JP2005266597A - Image forming method and developer for electrostatic latent image development - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer for electrostatic latent image development and an image forming method, such that developer volume density is stable, regardless of the environment and toner density is controlled to obtain superior images over a long period. <P>SOLUTION: The developer, which contains a toner and a carrier and is for toner density control using magnetic permeability variation, has a titanium compound A on the toner surface and a titanium compound B on the carrier surface, and has a toner shape coefficient (SF1) of 115 to 140; a lower quantity granularity distribution index of the toner satisfying lower GSDp=D50p/D16p≤1.27 [where D50p is the grain size value at which accumulation bis 50% from a toner grain size quantity distribution small-diameter side and D16p is the grain size value, at which accumulation is 16%]; 1×10<SP>9</SP>Ωcm ≤Rv≤5×10<SP>12</SP>Ωcm [where Rv is the volume resistivity of the carrier at 10,000 V/cm field strength]; and 100×R(A)<R(B) [where R(A) and R(B) are volume resistivity values of the titanium compounds A and B at 10,000 V/cm field strength]. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an image forming method and a developer for developing an electrostatic latent image used when developing an electrostatic latent image with a two-component developer in electrophotography and electrostatic recording.

  In electrophotography, an electrostatic latent image is formed on a latent image carrier (photoreceptor) by a charging process and an exposure process, developed in a developing process to form a developed image, and the developed image is transferred onto a transfer body. In the fixing step, the image is fixed by heating or the like. Developers used in such an electrophotographic method can be roughly classified into a one-component developer using a toner in which a colorant is dispersed in a binder resin and a two-component developer composed of a toner and a carrier. it can. The two-component developer has a relatively large surface area of the carrier, so that it can be easily charged with toner, and by using magnetic particles for the carrier, it can be relatively easily transported by a mag roll or the like. Is currently widely used. On the other hand, since the charge amount of the two-component developer depends to some extent on the amount of toner in the developer, the mixing ratio of the toner and the carrier (hereinafter sometimes referred to as toner concentration) is maintained at a certain ratio. There is a need. Therefore, it is necessary to newly add toner consumed by the development process and control the toner density.

  In recent years, digitization processing has been adopted as a means for achieving high image quality, and high-speed processing of complex images has become possible through digitization processing. Further, a laser beam is used in the process of forming an electrostatic latent image on the latent image carrier, and the electrostatic latent image has been made finer by the development of the exposure technique using a small laser beam. With such development of image processing technology, electrophotography is being developed for light printing and the like. For this reason, it is necessary to faithfully visualize the finer latent image with a developer. In addition, since recent electrophotographic apparatuses are required to be faster and smaller, a technique for highly controlling toner charging and toner density is required to faithfully visualize a finer latent image. ing.

  Currently, there are two main methods for controlling the toner density. One is a method of optically detecting the developed toner image density and controlling the toner density. For example, a patch image is formed as a latent image on a latent image carrier, developed, and the amount of reflected light is measured by irradiating the developed toner image with light, and the toner density is detected by detecting the toner development amount. For example, a developed image developed on a transparent pseudo latent image carrier or a transferred image transferred to a transparent intermediate transfer member is irradiated with light, and the density of the developed image or transferred image is adjusted by the amount of transmitted light. This is a method for detecting and controlling the toner density.

  The other method is a method in which the magnetic permeability, amount, fluidity, and the like of the developer are detected, and the toner density is detected and controlled based on such changes. For example, a control method using a magnetic permeability sensor using an inductance component of a coil can be mentioned. In this method, set values are set in advance, the permeability, amount, fluidity, etc. in a fixed volume are detected, and the magnitude of these permeability, amount, fluidity, etc. relative to this set value is read to supply toner. Is a method for controlling the toner density.

  Among these control means, the former, that is, the method of optically detecting the image density and controlling the toner density is based on changes in the latent image potential due to wear of the latent image carrier due to long-term use, contamination of the sensor light source due to toner scattering, etc. A change in detection accuracy may occur, which is a problem when an optical detection method is used.

  On the other hand, the magnetic permeability method is becoming mainstream because the sensor is not affected by toner contamination, the sensor is small, and the cost is low. However, even in this method, the bulk density may change due to the deterioration of the developer depending on the use environment and the use period, and the apparent permeability of the developer changes with the change in the bulk density. There is a problem that the toner density cannot be detected.

  In general, the charging characteristics of a developer are greatly affected by temperature and humidity, and the developer resistance increases at low temperatures and low humidity, and the charge exchange between carriers decreases. For this reason, the charge held by the carrier generated by frictional charging with the toner is difficult to be relaxed. In such a case, the charge held by the carriers is accumulated and the electrostatic repulsion between the carriers increases. As a result, the apparent density of the developer decreases because the distance between the carriers increases.

  On the other hand, under high temperature and high humidity, the developer resistance is relatively low and the charge exchange between carriers is improved, so that the charge held by the carrier is likely to leak. As a result, the charge held by the carrier is reduced, the electrostatic repulsive force between the carriers is reduced, and the distance between the carriers is reduced, so that the apparent bulk density of the developer is increased.

  Thus, the apparent bulk density of the developer is greatly affected by the developer charging characteristics and the temperature and humidity.

  In order to solve the above problems, a sequence that changes the generated magnetic field strength of the sensor depending on the environment and a sensor that changes the generated magnetic field strength depending on the environment have been studied. Depending on the characteristics of the developer, the toner density control does not function, the development defect due to the high charge amount at low temperature and low humidity, the fog on the non-image area due to the deterioration of the charge exchange property when adding the toner, the image In-machine contamination due to density unevenness and toner scattering, fogging to non-image areas due to low charge at high temperature and high humidity, low resistance of developer magnetic brush in development area, and latent image charge injected into carrier In some cases, image deterioration may occur in which carriers adhere to the latent image carrier (hereinafter sometimes referred to as a photoconductor).

  For example, in Japanese Patent Application Laid-Open No. 8-190274, as a developer for detecting the magnetic permeability and controlling the toner density, the charge amount difference between the developer in the developing device, the carrier in the developing device, and the replenishing toner is constant. A range of developers is disclosed. Although the developer charge amount is constant and the bulk density is not affected by the toner charge control factor, depending on the carrier structure and the characteristic value, the charge held by the carrier accumulates as described above, and the electrostatic charge is generated between the carriers. Since the repulsive force is increased and the distance between the carriers is increased, the developer bulk density is decreased. As a result, image density unevenness due to development failure, fogging to non-image areas due to deterioration of charge exchange property when adding toner, image density unevenness, internal contamination due to toner scattering, and the like occur.

  Further, the bulk density of the developer changes not only the charge of the developer but also the porosity in the developer depending on the toner shape and particle size distribution. For this reason, the developer bulk density may become unstable depending on the shape and particle size distribution of the toner to be replenished even if the charge amount difference between the developer in the developer, the carrier in the developer, and the replenishment toner is constant.

Japanese Patent Laid-Open No. 2003-162140 discloses a technique in which a bulk density sensor and a carrier containing particles having a particle size larger than the resin coating layer thickness are combined as a toner concentration control method. This is because the particles in the resin coating layer act as a spacer to stabilize the bulk density of the carrier, prevent toner deterioration and stabilize toner charging, and the carrier core material and the particles are in contact with each other. Therefore, depending on the resistance of the particles, low temperature and low humidity charge-up is suppressed, and the developer bulk density is stabilized. However, since the developer magnetic brush has a low resistance, there is a case where the image is deteriorated in which the carrier adheres to the photoreceptor at high temperature and high humidity. Moreover, the usable range with respect to the particle diameter and addition amount of the particles is narrow, the dispersion state in the resin coating layer is deteriorated, the strength of the resin coating layer is lowered, and it may not be able to withstand long-term use.
JP-A-8-190274 Japanese Patent Laid-Open No. 2003-162140

  As described above, in order to stably control the toner density regardless of the environment, the sensing method alone is not enough to control the toner density, and the image density unevenness at low temperature and low humidity, toner scattering and fogging, and the image density control at high temperature and high humidity. Image degradation due to toner scattering, carrier adhesion, and the like becomes a problem.

  Thus, in order to obtain a high image quality with more precise toner density control accuracy, it is necessary to further improve the developer characteristics.

