JP5429312B2 - Toner, developer, and image forming apparatus - Google Patents

Description

  The present invention relates to a toner suitably used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, an efficient manufacturing method thereof, a developer using the toner, a container containing toner, a process cartridge, an image The present invention relates to a forming apparatus and an image forming method.

  Image formation by electrophotography generally forms an electrostatic image on a photoreceptor (electrostatic image carrier), develops the electrostatic image with a developer to form a visible image (toner image), The visible image is transferred to a recording medium such as paper and fixed to form a fixed image (see Patent Document 1). On the other hand, toner remaining on the photoreceptor without being transferred to the recording medium is cleaned by a cleaning member such as a blade disposed in pressure contact with the surface of the photoreceptor.

  As the developer, a one-component developer using a magnetic toner or a non-magnetic toner alone and a two-component developer composed of a toner and a carrier are known. Further, as the toner, a toner produced by a kneading and pulverizing method is generally used in which a thermoplastic resin is melt-kneaded with a release agent such as a pigment and wax, a charge control agent, etc., and then finely pulverized and further classified. Yes. If necessary, inorganic fine particles or organic fine particles may be added to the surface of the toner particles for the purpose of improving fluidity and cleaning properties.

  However, the toner obtained by the kneading and pulverization method generally has a wide particle size distribution, unevenness in the triboelectric chargeability of the toner, and fog and the like are likely to occur. In addition, due to production efficiency, it is difficult to obtain a small particle diameter toner having a volume average particle diameter of 2 to 8 μm, and there is a problem that it is difficult to meet the demand for high image quality.

Thus, attention has been drawn to toner obtained by granulation in an aqueous phase. The toner has a narrow particle size distribution, can be easily reduced in size, can obtain a high-quality and high-definition image, and is excellent in offset resistance and low-temperature fixability due to high dispersion of a release agent. . In addition, the transfer uniformity is excellent due to the uniformity of charging, and the fluidity is good, and the design of the developing device is advantageous in that the design of the hopper and the torque for rotating the developing roll can be reduced. .
As a toner obtained by granulating in the aqueous phase, a toner obtained by a polymerization method or an emulsification dispersion method (hereinafter sometimes referred to as “chemical toner”) has been developed.

  Various methods are known as polymerization methods. Among them, monomers, a polymerization initiator, a colorant, a charge control agent, and the like are added to an aqueous phase containing a dispersion stabilizer while stirring to form oil droplets. A suspension polymerization method is widely known in which toner particles are obtained by raising the temperature and causing the polymerization reaction to proceed. Further, an association method has been proposed in which toner particles are obtained by forming fine particles by emulsion polymerization or suspension polymerization, aggregating the fine particles, and further fusing the agglomerated fine particles.

  However, although the toner obtained by the polymerization method or the association method can reduce the particle size of the toner particles, since the main component of the binder resin is limited to a vinyl polymer capable of radical polymerization, a color toner A polyester resin or an epoxy resin suitable for the above cannot be used. In addition, the polymerization method has problems that it is difficult to reduce VOC (volatile organic compounds composed of unreacted monomers) and that it is difficult to obtain a toner having a narrow particle size distribution.

The emulsification dispersion method is a method in which, for example, a mixture of a binder resin and a colorant is mixed with an aqueous phase and emulsified to obtain toner particles (see Patent Documents 2 to 3). Not only can particle size reduction and spheroidization be performed easily, but there is a wider range of choice of binder resin compared to the polymerization method, and it is easy to reduce residual monomers. There is an advantage that the density can be arbitrarily changed from a low density to a high density.
Here, the binder resin is preferably a resin having a relatively low fixing temperature, which melts sharply at the time of fixing and easily smoothes the image surface. For example, a polyester resin is preferable to a styrene-acrylic resin. For the toner, a polyester resin excellent in flexibility is preferable. Therefore, in recent years, attention has been focused on producing a small particle size toner using a polyester resin, which could not be produced by the above-described polymerization method, as a binder resin by using an emulsification dispersion method.

  However, even in the toner manufactured by the emulsification dispersion method, the fixing temperature is not sufficiently reduced and the offset temperature range is widened, and the generation of fine particles is inevitable in the manufacturing process. Since emulsification loss also occurs, there is a problem that the yield of the toner is lowered and the productivity is inferior.

