly dissolved and dispersed to prepare a toner material solution.
706 parts of ion exchange water 10% suspension of hydroxyapatite (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.)
294 parts Sodium dodecylbenzenesulfonate 0.2 part The above raw materials were placed in a beaker and dissolved uniformly. Thereafter, the temperature was raised to 50 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 11000 rpm with a TK homomixer. The mixture was then transferred to a stir bar and a flask equipped with a thermometer, heated to 30 ° C., the solvent was removed under reduced pressure, filtered, washed, dried, and then subjected to air classification to obtain toner particles. The volume average particle diameter was 5.0 μm. The average value Fa of the interparticle force was measured using particles having different particle diameters D of the base colored particles, and the value x in the equation (1) was determined from the relationship between the particle diameter D and Fa. Moreover, the average circularity was calculated | required. This time, interparticle force was measured using base particles having a particle diameter D of 4.1 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner. To 100 parts of the toner particles, an additive was mixed under the following mixing conditions to obtain a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

-Example 6-
Powders were produced and classified by the same raw materials and production method as in Example 5, and the interparticle force was measured using base particles having a particle diameter D of 4.8 μm.
Further, in the same manner as in Example 5, 100 parts of the base colored particles were mixed with an additive under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

-Example 7-
Powders were produced and classified by the same raw materials and production methods as in Example 5, and the interparticle force was measured using base particles having a particle diameter D of 5.2 μm.
Further, in the same manner as in Example 5, 100 parts of the base colored particles were mixed with an additive under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

-Example 8-
Powders were produced and classified by the same raw materials and production method as in Example 5, and the interparticle force was measured using base particles having a particle diameter D of 5.6 μm.
Further, in the same manner as in Example 5, 100 parts of the base colored particles were mixed with an additive under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

-Example 9-
Resin Polyester resin 100 parts (Propylene oxide adduct of bisphenol A, polyester synthesized from terephthalic acid, succinic acid derivative)
Copper phthalocyanine blue pigment (CI Pigment Blue 15: 3) 4 parts (Lionol Blue FG-7351; manufactured by Toyo Ink)
Charge control agent Zinc salicylate 5 parts (Bontron E84; manufactured by Orient Chemical Co., Ltd.)
Release agent 5 parts of low molecular weight polyethylene After sufficiently mixing the above raw materials with a mixer, the mixture was melt-kneaded with a twin screw extruder at a barrel temperature of 100 ° C. and a kneader rotation speed of 110 rpm. The kneaded product was rolled and cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then classified into a particle size distribution having a volume average particle size of 5.6 μm using a swirling air classifier. Thereafter, particles were spheroidized using a hybridization system (manufactured by Nara Machinery Co., Ltd.) to obtain matrix colored particles. The average value Fa of the interparticle force was measured using particles having different particle diameters D of the base colored particles, and the value x in the equation (1) was determined from the relationship between the particle diameter D and Fa. Moreover, the average circularity was calculated | required. This time, the interparticle force was measured using base particles having a particle diameter D of 4.4 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

-Example 10-
Powders were produced and classified by the same raw materials and production method as in Example 9, and the interparticle force was measured using base particles having a particle diameter D of 5.0 μm.
Further, in the same manner as in Example 9, 100 parts of the base colored particles were mixed with an additive under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

-Example 11-
Powders were produced and classified by the same raw materials and production method as in Example 9, and the interparticle force was measured using base particles having a particle diameter D of 5.6 μm.
Further, in the same manner as in Example 9, 100 parts of the base colored particles were mixed with an additive under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

-Example 12-
Powders were produced and classified by the same raw materials and production method as in Example 9, and the interparticle force was measured using base particles having a particle diameter D of 5.9 μm.
Further, in the same manner as in Example 9, 100 parts of the base colored particles were mixed with an additive under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

-Comparative Example 1-
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 1, and the particles were classified into a particle size distribution with a volume average particle size of 5.5 μm. Base colored particles were produced without spheroidizing treatment. The interparticle force Fa was measured using particles having different particle diameters D of the base colored particles, and the value of x in the equation (1) was determined from the relationship between the particle diameter D and the interparticle force Fa. Moreover, the average circularity was calculated | required. This time, the interparticle force was measured using base particles having a particle diameter D of 5.1 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

—Comparative Example 2—
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Comparative Example 1, and the interparticle force was measured using base particles having a particle diameter D of 5.5 μm.
Further, in the same manner as in Comparative Example 1, 100 parts of the base colored particles were mixed with an additive under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

—Comparative Example 3—
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Comparative Example 1, and the interparticle force was measured using base particles having a particle diameter D of 6.0 μm.
Further, in the same manner as in Comparative Example 1, 100 parts of the base colored particles were mixed with an additive under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
(R972; manufactured by Nippon Aerosil Co., Ltd.)
Titanium oxide fine powder 0.3 part
(MT-150A; manufactured by Teika)
Mixing speed 2000rpm
Mixing time 150 sec
Mixer Q mixer

After the toner was prepared, the toner fluidity was measured by the conical rotor method, and the results are shown in Table 1.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.

  FIG. 4 is a graph showing the results of Table 1. It can be seen that the examples of the present invention are superior in dot reproducibility and toner transportability as compared with the comparative example. In order to obtain a toner with good fluidity necessary for obtaining high image quality with good dot reproducibility under toner conditions with a high degree of circularity and a small particle size as in this example, the interparticle force between toner base particles In the relational expression (1) between the toner particles and the toner base particles, it has been found that it is preferable to set the x value to 1.0 to 1.4 and the average value of the interparticle force to 20 to 80 nN. .

According to the present invention, by appropriately controlling the inter-particle force between toner base particles, the can Ru toner for developing an electrostatic image of the good quality dot reproducibility can be stably the toner for electrostatic charge development obtained A manufacturing method can be provided.

FIG. 5 is a diagram showing a force change when scanning is performed after pressing toner particles once on the surface of a toner powder phase that has been compacted, and then separating them. It is a figure which shows the outline | summary of an AFM apparatus. FIG. 6 is a diagram illustrating a relationship between an interparticle force between toner base particles and a toner base particle size. It is a graph which shows the result of the Example and comparative example of this invention. FIG. 6 is a diagram for explaining an example of a developing device to which the toner in the present invention can be preferably applied. It is the schematic which shows the structure of the process cartridge of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Substrate stage 12 Consolidated toner powder phase 13 Toner base particle 14 Probe 15 Piezo scanner 16 Laser generator 33 Doctor roller 34 Supply roller 50 Developing device 56 Toner cartridge 90 Process cartridge

Claims (1)

Using toner base particles having an average circularity of 0.97 to 0.99 including at least a resin and a pigment before adhering or fixing the additive to the surface, one toner base particle is placed at the tip of the probe or its tip The probe is attached to the periphery, and once pressed against one particle on the surface of the compacted toner powder phase composed of the same toner base particles by AFM, the operation of pulling the probe apart is repeated 10 to 50 times. The average value Fa of the interparticle force between the toner base particles obtained by the difference in force acting on the probe when the needle is brought close to and away from the needle satisfies the following formula (1) with the toner base particle diameter D, and The average value Fa is calculated by using the value of the toner base particle diameter D in the toner evaluation method for electrostatic charge development for evaluating whether the average value Fa satisfies 20 to 80 nN. Production of toner by Fa It manages the quality of toner base particles in extent, the production method of the toner for developing an electrostatic image, wherein the toner is produced.
Fa = A × D ^2x (1)
(A: Coefficient)
(x: 1.0 to 1.4)

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