  Accordingly, the object of the present invention has been made in view of the above problems, and the developer bulk density is stable and the toner density is controlled regardless of the environment, the toner scattering is small, the image density is stable without fogging and white spots. To provide a developer for developing an electrostatic latent image and an image forming method capable of obtaining a good image over a long period of time.

  As a result of repeated detailed studies on the above problems, the inventors of the present invention not only changed the developer's bulk density but also the developer's powder characteristics (fluidity, packing properties, etc.), as well as the developer's electrical resistance characteristics and charging. Since the characteristics also have a great influence, by defining the developer in a specific structure in an electrophotographic apparatus having means for controlling the toner concentration as a change in magnetic permeability of the developer, the bulk density of the developer can be increased regardless of the environment. It has been found that an electrostatic latent image developing developer and an image forming method capable of obtaining a good image that solves the above-mentioned various problems over a long period of time can be obtained. That is, the present invention

<1> A step of developing a latent image on a latent image carrier using a developer for developing an electrostatic latent image including at least a toner and a carrier, and controlling the toner concentration as a change in magnetic permeability of the developer. In the image forming method to
The developer for developing an electrostatic latent image, wherein the titanium compound A is adhered to the toner surface, the titanium compound B is adhered to the carrier surface, and satisfies the following condition: It is.
Condition (1): The toner shape factor (SF1) is 115 to 140.
Condition (2): Lower toner particle size distribution index: Lower GSDp = D50p / D16p ≦ 1.27 [where D50p: toner particle size distribution, particle size at which accumulation is 50% from the smaller diameter side, D16p: toner Particle size distribution The particle size at which accumulation is 16% from the smaller diameter side]
Condition (3): 1 × 10 ⁹ Ω · cm ≦ Rv ≦ 5 × 10 ¹² Ω · cm [where Rv: volume resistivity of carriers at electric field strength of 10000 V / cm]
Condition (4): 100 × R (A) <R (B) [where R (A): volume resistivity of titanium compound A at an electric field strength of 10,000 V / cm, R (B): at an electric field strength of 10,000 V / cm Volume resistivity of titanium compound B]

<2> A developer for developing an electrostatic latent image for controlling toner density using at least a toner and a carrier and using a change in magnetic permeability of the developer,
A developer for developing an electrostatic latent image, wherein a titanium compound A is adhered to the toner surface, a titanium compound B is adhered to the carrier surface, and the following conditions are satisfied.
Condition (1): The toner shape factor (SF1) is 115 to 140.
Condition (2): Lower toner particle size distribution index: Lower GSDp = D50p / D16p ≦ 1.27 [where D50p: toner particle size distribution, particle size at which accumulation is 50% from the smaller diameter side, D16p: toner Particle size distribution The particle size at which accumulation is 16% from the smaller diameter side]
Condition (3): 1 × 10 ⁹ Ω · cm ≦ Rv ≦ 5 × 10 ¹² Ω · cm [where Rv: volume resistivity of carriers at electric field strength of 10000 V / cm]
Condition (4): 100 × R (A) <R (B) [where R (A): volume resistivity of titanium compound A at an electric field strength of 10,000 V / cm, R (B): at an electric field strength of 10,000 V / cm Volume resistivity of titanium compound B]

  <3> The electrostatic latent image developing developer according to <2>, wherein the coverage F of the titanium compound A with respect to the toner satisfies a relationship of 3% ≦ F ≦ 10%.

  <4> The electrostatic latent image developing developer according to <2> or <3>, wherein the titanium compound A has a particle size of 40 to 200 nm.

<5> Volumetric resistance 1 × 10 ¹² to 1 × 10 ¹⁶ Ω · cm at an electric field strength of 10,000 V / cm of the titanium compound B is described in any one of <2> to <4> It is a developer for developing an electrostatic latent image.

  According to the present invention, the developer bulk density is stable regardless of the environment, the toner density is controlled, the toner scattering is small, and a stable image with good image density without fogging and carrier adhesion can be obtained over a long period of time. An electrostatic latent image developing developer and an image forming method can be provided.

  Hereinafter, the present invention will be described in detail. The developer will be described together with the image forming method.

  As described above, the present invention is an image forming method for controlling the toner density as a change in the permeability of the developer, and controls the change in the charge amount of the developer even under high temperature and high humidity or low temperature and low humidity. This suppresses the change in the bulk density of the developer and facilitates the toner concentration control by the change in magnetic permeability.

  In contact charging between the toner (toner particles) and the carrier, frictional charging occurs near the contact portion. Therefore, the toner having a shape close to a sphere can be charged uniformly. Similarly, with respect to the particle size distribution, the smaller the fine toner particles, that is, the narrower the particle size distribution, the more uniformly charged the toner can be. Further, the external additive adhering to the toner surface can be controlled more uniformly on the toner surface and with less difference in adhering amount between the toners as the toner shape is closer to a sphere and the particle size distribution of the toner is narrower.

  Accordingly, the volume resistance of the carrier is regulated within an appropriate range, and the titanium compound A is adhered to the toner (toner particles) and the titanium compound B is adhered (externally added) to the carrier while ensuring charge exchange with the toner. Thus, the charge amount of the developer can be controlled regardless of the environment. That is, the appropriate volume resistance of the titanium compound A on the toner surface maintains the charge amount even under high temperature and high humidity, suppresses the decrease in electrostatic repulsion between carriers, and the volume of the titanium compound B on the carrier surface. By maintaining the charge exchange property between the carriers under low temperature and low humidity, the resistance suppresses the charge-up and suppresses the increase in electrostatic repulsion between the carriers. Further, the volume resistance between the titanium compound A and the titanium compound B is reduced to a certain extent with respect to the titanium compound A, thereby balancing the chargeability of the toner and the charge exchangeability of the carrier and stabilizing the developer charge. , The change in bulk density can be suppressed.

  According to the present invention, the toner density can be controlled more accurately by setting the toner shape SF1 to a toner shape of 115 to 140 (condition (1)). In terms of stabilization of the bulk density, a toner shape having a small porosity tends to be stable when the shape is close to a sphere. However, a spherical toner having a toner shape of less than 115 may not be able to detect the actual magnetic permeability of the developer in a developing machine employing the magnetic permeability method because the replacement of the developer is poor. On the other hand, in the irregular toner whose toner shape exceeds 140, the change in the porosity of the developer is large, and the magnetic permeability of the developer is difficult to stabilize. Further, the shape is likely to be deformed by mechanical stress, and the porosity in the developer changes with time, so that the magnetic permeability becomes unstable and toner density control may be difficult.

  Further, according to the present invention, the toner concentration can be controlled more accurately by setting the toner particle size distribution to the lower number particle size distribution index: lower GSDp ≦ 1.27 (condition (2)). In general, the smaller the diameter of toner, the higher the charge amount and the harder it is to develop. Therefore, by controlling the amount of the small diameter toner, it is possible to facilitate the replacement of the toner and to control the toner density due to the change in magnetic permeability. If the lower GSDp is out of the range, the amount of small-diameter toner increases, so the amount of toner to be developed decreases with respect to the charge amount, and problems such as a decrease in toner density may occur.

In addition, according to the present invention, by controlling the volume resistivity Rv of the carrier in the range of 1 × 10 ⁹ Ω · cm to 5 × 10 ¹² Ω · cm, the amount of charge held by the carrier at low temperature and low humidity can be reduced. Increase (charge up), excessive decrease in developer resistance under high temperature and high humidity, and occurrence of problems such as adhesion of carriers to the photoreceptor due to charge injection of image charges onto the latent image carrier. (Condition (3)).

Here, the preferred carrier volume resistivity is 5 × 10 ⁹ Ω · cm to 1 × 10 ¹² Ω · cm, more preferably 1 × 10 ¹⁰ Ω · cm to 1 × 10 ¹² Ω · cm. This is preferable in that the amount difference can be controlled. The volume resistivity of the carrier is a value at an electric field strength of 10,000 V / cm.

  In addition, according to the present invention, the carrier can be further improved in charge exchange between the carriers by externally adding titanium compound B to the surface, thereby independently controlling the resistance of the carrier particles and the carrier surface resistance to some extent. be able to.