  As a manufacturing method for solving such a problem, for example, a method of manufacturing toner particles by emulsifying and dispersing a polyester resin as a binder resin and then aggregating and further fusing the obtained fine particles. It has been proposed (see Patent Documents 4 to 5). According to this production method, since there is no generation of ultrafine particles, it is possible to produce a classification-free toner with no emulsification loss and a sharp particle size distribution. Low viscosity is the main component, and it is impossible to achieve both low temperature fixability and high temperature offset resistance. In particular, it lacks the appropriateness for the recently desired oilless heat roll fixing. It was a thing.

  Further, these chemical toners inevitably become spherical due to the interfacial tension of the droplets generated in the dispersion process. Spherical toner has good fluidity even with a small particle size, and it is advantageous for developing device design such as hopper design and lower torque for rotating the developing roll, but it is difficult to clean with some cleaning methods. There was a problem. That is, the surface of the photoconductor after the toner image is transferred is cleaned by means such as a blade, a fur brush, or a magnetic brush, but a blade cleaning method with a simple structure and good cleaning properties is generally used. In many cases, it is frequently used. In the case of this method, spherical toner rotates between the cleaning blade and the photosensitive member and enters into the gap, which causes a serious problem that it is difficult to clean.

Therefore, in order to adapt the chemical toner to the blade cleaning method, for example, a method is proposed in which high-speed stirring is performed before the polymerization is completed and mechanical force is applied to the particles to make the polymer particles amorphous (see Patent Document 6). Has been. However, in this method, since a stable dispersion state is broken, there is a possibility that the association between particles proceeds and eventually a bulk polymer may be formed.
In addition, for example, a method of improving the cleaning property by aggregating particles by using polyvinyl alcohol having a specific saponification degree as a dispersant to form aggregated particles of 5 to 25 μm (see Patent Document 7). ) Has been proposed. However, this method is not suitable for the production of a small particle size toner because the particle size of the aggregate particles tends to be large.
Furthermore, for example, after phase inversion emulsification, the removal of the organic solvent is stopped halfway, and then a method of forming irregular particles by aggregating and fusing (see Patent Document 8) is known. However, this method requires a self-emulsifying resin, and the material selectivity is poor because the type and acid value of the resin are greatly restricted. In addition, the shape control method for stopping the removal of the organic solvent on the way requires fine adjustment and control in several steps, which increases the cost in terms of equipment and production efficiency, and is not suitable for practical mass production.

  Therefore, while maintaining the advantages of a chemical toner that has a small particle size, a narrow particle size distribution, and excellent fluidity, the deformed toner has excellent cleaning properties (for example, without poor cleaning by a blade) and can provide high image quality. Is not provided yet.

US Pat. No. 2,297,691 JP-A-5-66600 JP-A-8-21655 JP-A-10-020552 JP 11-007156 A Japanese Patent Laid-Open No. 62-266550 JP-A-2-511164 JP 2002-351139 A

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention provides a toner having a potato shape formed by coalescing a plurality of spherical particles with a small particle diameter, which has excellent cleaning properties and high image quality, and high image quality using the toner. An object is to provide a developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method.

Means for solving the problems are as follows. That is,
<1> A toner obtained by granulating a toner material containing at least a binder resin and a colorant in an aqueous medium, and the toner includes a plurality of primary oil droplets of an organic phase in the aqueous medium. The toner has a potato shape formed as described above.
<2> The toner according to <1>, wherein the organic phase is a solution or dispersion obtained by dissolving or dispersing at least a binder resin and a colorant in an organic solvent.
<3> The toner according to <1>, wherein the organic phase contains at least a polymerizable monomer and a colorant.
<4> When the diameter of spherical particles that are primary oil droplets of the organic phase is R (μm) and the length in the depth direction of the coalescing portion between the spherical particles is L (μm), The toner according to any one of <1> to <3>, wherein the formula satisfies 0.1R ≦ L <1.0R.
<5> The toner according to any one of <1> to <4>, wherein the toner contains 30 to 100% by number of toner particles having a potato shape out of 100 toner particles observed by electron micrograph.
<6> The toner has a shape in which 2 to 20 spherical particles, which are primary oil droplets of an organic phase, are fused, and a toner having a potato shape out of 100 toner particles observed with an electron micrograph. The toner according to any one of <1> to <5>, wherein the toner has 30 to 100% by number of particles, and the number average of diameters R of virtual circles drawn along the spherical particles is 0.5 to 7 μm. It is.
<7> A toner granulated in an aqueous medium containing at least a binder resin and a colorant, and 50 g of a developer composed of 2.5 g of the toner and 47.5 g of a carrier are painted in a 100 ml bottle. The ratio of the number of broken or disintegrated toners out of 1000 toner particles observed with a scanning electron micrograph after stirring at 50 Hz for 30 minutes using a conditioner is 10% or less. Toner.
<8> The toner according to any one of <1> to <7>, wherein the toner has an average circularity of 0.900 to 0.980.
<9> The toner according to any one of <1> to <8>, wherein the glass transition temperature (Tg) of the toner is 40 to 70 ° C.
<10> The toner according to any one of <1> to <9>, wherein the toner has a volume average particle diameter (Dv) of 3 to 8 μm.
<11> The toner according to any one of <1> to <10>, wherein a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner is 1.05 to 1.25. Toner.
<12> The toner according to any one of <1> to <11>, wherein the toner has an acid value of 1.0 to 50.0 (KOHmg / g).
<13> A toner solution is prepared by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, a colorant, and a release agent in an organic solvent. After that, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. The toner according to any one of <1> to <12>, which is obtained by reacting to form an adhesive base material in the form of particles and removing the organic solvent.
<14> The toner according to <13>, wherein the polymer having a site capable of reacting with the compound having an active hydrogen group has a weight average molecular weight (Mw) of 3,000 to 40,000.
<15> The toner according to any one of <1> to <14>, wherein the binder resin contains a polyester resin, and a content of the polyester resin in the toner is 50 to 100% by mass.
<16> The toner according to <15>, wherein the polyester resin has a THF-soluble component having a weight average molecular weight (Mw) of 1,000 to 30,000.
<17> The toner according to any one of <15> to <16>, wherein the acid value of the polyester resin is 1.0 to 50.0 (KOH mg / g).
<18> The toner according to any one of <15> to <17>, wherein the polyester resin has a glass transition temperature (Tg) of 35 to 70 ° C.
<19> The toner according to any one of <1> to <18>, wherein the toner contains a crystalline polyester resin.
<20> The toner according to <19>, wherein the crystalline polyester resin has a DSC endothermic peak temperature of 50 to 150 ° C.
<21> The molecular weight distribution by GPC of the soluble portion of orthodichlorobenzene of the crystalline polyester resin is 1000 to 30000 in weight average molecular weight (Mw), 500 to 6000 in number average molecular weight (Mn), and Mw. The toner according to any one of <19> to <20>, wherein / Mn is 2 to 8.
<22> From the above <19> to <21, in the infrared absorption spectrum of the crystalline polyester resin, any of 965 ± 10 cm ⁻¹ and 990 ± 10 cm ⁻¹ has absorption based on δCH (out-of-plane variable angular vibration) of olefin. > The toner according to any one of the above.
<23> A developer comprising the toner according to any one of <1> to <22>.
<24> A toner-containing container filled with the toner according to any one of <1> to <22>.
<25> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to <22> to be a visible image And a developing means for forming the process cartridge.
<26> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <1> to <22> An image comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is a forming method.
<27> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image according to <1> to <22> At least development means for forming a visible image by developing with toner, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transfer image transferred to the recording medium An image forming apparatus including the image forming apparatus.

In the first embodiment, the toner of the present invention is a toner obtained by granulating a toner material containing at least a binder resin and a colorant in an aqueous medium, and the toner is an organic phase in the aqueous medium. It has a potato shape formed by combining a plurality of primary oil droplets. As a result, according to the toner of the present invention, the cleaning property is excellent, the low temperature fixing property is good, and the high image quality is obtained.
In the second embodiment, the toner of the present invention is a toner granulated in an aqueous medium containing at least a binder resin and a colorant, and 50 g of a developer comprising 2.5 g of the toner and 47.5 g of the carrier. The ratio of the number of broken or disintegrated toners is less than 10% out of 1000 toners observed with a scanning electron micrograph after stirring in a 100 ml bottle at 50 Hz for 30 minutes using a paint conditioner. It is. As a result, according to the toner of the present invention, the cleaning property is excellent, the low temperature fixing property is good, and the high image quality is obtained.