  Therefore, the resistance of the carrier is controlled by the resistance adjusting agent type and addition amount in the resin coating film, and the carrier surface resistance is controlled by the characteristics and addition amount of the externally added titanium compound B, and the carrier is charged at low temperature and low humidity. Thus, it is possible to prevent a reduction in charge amount due to excessive charge exchange under high temperature and high humidity.

  In addition, by adding titanium compound B externally to the surface of the carrier, it exhibits the function of a flow agent and improves the flowability and packing property of the developer, and prevents an excessive increase in bulk density due to the spherical shape of the toner. can do.

  Further, according to the present invention, a preferable charge amount can be obtained by attaching (externally adding) the titanium compound A to the toner surface. As described above, the toner charged in contact with the carrier is charged only at the contact portion, but since most of the toner uses an insulating polymer resin as a binder resin, its own volume resistance is high, and the toner surface Since the charged charge generated in the toner is unevenly distributed only at the contact portion of the toner surface, the external addition of the titanium compound A can reduce the uneven distribution of the charge and make the charge on the toner surface uniform.

  Further, according to the present invention, the volume resistance R (A) of the titanium compound A externally added to the toner surface and the volume resistance R (B) of the titanium compound B externally added to the carrier surface are 100 × R (A). <R (B) must be in the range (condition (4)).

  Even if the carrier surface resistance is lowered, if the coverage of toner (toner particles) having a higher surface resistance is increased, that is, if the toner concentration is increased, the charge exchange property between carriers is lowered. The presence of the titanium compound A having a lower resistance than the titanium compound B on the carrier surface on the toner surface locally lowers the resistance of the toner surface. That is, the presence of a titanium compound that functions as a charge exchange site on a part of the toner surface enables charge exchange between carriers, thereby reducing the electrostatic repulsion between carriers and stabilizing the bulk density.

  On the other hand, when the toner concentration is lowered, the charge exchange property between the carriers is increased, but the excessive charge exchange property can be suppressed by the titanium compound B on the carrier surface.

  That is, since the developer tends to decrease the charge amount under high temperature and high humidity, it is necessary to decrease the toner concentration, and the charge exchange property between the carriers is decreased by the titanium compound B on the carrier surface. Since the amount of charge tends to increase below, the electrostatic charge between carriers can be reduced against changes in the amount of charge due to changes in the environment and toner density by securing charge exchange with the lower resistance titanium compound A. It suppresses the change in the bulk density of the developer derived from repulsion and suppresses the influence on the magnetic permeability.

Here, the volume resistance R (A) of the titanium compound A and the volume resistance R (B) of the titanium compound B must have a relationship of 100 × R (A) <R (B). The typical volume resistivity is preferably about 1 × 10 ¹⁰ to 1 × 10 ¹³ Ω · cm.

Further, the volume resistivity of the titanium compound B is preferably in the range of 1 × 10 ¹² to 1 × 10 ¹⁶ Ω · cm, and more preferably 1 × 10 ¹³ to 1 × 10 ¹⁵ Ω · cm, from the viewpoint of charge exchange. If the volume resistivity is less than 1 × 10 ¹² Ω · cm, the charge exchange property is improved, but charge leakage occurs in an environment of high temperature and high humidity, and the amount of charge becomes low, so fogging occurs. When the volume resistivity exceeds 1 × 10 ¹⁶ Ω · cm, a sufficient charge exchange property cannot be obtained, and not only the bulk density is reduced particularly in a low-temperature and low-humidity environment, but also the toner additional property. May worsen and toner scattering may occur.

  In addition, the volume resistivity of the titanium compounds A and B is a value at an electric field strength of 10000 V / cm.

  The titanium compound A and the titanium compound B are not particularly limited as long as they are titanium compounds in the volume resistivity range described above. Examples thereof include titanium mixed crystal compounds such as titanium oxide, metatitanic acid, barium titanate, magnesium titanate, strontium titanate, titanium-silica mixed crystal compounds, and titanium surface treatment compounds. More preferably, titanium oxide, metatitanic acid, or barium titanate can be used.

  In the present invention, if the coverage F of the titanium compound A in the developer with respect to the toner is 3% ≦ F ≦ 10%, the balance between charge exchange and chargeability can be further improved. When the coverage F is less than 3%, the low resistance area on the toner surface is small and the effects of the present invention may not be realized. On the other hand, when the coverage F exceeds 10%, the charge exchange property is improved, but the toner surface is lowered in resistance, so that a desired charge amount cannot be obtained and toner scattering and fogging occur. There is a case.

The coverage F can be obtained by the following equation.
Formula: F = 3 ^0.5 / (2π) × (Dt / Da) × (ρt / ρa) × C × 100
Here, Dt is the toner particle diameter, Da is the particle diameter of the titanium compound A, ρt is the true specific gravity of the toner, ρa is the true specific gravity of the titanium compound A, and C is the titanium compound weight / (toner weight + titanium compound weight). means.

  Further, if the particle size of the titanium compound A is 40 to 200 nm, it is preferable from the viewpoint of embedding and detaching from the toner surface, and more preferably 50 to 150 nm. When the particle size is less than 40 nm, in an environment in which the toner is excessively stressed, it may be easily embedded in the toner surface and may not be sufficient to exhibit the function of the present invention. On the other hand, when it exceeds 200 nm, it is difficult to adhere to the toner surface, which may be insufficient for expressing the function of the present invention. Furthermore, since the state of adhesion to the toner becomes non-uniform, the charge distribution becomes wide, and toner scattering and fogging may occur.

Next, a method for producing the toner used in the present invention will be described.
The toner used in the present invention is not particularly limited as long as it can form particles having a lower GSDp representing the lower number particle size distribution index of 1.27 or less and a shape factor SF1 in the range of 115 to 140. However, the emulsion polymerization aggregation method is particularly preferable.

  In the emulsion polymerization aggregation method, a resin particle dispersion in which resin particles having a particle diameter of 1 μm or less are dispersed, a colorant dispersion in which a colorant is dispersed, and the like are mixed to aggregate the resin particles and the colorant into a toner particle diameter. (Hereinafter, sometimes referred to as “aggregation step”), a step of heating the resin particles to a temperature equal to or higher than the glass transition point of the resin particles to fuse the aggregates to form toner particles (hereinafter, sometimes referred to as “fusion step”). including.

  In the aggregation step, the resin particle dispersion, the colorant dispersion, and, if necessary, the particles in the release agent dispersion are aggregated to form aggregated particles. The agglomerated particles are formed by heteroaggregation or the like. For the purpose of stabilizing the agglomerated particles and controlling the particle size / particle size distribution, the ionic surfactant having a polarity different from that of the agglomerated particles, or a monovalent or more monovalent metal salt or the like is used. A charged compound is added.

  In the fusion step, the resin particles in the aggregated particles are melted at a temperature condition equal to or higher than the glass transition point, and the aggregated particles change from an indeterminate shape to a spherical shape. At this time, the shape factor SF1 of the agglomerated particles is 150 or more. However, the shape factor SF1 can be controlled by stopping the heating of the toner when the desired shape factor is reached. Thereafter, the agglomerates are separated from the aqueous medium, and washed and dried as necessary to form toner particles.

  Further, a suspension polymerization method can also be preferably used as a method for producing the toner used in the present invention. In the suspension polymerization method, colorant particles, release agent particles and the like are suspended in an aqueous medium to which a dispersion stabilizer and the like are added together with a polymerizable monomer as required, and a desired particle size and particle size distribution are obtained. In this method, the polymerizable monomer is polymerized by means of heating or the like, and then the polymer is separated from the aqueous medium, and washed and dried as necessary to form toner particles.

  In addition, as a method for producing the toner used in the present invention, a solution suspension granulation method can be used. In the dissolution suspension granulation method, a polymerizable monomer, a polymerization initiator, a release agent, and magnetic metal fine particles are dispersed in a polymer solution in which a polymerizable monomer is preliminarily polymerized. In the presence of an inorganic or organic dispersant, a mechanical shearing force is applied to suspend the mixture, and then a polymerizable monomer is polymerized by applying thermal energy while applying stirring shear to obtain toner particles. It is a manufacturing method.