  The developer of the present invention contains the toner of any one of the first and second aspects of the present invention. For this reason, when an image is formed by electrophotography using the developer, a high-quality image with high image density and high sharpness is formed.

  The toner container of the present invention is filled with the toner of any one of the first and second embodiments of the present invention. For this reason, when an image is formed by electrophotography using the toner of the present invention filled in the toner-containing container, a high-quality image with high image density and high sharpness is formed.

  The process cartridge of the present invention develops an electrostatic latent image carrier and the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to any one of the first and second embodiments of the present invention. And at least developing means for forming a visible image. The process cartridge is detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that a high quality image with high image density and high sharpness can be formed.

  The image forming apparatus of the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. Development means for forming a visible image by developing with the toner of any one of the first and second forms, transfer means for transferring the visible image to a recording medium, and a transfer image transferred to the recording medium Fixing means for fixing. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the toner of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, a high-quality image with high image density and high sharpness is formed.

  The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and the electrostatic latent image is one of the first and second aspects of the present invention. A developing process for forming a visible image by developing the toner, a transfer process for transferring the visible image to a recording medium, and a fixing process for fixing the transferred image transferred to the recording medium. In the image forming apparatus, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, a high-quality image with high image density and high sharpness is formed.

  According to the present invention, it is possible to solve various problems in the prior art, a toner having a potato shape formed by coalescing a plurality of spherical particles having a small particle diameter, which has excellent cleaning properties and high image quality, and Further, it is possible to provide a developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method capable of improving the image quality using the toner.

1A is an electron micrograph of a toner having a potato shape produced in Example 1. FIG. FIG. 1B is a schematic diagram of FIG. 1A. FIG. 2 is an example of a graph showing the Casson yield value. FIG. 3 a is an explanatory diagram showing an example of convergence when an oil droplet having a large particle diameter exhibits non-Newtonian viscosity. FIG. 3 b is an explanatory diagram illustrating an example of convergence when a small-diameter oil droplet exhibits a non-Newtonian viscosity. FIG. 4 is an explanatory diagram showing an example of organic solvent removal when oil droplets exhibit non-Newtonian viscosity. FIG. 5 is a schematic view showing an example of the process cartridge of the present invention. FIG. 6 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 7 is a schematic explanatory view showing another example in which the image forming method of the present invention is implemented by the image forming apparatus of the present invention. FIG. 8 is a schematic explanatory view showing an example of carrying out the image forming method of the present invention by the image forming apparatus (tandem color image forming apparatus) of the present invention. FIG. 9 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG. FIG. 10 is an SEM photograph of the toner produced in Comparative Example 1. FIG. 11A is an SEM photograph (magnification: 1500 times) of the toner produced in Example 7. FIG. 11B is an SEM photograph (magnification: 3000 times) of the toner produced in Example 7. FIG. 12A is a graph showing an example of a flow curve of a flow tester used in the evaluation of thermal characteristics. FIG. 12B is a graph showing an example of a flow curve of a flow tester used in the evaluation of thermal characteristics.

(toner)
In the first embodiment, the toner of the present invention is a toner obtained by granulating a toner material containing at least a binder resin and a colorant in an aqueous medium, and the toner is an organic phase in the aqueous medium. The primary oil droplets (spherical particles) have a potato shape formed by coalescence.

The organic phase is preferably a solution or dispersion obtained by dissolving or dispersing at least a binder resin and a colorant in an organic solvent.
The organic phase preferably contains at least a polymerizable monomer and a colorant. A plurality of primary oil droplets (spherical particles) may be coalesced in a state where the primary oil droplets of the organic phase are in a state in which the polymerization reaction of the monomer is proceeding or in a viscous state. When agglomerating resin particles that have been polymerized, unlike the case where heat is applied to the agglomerates, coalescence of a plurality of primary oil droplets (spherical particles) can proceed in a viscous fluid state. It is possible to produce a toner with very little cracking or disintegration at the toner bonding interface. Further, since the heating process up to the melting temperature or the softening temperature, which has a large energy load in toner production, can be omitted, the productivity can be greatly improved.