  Further, as a method for producing the toner used in the present invention, a dissolution suspension method can also be used. In the dissolution suspension method, a solution in which a binder resin, a release agent, a colorant, and the like are dissolved in an organic solvent is suspended by applying a mechanical shear force in the presence of an inorganic or organic dispersant, In this method, toner particles are obtained by removing the solvent.

  Further, as a method for producing the toner used in the present invention, a solution emulsion aggregation coalescence method can be used. The dissolution emulsification aggregation coalescence method is a method in which a solution in which a binder resin is dissolved in an organic solvent is desolvated by emulsifying mechanical shearing force in the presence of an anionic surfactant or the like, and a resin of at least 1 μm or less. After obtaining the fine particles, the step of cooling below the glass transition temperature of the binder resin to prepare a resin fine particle dispersion solution, the resin fine particle dispersion solution, a colorant fine particle dispersion in which the colorant fine particles are dispersed, and An aggregating step of mixing the release agent fine particle dispersion in which the release agent fine particles are dispersed to form aggregated particles of the resin fine particles, the colorant fine particles and the release agent fine particles, and the aggregated particles, the glass transition point or melting point of the resin fine particles This is a manufacturing method having a fusion / unification step of fusing and uniting by heating to the above temperature.

  Among these methods, the emulsion polymerization aggregation method is most suitable from the viewpoints of controllability of the particle size distribution and controllability of the toner shape. The reason is that since there is no shearing force at the time of granulation, there is little generation of coarse and fine powder, and the particle size can be controlled from an irregular shape to a spherical shape.

  The binder resin used for the toner includes styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate. , Α-methylene aliphatic monocarboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Examples include homopolymers and copolymers of vinyl ethers such as esters, vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropenyl ketone, etc. In particular, typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, and styrene-anhydride copolymer. Mention may be made of maleic acid copolymers, polyethylene, polypropylene and the like. Further examples include polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like.

  In order to improve the chargeability with the carrier, the binder resin may contain a dissociable vinyl monomer together with the monomer constituting the binder resin when the binder resin is polymerized. Examples of the dissociative vinyl monomer include acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, ethyleneimine, vinylpyridine, vinylamine and other polymer acids and polymer base materials. Any of the monomers can be used. Polymer acids are preferred because of the ease of polymer formation reaction, among others, dissociable vinyl monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, etc. It is preferable from the viewpoint of controllability. In addition, these dissociative vinyl monomers can be used by copolymerizing usually at the time of binder resin polymerization.

  In the toner of the present invention, a chain transfer agent can be used during the polymerization of the binder resin. Although there is no restriction | limiting in particular as a chain transfer agent, The compound which has a thiol component can be used. Specifically, alkyl mercaptans such as hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, and dodecyl mercaptan are preferred, and in particular, the molecular weight distribution is narrow, so that the storage stability of the toner at high temperature is improved. preferable.

  A cross-linking agent may be added to the binder resin in the present invention as necessary. Specific examples of such crosslinking agents include aromatic polyvinyl compounds such as divinylbenzene and divinylnaphthalene; divinyl phthalate, divinyl isophthalate, divinyl terephthalate, divinyl homophthalate, divinyl trimesate / trivinyl, naphthalene dicarboxylate Polyvinyl esters of aromatic polyvalent carboxylic acids such as divinyl acid and diphenyl biphenyl carboxylate; Divinyl esters of nitrogen-containing aromatic compounds such as divinyl pyridine dicarboxylate; Vinyl pyromutate, vinyl furan carboxylate, pyrrole-2- Vinyl esters of unsaturated heterocyclic compounds such as vinyl carboxylate and vinyl thiophenecarboxylate; butanediol methacrylate, hexanediol acrylate, octanediol methacrylate, decanediol acrylate (Meth) acrylic acid esters of linear polyhydric alcohols such as dodecanediol methacrylate; branches such as neopentylglycol dimethacrylate and 2-hydroxy-1,3-diacryloxypropane; ) Acrylic acid esters; Polyethylene glycol di (meth) acrylate, Polypropylene polyethylene glycol di (meth) acrylates; Divinyl succinate, divinyl fumarate, vinyl / divinyl maleate, divinyl diglycolate, vinyl / divinyl itaconate, acetone Divinyl dicarboxylate, divinyl glutarate, divinyl 3,3′-thiodipropionate, trans-aconite divinyl / trivinyl, divinyl adipate, divinyl pimelate, divinyl suberate, dizelaline Alkenyl, sebacate, divinyl dodecanedioate divinyl, the polyvinyl esters of polycarboxylic acids such as oxalic acid, divinyl; and the like.

  In the present invention, these crosslinking agents may be used alone or in combination of two or more. Among the above crosslinking agents, as the crosslinking agent in the present invention, (meth) acrylic acid esters of linear polyhydric alcohols such as butanediol methacrylate, hexanediol acrylate, octanediol methacrylate, decanediol acrylate, and dodecanediol methacrylate are used. Branched chains such as neopentyl glycol dimethacrylate and 2-hydroxy-1,3-diacryloxypropane, (meth) acrylic acid esters of substituted polyhydric alcohols; polyethylene glycol di (meth) acrylate, polypropylene polyethylene glycol di ( It is preferable to use (meth) acrylates.

  The content of the crosslinking agent is preferably in the range of 0.05 to 5% by weight, more preferably in the range of 0.1 to 1.0% by weight, based on the total amount of polymerizable monomers.

  The resin used for the toner in the present invention can be produced by radical polymerization of a polymerizable monomer. There is no restriction | limiting in particular as an initiator for radical polymerization used here. Specifically, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide Ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, tert-butyl hydroperoxide pertriphenyl acetate, tert-butyl formate, Peroxides such as tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, tert-butyl perN- (3-toluyl) carbamate, 2,2 '-Azobisp Bread, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2 ′ -Azobis (2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2- Methyl methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (1 -Sodium methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihy Roxymethylphenylazo-2-methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 2,2′-azobis-2-methylvaleronitrile, 4,4′-azobis-4 -Dimethyl cyanovalerate, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'- Azobis-1-chlorophenylethane, 1,1′-azobis-1-cyclohexanecarbonitrile, 1,1′-azobis-1-cycloheptanenitrile, 1,1′-azobis-1-phenylethane, 1,1 ′ -Azobiscumene, 4-nitrophenylazobenzyl cyanoacetate ethyl, phenylazodiphenylmethane, phenylazotriphenylmeth Tan, 4-nitrophenylazotriphenylmethane, 1,1′-azobis-1,2-diphenylethane, poly (bisphenol A-4,4′-azobis-4-cyanopentanoate), poly (tetraethylene glycol) -2,2'-azobisisobutyrate) and the like, 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazene and the like Can be mentioned.

  Examples of the colorant used in the toner of the present invention include magnetic powders such as magnetite and ferrite, carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue. , Malachite green oxalate, lamp black, rose bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 can be cited as a representative example.

  The release agent used in the toner of the present invention includes low molecular weight polyolefins such as polyethylene, polypropylene and polybutene: silicones having a softening point upon heating: oleic amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, etc. Fatty acid amides such as: carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil etc. Plant waxes: animal waxes such as beeswax: montan wax, ozokerite, ceresin, paraffin wax, microcrystalline Examples thereof include minerals such as waxes, Fischer-Tropsch waxes, and petroleum-based waxes, and modified products thereof.

  Further, in the preparation of the toner of the present invention, when an aqueous medium is used, for example, as in the emulsion polymerization aggregation method as described above, a surfactant is used for the purpose of improving the dispersibility, emulsifiability, etc. of the material in the aqueous medium. Can also be used.

  Examples of the surfactant include sulfate surfactants, sulfonates, phosphates, soaps, and the like; amine surfactants, quaternary ammonium salt and other cationic surfactants; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable.

  In addition, a charge control agent may be added to the toner of the present invention as necessary. Known charge control agents can be used, but azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups can be used. When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. The colored particles in the present invention may be either magnetic containing a magnetic material or non-magnetic colored particles not containing a magnetic material.

  These colorants, mold release agents, charge control agents, etc. are dispersed by known methods, for example, rotary shear type homogenizers, media type dispersers such as ball mills, sand mills, and attritors, high pressure opposed collision type dispersions. A machine or the like is preferably used.

  The additive externally added to the toner of the present invention may use other inorganic fine particles in addition to the titanium compound A. Other inorganic fine particles include silica, titanium oxide, metatitanic acid, aluminum oxide, magnesium oxide, alumina, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, chromium oxide, antimony trioxide, and oxidation. Fine particles such as magnesium and zirconium oxide are exemplified. Among these, it is desirable to use one selected from silica, titanium oxide, and metatitanic acid from the viewpoint of precise toner charge control.

  In addition, for the purpose of removing deposits and deteriorated substances on the surface of the photoreceptor, inorganic fine particles, organic fine particles, composite fine particles obtained by attaching inorganic fine particles to the organic fine particles, and the like can be added.

  The toner used in the present invention can be produced by mixing with an external additive using a Henschel mixer or a V blender. Further, when the colored particles are produced by a wet method, they can be externally added by a wet production method.

Next, the constituent material and structure of the carrier of the present invention will be described.
The carrier of the present invention is a so-called coat carrier having a resin coating layer on a core material. As said core material, well-known things, such as metal powder which shows ferromagnetism, such as ferrite, magnetite, iron, cobalt, nickel, can be used. Among these, ferrite particles having a low specific gravity are suitable for suppressing carrier coat peeling due to stress received in the developing machine and spent toner components on the carrier surface. As the ferrite, magnetic particles formed by using, as main components, an oxide of one or more elements selected from Li, Mg, Ca, Mn, Ni, Cu, and Zn and Fe ₂ O ₃ are used in the present invention. In order to obtain the desired magnetic susceptibility, magnetic particles mainly composed of an oxide of one or more elements selected from Li, Mg, and Mn and Fe ₂ O ₃ are more preferable.

  The volume average particle diameter of the magnetic particles is preferably in the range of 10 to 55 μm because the charging characteristics of the toner can be kept stable. When the volume average particle size of the magnetic particles is less than 10 μm, it is necessary to increase the coverage of the toner with respect to the carrier in order to obtain an appropriate charge amount, and the spent of the toner component is deteriorated. For this reason, it may be difficult to keep the charging characteristics of the carrier stable. Further, since the magnetic force per carrier particle becomes small, the magnetic binding force of the chain on the magnetic brush becomes weaker than the developing electric field, so that the carrier is developed on the photosensitive member. On the other hand, if the volume average particle size exceeds 55 μm, the resin coating layer is easily peeled off due to stress in the developing machine, and the charging characteristics and resistance of the carrier may be reduced.

  In addition, the magnetic force of the magnetic particles preferably has a saturation magnetic value at 3000 oersted of 50 emu / g or more, more preferably 60 emu / g or more. With a magnetic force whose saturation magnetic value is weaker than 50 emu / g, the magnetic binding force of the chain on the magnetic brush becomes weaker than the developing electric field, so that the carrier may be developed on the photoreceptor.

  The resin used for the resin coating layer may be selected from any resins that can be used in the industry as the carrier coating layer, and may be used alone or in combination of two or more. As the coating resin, it is preferable to use a charge imparting resin for imparting chargeability to the toner and a low surface energy material for preventing the toner component from being transferred to the carrier.

  Examples of the charge imparting resin for imparting negative chargeability to the toner include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinylidene resins, acrylic resins, polymethyl methacrylate resins, polystyrene resins such as styrene-acrylic copolymer resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, ethyl cellulose resins, etc. Examples thereof include cellulose resins. Examples of the charge imparting resin for imparting positive chargeability to the toner include polystyrene resins, halogenated olefin resins such as polyvinyl chloride, polyester resins such as polyethylene terephthalate resins and polybutylene terephthalate resins, and polycarbonate resins. Can be mentioned. Low surface energy materials for preventing the transfer of toner components to the carrier include polystyrene resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, fluorocarbon resin. Fluoroterpolymers such as copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and vinyl fluoride, terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, And silicone resin.

Conductive powder may be added to the carrier coating resin layer for the purpose of adjusting the volume resistance of the carrier necessary for the present invention. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm and dispersion is poor in the coating resin layer, when it becomes difficult to control the electric resistance, the strength of the coating resin layer is lowered and the electric resistance characteristics and charging characteristics of the carrier are maintained. May be difficult to do. The conductivity of the conductive powder itself is preferably 10 ¹⁰ Ωcm or less, and more preferably 10 ⁹ Ωcm or less. Furthermore, a plurality of conductive resins and the like can be used in combination as necessary.

  The content of the conductive powder in the resin coating layer is preferably 0.05 to 1.5 parts by weight, and more preferably 0.1 to 1.0 parts by weight with respect to 100 parts by weight of the coating resin. When the content is less than 0.05 parts by weight, the volume resistance of the carrier is increased as described above, the charge exchange property between the carriers is lowered, and the bulk density of the developer is increased. In addition, the reproducibility of a solid-solid image may be inferior because it becomes difficult to function as a developing electrode and an edge effect occurs particularly in a solid portion. On the other hand, when the amount exceeds 1.5 parts by weight, the volume resistance of the carrier decreases, the charge exchange property between the carriers increases, and the bulk density of the developer decreases. In addition, image quality defects such as white spots may be caused by developing a carrier in the image area.

  Further, the resin coating layer of the carrier may contain resin fine particles for the purpose of charge control. Specific examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene; polyvinyl and polyvinylidene resins such as polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polychlorinated. Vinyl, polyvinyl carbazole, polyvinyl ether and polyvinyl ketone; vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; straight silicone resin composed of an organosiloxane bond or a modified product thereof; fluororesin such as polytetrafluoroethylene, Examples thereof include polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene; polyester; polycarbonate and the like.

  Examples of thermosetting resins include phenol resins; amino resins such as urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins; epoxy resins and the like.

  The particle size of the resin particles is preferably 0.1 to 1.5 μm. When the particle size is less than 0.1 μm, the dispersibility is poor and the resin coating layer is aggregated, and the exposure amount on the surface of the carrier becomes unstable, making it difficult to keep the charging characteristics stable. In addition, the film strength of the resin coating layer may be reduced at the interface of the aggregates and easily cracked. On the other hand, when the thickness exceeds 1.5 μm, detachment from the coating layer is likely to occur, and the function of imparting charge may not be exhibited.

  The content of the resin particles in the resin coating layer is preferably 0.05 to 1.0 part by weight, more preferably 0.1 to 0.6 part by weight. If the content is less than 0.05 parts by weight, the charge stability and charge maintaining property may be insufficient. On the other hand, when the amount exceeds 1.0 part by weight, the strength of the resin coating layer may be reduced and the coating layer may be easily broken.

  The weight ratio of the carrier core (core) to the resin coating layer is preferably 100: 2.0 to 100: 4.0. When the resin coating ratio is 2.0 or less, it is difficult to maintain the volume resistance of the carrier for a long time, and when it is 4.0 or more, the carrier productivity is difficult and the flowability of the developer in the developing machine is difficult. It deteriorates and it becomes difficult to express the function of the present invention.

  As a typical method for forming a coating resin on a carrier core material, a raw material solution for forming a resin coating layer (a matrix resin, nitrogen-containing resin fine particles, conductive fine powder, etc. are appropriately contained in a solvent) is used. Dipping method in which core powder or charge imparting member is immersed in resin coating layer forming solution, spray method in which resin coating layer forming solution is sprayed on the surface of carrier core material or charge imparting member, carrier core material in flowing air The fluidized bed method in which the solution for forming the resin coating layer is sprayed in a state of being suspended by the above, the kneader coater method in which the carrier core material and the solution for forming the resin coating layer are mixed in the kneader coater, and then the solvent is removed. However, it is not particularly limited to those using a solution, and depending on the carrier core material and the charge imparting member to be applied, it may be a powder coating method in which the resin powder is heated and mixed. It can be appropriately employed in the.

  The solvent used in the raw material solution for forming the resin coating layer is not particularly limited as long as it dissolves the matrix resin. For example, aromatic hydrocarbons such as xylene and toluene, acetone , Ketones such as methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, halides such as chloroform and carbon tetrachloride, and the like can be used.