  Here, the potato shape formed by coalescing the plurality of primary oil droplets (spherical particles) is an electron micrograph of FIG. 1A and a schematic view thereof, as shown in FIG. 1B. It means a shape in which spherical particles are connected via a joining part (bonding part), the diameter of the spherical particles is R (μm), and the length in the depth direction of the joining part between the spherical particles is L (μm). ), A shape satisfying the following formula, 0.1R ≦ L <1.0R is preferable, and 0.3R ≦ L ≦ 0.9R is more preferable.

  The measurement of the diameter R (μm) of spherical particles, which are primary oil droplets of the organic phase, and the length L (μm) in the depth direction of the coalescing part between the spherical particles is performed, for example, by a scanning electron microscope (SEM). Can be used.

The toner preferably contains 30 to 100% by number, more preferably 40 to 100% by number of toner particles having the potato shape out of 100 toner particles observed by electron micrograph. If the toner particles having the potato shape are less than 30% by number, the cleaning property may be deteriorated.
The toner has a shape in which 2 to 20 (preferably 3 to 15) spherical particles are coalesced, and out of 100 toner particles observed by electron micrograph, the toner having the potato shape. The number average of diameters R of virtual circles having 30 to 100% by number (preferably 40 to 100% by number) of particles and drawn corresponding to the spherical particles is 0.5 to 7 μm (preferably 1 to 6 μm). It is preferable that

In the second embodiment, the toner of the present invention is a toner that is granulated in an aqueous medium containing at least a binder resin and a colorant, and is cracked or disintegrated out of 1,000 toners according to a predetermined crack resistance test. The ratio of the number is 10% or less, and further contains other components as necessary. The ratio of the number of broken or disintegrated toners out of 1,000 toners by the crack resistance test is 10% or less, preferably 5% or less, more preferably 1% or less, and most preferably 0%.
If the percentage of the toner that is cracked or disintegrated is too large, fine powder may be generated to contaminate the carrier, the image quality may be deteriorated, and it may be difficult to ensure the chargeability of the cracked surface, resulting in a decrease in image quality. is there. In the present invention, since the polyester resin is dissolved in an organic solvent to create a non-Newtonian state, each of the granulated particles is in a state in which the resin is dissolved in the solvent, so there is no interface when the particles are bonded together. It is possible to prevent cracking or collapse from occurring.
The cracked or disintegrated toner includes all of the toner that is partially cracked, about half of the toner is cracked, and most of the toner is cracked (collapsed). .

  Here, in the crack resistance test, 50 g of a developer composed of 2.5 g of toner and 47.5 g of a carrier is placed in a 100 ml bottle (manufactured by Nidec Rika Glass Co., Ltd.), and the condition is 50 Hz for 30 minutes using a paint conditioner. Then, the toner was separated by electric field separation and observed with a scanning microscope (SEM). By this SEM observation, it is possible to obtain the ratio (%) of the number of broken or broken toners in 1000 toners.

  The toner according to the first and second embodiments of the present invention is not particularly limited as long as the production method and material satisfy the above conditions, and can be appropriately selected according to the purpose. It is preferable that the toner is manufactured by the toner manufacturing method according to the embodiment and the second embodiment.

The first aspect of the method for producing the toner includes at least the step of emulsifying or dispersing an oil phase in an aqueous phase to form oil droplets and converging the oil droplets. Non-Newtonian viscosity.
The second aspect of the method for producing the toner includes at least the step of emulsifying or dispersing an oil phase containing an organic solvent in an aqueous phase to form oil droplets, and removing the organic solvent from the oil droplets. The oil droplets upon removal of the organic solvent exhibit non-Newtonian viscosity.

  In a preferred embodiment of the toner of the present invention, an oil phase is prepared by dissolving or dispersing a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an organic solvent. The oily phase is emulsified or dispersed in an aqueous phase, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous phase to form an adhesive substrate. Examples thereof include a toner produced by producing particles containing at least.