  The method for attaching the titanium compound B to the surface of the resin coating layer is not particularly limited as long as it is a commonly used mixing apparatus. Specific examples include addition methods using a V-type blender, cement mixer, paint shaker, Henschel mixer, kneader coater, and the like.

The image forming method of the present invention will be described in detail below.
The image forming method of the present invention is formed on the surface of the latent image carrier using at least a latent image forming step for forming an electrostatic latent image on the surface of the latent image carrier and a developer containing at least a toner and a carrier. A developing step of developing the electrostatic latent image to form a toner developed image, a step of transferring a toner image formed on the surface of the latent image carrier onto a recording medium, and a toner image transferred on the surface of the recording medium The toner concentration is controlled as a change in magnetic permeability of the developer, and the developer for developing an electrostatic image of the present invention is used as the developer.

  The control of the toner concentration as the change in the magnetic permeability of the developer can be realized by a known means.

  The latent image forming step is a step of forming an electrostatic latent image by uniformly charging the surface of the latent image carrier with a charging means and then exposing the latent image carrier with a laser optical system or an LED array. It is. Examples of the charging means include a non-contact charger such as corotron and scorotron, and a contact method in which a latent image carrier surface is charged by applying a voltage to a conductive member in contact with the latent image carrier surface. Any type of charger may be used. However, a contact charging type charger is preferable from the viewpoint that the amount of ozone generated is small and the effect of excellent printing durability is exhibited. In the contact charging type charger, the shape of the conductive member may be any of a brush shape, a blade shape, a pin electrode shape, a roller shape, and the like, but a roller-like member is preferable. The image forming method of the present invention is not subject to any particular limitation in the latent image forming process.

  The developing step is a step of bringing a developer carrying member having a developer layer containing at least toner on the surface thereof into contact with or approaching the surface of the latent image carrying member to the electrostatic latent image on the surface of the latent image carrying member. In this step, particles are adhered to form a toner image (development image) on the surface of the latent image carrier. The development method can be performed using a known method, but examples of the development method using a two-component developer include a cascade method and a magnetic brush method. The image forming method of the present invention is not particularly limited with respect to the developing method.

  The transfer step is a step of transferring a toner image formed on the surface of the latent image carrier to form a transfer image. Examples of a transfer device for transferring a toner image from a latent image carrier onto paper or the like include conventional corotron and scorotron transfer, but a method using a conductive bias transfer roll made of an elastic material with less generation of ozone or the like Is mentioned. As a transfer roll, a metal roll whose surface is covered with a rubber layer and this surface rubber layer is fluorine treated is often used. Further, in order to effectively avoid the situation where residual toner or the like adheres to this type of transfer roll, a cleaning device is provided in which a cleaning blade is placed in contact with the transfer roll. Here, as the cleaning blade, for example, an elastic body such as urethane rubber is used so as not to damage the fluorine-treated film that is the surface coating layer of the transfer roll. However, the transfer blade member and the roll cleaning means are particularly limited. It is not a thing. At the time of transfer, the bias transfer roll is brought into pressure contact with the latent image carrier at a pressure of 5 g / cm or more to perform contact transfer for transferring a toner image onto a sheet.

  The fixing step is a step of fixing the toner image transferred on the surface of the recording medium with a fixing device. As the fixing device, a heat fixing device using a heat roll is preferably used. The heat fixing device includes a fixing roller having a heater lamp for heating inside a cylindrical metal core, a so-called release layer formed on the outer peripheral surface by a heat resistant resin film layer or a heat resistant rubber film layer, and the fixing roller. The pressure roller or pressure belt is disposed in pressure contact with the roller and has a heat-resistant elastic layer formed on the outer peripheral surface of the cylindrical metal core or the surface of the belt-like base material. The fixing process of an unfixed toner image is performed by inserting a recording medium on which an unfixed toner image is formed between a fixing roller and a pressure roller or a pressure belt to heat the binder resin, additive, etc. in the toner. Fix by melting. In the image forming method of the present invention, the fixing method is not particularly limited.

  In the image forming method of the present invention, when producing a full-color image, each of the plurality of latent image carriers has a developer carrier of each color, and the plurality of latent image carriers and developer carriers. Through a series of processes consisting of a latent image forming process, a developing process, and a transfer process, each color toner image is sequentially stacked on the same recording medium surface, and the stacked full-color toner images are fixed. An image forming method in which heat fixing is performed in the process is preferably used. By using the developer for developing an electrostatic image in the image forming method, stable development, transfer, and fixing performance can be obtained even in a tandem system suitable for, for example, miniaturization and color acceleration. .

  Examples of the recording medium to which the toner image is transferred include plain paper, OHP sheet, and the like used for electrophotographic copying machines and printers. In order to further improve the smoothness of the image surface after fixing, the surface of the recording medium is preferably as smooth as possible. For example, coated paper in which the surface of plain paper is coated with a resin, art paper for printing, etc. Can be preferably used.

  Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. In the following description, “parts” means “parts by weight” unless otherwise specified.

  In addition, each characteristic value of the toner, carrier and developer of Examples and Comparative Examples was measured by the following method.

- toner shape factor SF1 (ML ² / A) -
The toner shape factor SF1 (ML ² / A) means a value calculated by the following formula. In the case of a true sphere, ML ² / A = 100.
Formula: ML ² / A = (maximum length) ² × π × 100 / (area × 4)

As a specific method for obtaining the toner shape factor, colored particles and toner images are taken from an optical microscope into an image analyzer (LUZEX III, manufactured by Nireco), the equivalent circle diameter is measured, and the maximum length and area are individually measured. The value of ML ² / A in the above formula was determined for the particles.

-Number particle size distribution index under toner, lower GSDp, particle size-
Lower number particle size distribution index: Lower GSDp and particle size measurement will be described. When the particle to be measured in the present invention is 2 μm or more, a Coulter counter TA-II type (manufactured by Beckman-Coulter) was used as the measuring apparatus, and ISOTON-II (manufactured by Beckman-Coulter) was used as the electrolyte.

  As a measuring method, 0.5 to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant. This was added to 100 to 150 ml of the electrolytic solution.

  The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the particle size distribution of particles of 2 to 60 μm is measured using the Coulter counter TA-II with an aperture diameter of 100 μm. Volume average distribution and number average distribution were determined. The number of particles to be measured was 50,000.

  Also, the lower number particle size distribution index of toner: lower GSDp and particle size were determined by the following methods. For the particle size range (channel) obtained by dividing the measured particle size distribution, draw the number cumulative distribution from the smaller particle size, define the particle size value to be 16% cumulative as D16p, and the particle size value to be 50% cumulative Is defined as D50p. The lower number particle size distribution index lower GSDp is the formula: lower GSDp = D50p / D16p.

  The particle size is defined as a particle size value in which the cumulative particle size distribution is drawn from the smaller particle size to the particle size range (channel) obtained by dividing the measured particle size distribution, and the particle size value at which accumulation is 50%.

  Moreover, when the particle | grains to measure in this invention are less than 2 micrometers, it measured using the laser diffraction type particle size distribution measuring apparatus (LA-700: made by Horiba, Ltd.). As a measurement method, a sample in a dispersion is adjusted to have a solid content of about 2 g, and ion exchange water is added thereto to make about 40 ml. This is put into the cell until an appropriate concentration is reached, waits for about 2 minutes, and is measured when the concentration in the cell becomes almost stable. The obtained particle size of each channel was accumulated from the smaller particle size, and the average particle size was determined when the accumulation reached 50%.

  When measuring powders such as external additives, 2 g of a measurement sample is added to 50 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, and dispersed for 2 minutes with an ultrasonic disperser (1000 Hz). Then, a sample was prepared and measured by the same method as the above-mentioned dispersion.

-Measurement of volume resistance-
The volume resistivity of the carrier and the titanium compound was measured using the apparatus shown in FIG. FIG. 1 is a configuration diagram for explaining a configuration for measuring a volume resistance value. In FIG. 1, the measurement sample 6 adjusted to the thickness H is sandwiched between the upper electrode 1 and the lower electrode 2, and the thickness is measured with the dial gauge 3 while being pressed by the pressurizing means 4 from above. The electrical resistance was measured with a high voltage ohmmeter 5 connected to the upper electrode 1 and the lower electrode 2 by wiring. Specifically, a measurement disk was prepared by applying a pressure of 500 kg / cm ^{2 to} the measurement sample with a molding machine. Next, the surface of the disk was cleaned with a brush, and sandwiched between the upper electrode 1 and the lower electrode 2 in the cell, and the thickness was measured with a dial gauge. Next, voltage was applied and the volume resistivity was obtained by reading the current value. The volume resistivity of the carrier is “Rv”, the volume resistivity of the titanium compound A externally added to the toner is “R (A)”, and the volume resistivity of the titanium compound B externally added to the carrier is “R (B)”. ".

-Average primary particle size of titanium compound-
The average primary particle size of the titanium compound was determined by observing with a scanning electron micrograph and taking the average of 50 samples of arbitrary data.

-Toner density measurement-
About 0.30 ± 0.05 g of the developer to be measured was collected and measured by a blow-off method using a charge amount measuring device (TB200: manufactured by Toshiba Corporation).

<Preparation of toner particles>
(Adjustment of resin fine particle dispersion)
-Styrene: 370 parts-n-Butyl acrylate: 30 parts-Acrylic acid: 8 parts-Dodecanethiol: 24 parts-Carbon tetrabromide: 4 parts

  6 g of nonionic surfactant (Nonipol 400: manufactured by Sanyo Kasei Co., Ltd.) and anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were prepared by mixing and dissolving the above components. Was subjected to emulsion polymerization in a flask in which 550 parts of ion-exchanged water was dissolved, and 50 parts of ion-exchanged water in which 4 g of ammonium persulfate was dissolved was added thereto while slowly mixing for 10 minutes. After carrying out nitrogen substitution, the inside of the flask was stirred and heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin fine particle dispersion in which resin particles of 150 nm, Tg = 58 ° C., and weight average molecular weight Mw = 12000 were dispersed was obtained.

(Adjustment of colorant dispersion)
・ Carbon black (Mogal L: Cabot): 60 parts ・ Nonionic surfactant (Nonipol 400: Sanyo Chemical Co., Ltd.): 6 parts ・ Ion-exchanged water: 240 parts

  The above components are mixed, dissolved, stirred for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA), then dispersed with an optimizer (color black (carbon black) having an average particle size of 250 nm) ) A colorant dispersant in which particles were dispersed was prepared.

(Adjustment of release agent dispersion)
Paraffin wax: 100 parts (HNP0190: manufactured by Nippon Seiwa Co., Ltd., melting point 85 ° C.)
-Cationic surfactant (Sanisol B50: manufactured by Kao Corporation): 5 parts-Ion exchange water: 240 parts

  The above components were dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA) for 10 minutes, and then dispersed with a pressure discharge type homogenizer, and the average particle size was 520 nm. A release agent dispersion in which the mold agent particles were dispersed was prepared.

(Preparation of toner particles 1)
-Resin fine particle dispersion: 234 parts-Colorant dispersion: 30 parts-Release agent dispersion: 40 parts-Polyaluminum hydroxide (Pho2S manufactured by Asada Chemical Co., Ltd.): 0.5 parts-Ion exchange water : 600 copies

  The above components were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then heated to 50 ° C. while stirring the inside of the flask in an oil bath for heating. . After maintaining at 50 ° C. for 30 minutes, it was confirmed that aggregated particles having a particle size of 4.9 μm were formed. Further, the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, and the particle size became 5.9 μm. Thereafter, 26 parts of the resin fine particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. The dispersion containing the aggregated particles was added with 1N sodium hydroxide to adjust the pH of the system to 7.0, and then the stainless steel flask was sealed and heated to 80 ° C. while continuing stirring using a magnetic seal. And held for 4 hours. After cooling, the toner particles were filtered off, washed four times with ion exchange water, and then lyophilized to obtain toner particles 1. Toner particle 1 had a D50 of 6.5 μm, a lower GSDp of 1.22, and a toner shape factor SF1 of 132.

(Preparation of toner particles 2)
Toner particles 2 were obtained by the same production method except that the pH of toner particles 1 was changed from 7.0 to 5.0. Toner particle 2 had a D50 of 6.7 μm, a lower GSDp of 1.23, and a toner shape factor SF1 of 117.

(Preparation of toner particles 3)
Toner particles 3 were obtained by the same production method except that the pH of toner particles 1 was changed from 7.0 to 7.5. Toner particle 3 had a D50 of 6.6 μm, a lower GSDp of 1.23, and a toner shape factor SF1 of 138.

(Preparation of toner particles 4)
Toner particles 4 were obtained by the same production method except that the pH of toner particles 1 was changed from 7.0 to 4.5. Toner particle 4 had a D50 of 6.5 μm, a lower GSDp of 1.23, and a toner shape factor SF1 of 110.

(Preparation of toner particles 5)
A mixture of 100 parts of a styrene-butyl acrylate copolymer (weight average molecular weight Mw = 150,000, copolymerization ratio 80:20), 5 parts of carbon black (Mogal L: manufactured by Cabot Corporation), and 6 parts of carnauba wax was obtained. The mixture was kneaded with a struder, pulverized with a jet mill, and then classified with a wind classifier to obtain toner particles 5. Toner particle 5 had a D50 of 6.6 μm, a lower GSDp of 1.26, and a toner shape factor SF1 of 145.

(Preparation of toner particles 6)
A mixture of 100 parts of a styrene-butyl acrylate copolymer (weight average molecular weight Mw = 150,000, copolymerization ratio 80:20), 5 parts of carbon black (Mogal L: manufactured by Cabot Corporation), and 6 parts of carnauba wax was obtained. After kneading with a struder, pulverization with a jet mill, spheronization with warm air was performed with a kryptron (manufactured by Kawasaki Heavy Industries), and classification with a wind classifier to obtain toner particles 6. Toner particle 6 had a D50 of 6.5 μm, a lower GSDp of 1.25, and a toner shape factor SF1 of 135.

(Preparation of toner particles 7)
A toner particle 7 having a D50 of 6.4 μm, a lower GSDp of 1.31, and a toner shape factor SF1 of 134 was obtained by the same production method as that of the toner particle 6.

(Carrier I adjustment)
Mn-Mg ferrite particles (volume average particle size: about 35 μm): 100 parts Toluene: 15 parts Styrene-methacrylate copolymer (component ratio 30:70): 1.85 parts Benzoguanamine resin particles: 0.3 Part (Eposter MS 0.3 μm; manufactured by Nippon Shokubai Co., Ltd.)
Carbon black (Regal 330; manufactured by Cabot): 0.35 part

  The above components excluding ferrite particles were stirred / dispersed with a stirrer for 60 minutes to prepare a coating layer forming raw material solution. Next, this raw material solution and ferrite particles were put into a vacuum degassing type solder, stirred at 60 ° C. for 30 minutes, and further degassed and dried while heating, thereby preparing carrier I.

(Carrier II adjustment)
Mn-Mg ferrite particles (volume average particle size: about 35 μm): 100 parts Toluene: 15 parts Styrene-methacrylate copolymer (component ratio 30:70): 1.95 parts Melamine resin particles (Epester S0. 3 μm; manufactured by Nippon Shokubai Co., Ltd.): 0.2 parts, carbon black (Regal 330; manufactured by Cabot Corporation): 0.35 parts

  Carrier II was produced by the same production method as Carrier I using the above components.

(Carrier III adjustment)
Mn-Mg ferrite particles (volume average particle size: about 35 μm): 100 parts Toluene: 15 parts Styrene-methacrylate copolymer (component ratio 30:70): 1.95 parts Melamine resin particles (Epester S0. 3 μm; manufactured by Nippon Shokubai Co., Ltd.): 0.3 part Carbon black (Regal 330; manufactured by Cabot Corporation): 0.25 part

  Carrier III was produced by the same production method as Carrier I using the above components.

(Carrier IV adjustment)
Mn-Mg ferrite particles (volume average particle size: about 35 μm): 100 parts Toluene: 15 parts Styrene-methacrylate copolymer (component ratio 30:70): 1.73 parts Benzoguanamine resin particles: 0.3 (Eposter MS 0.3μm; manufactured by Nippon Shokubai Co., Ltd.)
Carbon black (Regal 330; manufactured by Cabot): 0.47 parts

  Carrier IV was produced by the same production method as Carrier I using the above components.