Examples of the viscosity of the oil droplet include Newtonian viscosity and non-Newtonian viscosity.
In the Newtonian viscosity, Newton's viscosity law is established, and the shear stress is proportional to the shear rate (ie, when the shear rate is gradually increased from 0, the shear stress is proportional to the increase in the shear rate, and the shear stress is also If the temperature is constant, the viscosity becomes constant.
On the other hand, in the non-Newtonian viscosity, Newton's law of viscosity is not established, and the apparent viscosity changes depending on the shear stress (or shear rate).
In the present invention, the Newtonian viscosity also includes a mode in which the structural viscosity is weak and close to the Newtonian viscosity even if it has a structural viscosity described later. Of 0.5 Pa or less is included.

Examples of the non-Newtonian viscosity include structural viscosity and dilatancy.
With the structural viscosity, when the shear stress increases, the apparent viscosity decreases, and conversely, with the dilatancy, the viscosity increases.
General structural viscosity is described in many books, and is described in, for example, “Rheology for chemists” (Shigeharu Onoki, Kagaku Dojinsha, p. 37). Yes.

Examples of the structural viscosity include thixotropy and rheopexy.
In the thixotropy, the shear rate depends on the shear stress and the time during which the shear stress is applied. That is, when a shearing force is applied, the viscosity is lowered and exhibits flow, but if left undisturbed, it returns to its original hardness.
Contrary to the thixotropy, the rheopexy increases the viscosity when flowing at a constant shear rate.

The Newtonian viscosity and the non-Newtonian viscosity are variable with each other by a viscosity conversion process that converts the viscosity of the oil droplets.
The viscosity conversion process generally includes a process for converting the non-Newtonian viscosity to the Newtonian viscosity and a process for converting the Newtonian viscosity to the non-Newtonian viscosity.

  In the present invention, since the oil droplets exhibit non-Newtonian viscosity at the time of convergence or removal of the organic solvent, the viscosity conversion treatment is not necessary, but the toner of the first aspect In the manufacturing method of the second aspect, it is necessary that the viscosity of the oil droplet is a non-Newtonian viscosity at the latest after the formation of the oil droplet until the time of convergence. Then, after the formation of the oil droplets, it is necessary that the oil droplets have a non-Newtonian viscosity at the latest before the removal of the organic solvent. If the viscosity of the oil droplet becomes a Newtonian viscosity after the convergence, the viscosity of the oil droplet is converted to a non-Newtonian viscosity by the viscosity conversion process before the organic solvent is removed. Can do.

There is no restriction | limiting in particular as the method of the viscosity conversion process which converts from the said non-Newtonian viscosity to the said Newtonian viscosity, According to the objective, it can select suitably, For example, a stirring process, a vibration process, etc. are mentioned.
There is no particular limitation on the viscosity conversion method for converting from the Newtonian viscosity to the non-Newtonian viscosity, and it can be appropriately selected according to the purpose. For example, a deforming agent (viscosity control agent, thixotropic property imparting) In the method of viscosity conversion processing for converting from the Newtonian viscosity to the non-Newtonian viscosity, oil droplets exhibiting non-Newtonian viscosity are stirred by the stirring processing or the like, and the structural viscosity In the case where is destroyed and temporarily exhibits a Newtonian viscosity, a method of recovering the structural viscosity lost with time by leaving the oil droplets is also included.

-Oil phase-
The oil phase includes, for example, any of a monomer, a polymer, an active hydrogen group-containing compound, and a polymer (prepolymer) that can react with the active hydrogen group-containing compound, and further, if necessary, a colorant, a release agent. It contains a toner material containing other components such as a mold agent and a charge control agent, and preferably contains an organic solvent, and the toner material is dissolved in the organic solvent.

The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, and methyl isobutyl ketone. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used alone or in combination of two or more.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous phase.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used alone or in combination of two or more. Among these, an alcoholic hydroxyl group is particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used alone or in combination of two or more. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) or those blocked (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
If the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may decrease. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin will be low. The hot offset resistance may be deteriorated.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. However, it can be appropriately selected from known resins, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used alone or in combination of two or more. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond generating group in the urea bond generating group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And what made the said active hydrogen group containing polyester resin react with polyisocyanate (PIC), etc. are mentioned.

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol A mixture with (TO), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycols, alkylene ether glycols, alicyclic diols, alkylene oxide adducts of alicyclic diols, bisphenols, alkylene oxide adducts of bisphenols, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to the trihydric or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tri- or higher valent polycarboxylic acid.
These may be used alone or in combination of two or more. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably a trivalent to octavalent or higher one, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate.
These can be used alone or in combination of two or more.