Example 1
Toner particles 1: 100 parts, titanium compound A1: organosilane, organopolysiloxane-treated titanium oxide (average particle size 50 nm, volume resistivity 3.2 × 10 ¹² ) 0.45 parts, rutile type titanium oxide (average particle size) Add 20 parts of 20 nm, 1.0 part of n-decyltrimethoxysilane) and 1.5 parts of silica (prepared by vapor phase oxidation method, volume average particle size 40 nm, silicone oil treatment), using a 5 liter Henschel mixer, After blending for 15 minutes at 30 m / s, coarse particles were removed using a sieve having an opening of 45 μm to prepare toner particles.

Further, 0.05 parts of decyltrimethoxysilane-treated titanium oxide (average primary particle size: 40 nm, volume resistance: 8.0 × 10 ¹⁴ Ω · cm) is added to 100 parts of carrier I, and a V-type blender (volume 5 L) After stirring at 40 rpm for 20 minutes, a titanium compound B externally added carrier was prepared by passing through a sieve having an opening of 75 μm. The volume resistivity of this carrier was measured and found to be 1.1 × 10 ¹¹ Ω · cm.

  100 parts of titanium compound externally added carrier and 9 parts of titanium compound externally added toner particles are mixed in a V-type blender (volume: 5 L), stirred at 40 rpm for 20 minutes, and then passed through a sieve having an aperture of 212 μm. A developer was obtained.

<< Examples 2 to 12 >>
An electrostatic latent image developer was obtained by the same production method except that Example 1 and the toner particles were changed according to Tables 1 and 2.

<< Comparative Examples 1-14 >>
An electrostatic latent image developer was obtained by the same production method except that Example 1 and the toner particles were changed according to Tables 1 and 2.

(Evaluation)
A print test was carried out under the following conditions, and it was clear that the toner shape and particle size distribution had a large effect when controlling the toner concentration by the magnetic permeability.

  Using the developer for developing an electrostatic latent image, an image area of 5% and the number of prints were obtained in a low temperature and low humidity (10 ° C., 20% RH) environment using a Docu Center Color 400 remodeling machine (manufactured by Fuji Xerox Co., Ltd.). 500,000 tests were performed. In addition, a print test of 500000 sheets with an image area of 10% was performed in an environment of high temperature and high humidity (30 ° C., 85% RH), and after leaving it in a high temperature and high humidity environment for 3 days, another 3000 print tests were performed. did. The toner density was measured every 100,000 sheets. As the image evaluation, the image density unevenness after 500,000 sheets, toner scattering, fogging, and carrier adhesion were evaluated.

  The image forming method using the Docu Center Color 400 remodeling machine (manufactured by Fuji Xerox Co., Ltd.) sets the permeability setting value Vs so that the toner concentration is 9% under low temperature and low humidity and the toner concentration is 7% under high temperature and high humidity. Set. In the toner density control, when the difference Δ = Vs−V between the sensor detection value V and the set value is positive, it is determined that the toner density is sufficient, and the toner supply is stopped. If the difference is negative, the toner density is insufficient. Therefore, toner replenishment was performed, and control was performed so that Δ was reduced.

  Further, the present image forming method includes a step of forming an electrostatic latent image on an electrostatic charge image carrier, a step of developing the electrostatic latent image using a developer to form a toner image, and the toner image It includes a step of transferring onto a transfer body and a step of thermally fixing the toner image, and the process speed was set to 350 mm / sec.

<Evaluation of toner density>
The toner concentration was measured every 100,000 sheets by the evaluation condition method. The set value ± 1.0% is indicated by ◯, the set value ± 1.5% is indicated by △, and the others are indicated by ×.

<Evaluation of uneven image density>
After taking a predetermined number of copies of each developer under a predetermined environment, the developer is left overnight to copy an image having a 2 cm × 5 cm patch, and an image densitometer (X-Rite 404A) : Manufactured by X-Rite). The difference between the maximum value and the minimum value of the measured values is less than 0.5, ◯ is 0.5 or more and less than 0.8, and 0.8 or more is ×.

<Evaluation of fogging and carrier adhesion in image>
After collecting a predetermined number of copies of each developer in a predetermined environment, the background portion is similarly transferred onto the tape, and using a loupe or a microscope, the number of toner and carrier per 1 cm ² is counted. Evaluation was made with ○ less than 100, Δ from 100 to 500, and × when more.

Also, for carrier adhesion in the image, copy the image that has two 2cm x 2cm patches, hard stop, and transfer the two development parts on the photoconductor onto the tape using adhesiveness respectively. The number of carriers attached per 1 cm ² attached to the tape was counted and evaluated.

  In addition, the carrier adhesion was evaluated as “◯” for less than 5 and “Δ” for 5 to 10, and “×” for 11 or more. The distinction between toner and carrier was determined mainly by the difference in particle size and shape.

  The results of each test are shown in Table 3. From this print test, the carrier concentration controlled by the conventional carrier resistance control means and the toner additive type can stabilize the toner concentration in each environment, but the toner concentration control and image quality can be controlled in any environment. It is difficult to achieve both. However, the developer of the present invention can achieve both toner density control and image quality regardless of the environment.

  From the results shown in Table 3, it can be seen that in the examples, good results were obtained for evaluation of toner density, image density, toner scattering, fogging, and carrier adhesion in both low temperature and low humidity environments. .

It is a block diagram for demonstrating the structure of measuring a volume resistance value.

Explanation of symbols

1 Upper electrode 2 Lower electrode 3 Dial gauge 4 Pressurizing means 5 High voltage resistance meter 6 Measurement sample

Claims (2)

At least a latent image forming step for forming an electrostatic latent image on the surface of the latent image carrier and a developer containing at least a toner and a carrier are used to develop the electrostatic latent image formed on the surface of the latent image carrier. A developing process for forming a toner developed image, a process for transferring the toner image formed on the surface of the latent image carrier onto a recording medium, and a fixing process for thermally fixing the toner image transferred to the surface of the recording medium. In the image forming method for controlling the toner concentration as a change in magnetic permeability of the developer,
The image forming method, wherein the developer has titanium compound A attached to the toner surface, titanium compound B attached to the carrier surface, and satisfies the following conditions.
Condition (1): The toner shape factor (SF1) is 115 to 140.
Condition (2): Lower number particle size distribution index of toner: Lower GSDp = D50p / D16p ≦ 1.27 [where D50p: toner particle number distribution, particle size value at which accumulation is 50% from the smaller diameter side, D16p: toner Particle size distribution The particle size at which accumulation is 16% from the smaller diameter side]
Condition (3): 1 × 10 ⁹ Ω · cm ≦ Rv ≦ 5 × 10 ¹² Ω · cm [where Rv: volume resistivity of carriers at electric field strength of 10000 V / cm]
Condition (4): 100 × R (A) <R (B) [where R (A): volume resistivity of titanium compound A at electric field strength of 10000 V / cm, R (B): electric field strength at 10,000 V / cm Volume resistivity of titanium compound B] A developer for developing an electrostatic latent image for controlling toner density using at least a toner and a carrier and using a change in magnetic permeability of the developer,
A developer for developing an electrostatic latent image, wherein a titanium compound A is adhered to the toner surface, a titanium compound B is adhered to the carrier surface, and the following conditions are satisfied.
Condition (1): The toner shape factor (SF1) is 115 to 140.
Condition (2): Lower toner particle size distribution index: Lower GSDp = D50p / D16p ≦ 1.27 [where D50p: toner particle size distribution, particle size at which accumulation is 50% from the smaller diameter side, D16p: toner Particle size distribution The particle size at which accumulation is 16% from the smaller diameter side]
Condition (3): 1 × 10 ⁹ Ω · cm ≦ Rv ≦ 5 × 10 ¹² Ω · cm [where Rv: volume resistivity of carriers at electric field strength of 10000 V / cm]
Condition (4): 100 × R (A) <R (B) [where R (A): volume resistivity of titanium compound A at an electric field strength of 10,000 V / cm, R (B): at an electric field strength of 10,000 V / cm Volume resistivity of titanium compound B]

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