As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing component are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 4/1 to 1.2 / 1. More preferred is 3/1 to 1.5 / 1.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 3,000 to 40,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 4000 to 30,000 is more preferable. When the weight average molecular weight (Mw) is less than 3,000, the heat resistant storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.

The measurement of the molecular weight distribution by the gel permeation chromatography (GPC) can be performed, for example, as follows.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or Toyo Soda Kogyo Co., Ltd. having a molecular weight of ^{6 × 10 2, 2.1 × 10} 2, 4 × 10 2, 1.75 × 10 4, 1.1 × 10 5, 3.9 × 10 5, 8.6 It is preferable to use those of × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, colorants, mold release agents, charge control agents, inorganic fine particles, fluidity improvers, cleaning improvers, magnetic properties, and the like. Materials, metal soaps, and the like.

The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used alone or in combination of two or more.

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.
When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used alone or in combination of two or more. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
When the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable.
When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used alone or in combination of two or more.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), Fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups, carbo Sill group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with each component of the toner when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1-10 mass parts is preferable, and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples include silicon and silicon nitride. These may be used alone or in combination of two or more.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 5.0% by mass.

The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having an alkyl fluoride group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium, and includes, for example, fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and the like. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

In the method for producing a toner according to the preferred embodiment of the present invention, the oil phase is prepared in the organic solvent by the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, the colorant, It can be carried out by dissolving or dispersing toner materials such as the release agent and the charge control agent.
In the toner material, components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound are added when the resin fine particles are dispersed in the aqueous phase in the preparation of the aqueous phase described later. You may add and mix in an aqueous phase, or when adding the said oil phase to the said aqueous phase, you may add to the said aqueous phase with this oil phase.

-Water phase-
The aqueous phase is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, a solvent miscible with water, a mixture thereof, and the like. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used alone or in combination of two or more.

  The aqueous phase can be prepared, for example, by dispersing resin fine particles in the aqueous phase. There is no restriction | limiting in particular as the addition amount in this water phase of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.

The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous phase, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. , Etc.
These may be used alone or in combination of two or more. Among these, at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin is preferable because an aqueous dispersion of fine spherical resin resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). ", Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate, and the like.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

-Emulsification or dispersion-
For emulsification or dispersion of the oil phase in the aqueous phase, the oil phase is preferably dispersed while stirring in the aqueous phase. The dispersion method is not particularly limited and can be appropriately selected according to the purpose. For example, the dispersion can be performed using a known disperser. Examples of the disperser include a low-speed shearing disperser. Machine, high-speed shearing disperser, friction disperser, high-pressure jet disperser, ultrasonic disperser, and the like. Among these, a high-speed shearing disperser is preferable in that the particle size of the oil droplet (dispersion) can be controlled to 3 to 8 μm.
When the high-speed shearing disperser is used, there are no particular restrictions on conditions such as the number of rotations, the peripheral speed of the stirring blade, the dispersion time, and the dispersion temperature, which can be appropriately selected according to the purpose. The rotation speed is preferably 1,000 to 30,000 rpm, more preferably 5,000 to 20,000 rpm, the peripheral speed of the stirring blade is preferably 5 to 30 m / s, and the dispersion time is batch. In the case of a system, 0.1 to 5 minutes are preferable, and the dispersion temperature is preferably 0 to 150 ° C, more preferably 10 to 98 ° C under pressure. The dispersion temperature is generally easier when the temperature is higher.

  In the method for producing a toner according to the preferable aspect of the present invention, when the emulsification or dispersion is performed, the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction. An adhesive substrate is produced.

-Adhesive substrate-
The adhesive substrate exhibits adhesiveness to a recording medium such as paper, and is formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous phase. It may contain at least a polymer and may further contain a binder resin appropriately selected from known binder resins.

There is no restriction | limiting in particular as a weight average molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 3,000 or more are preferable and 5,000-1,000,000 are more preferable. 7,000 to 500,000 are particularly preferred.
When the weight average molecular weight is less than 3,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as a glass transition temperature (Tg) of the said adhesive base material, Although it can select suitably according to the objective, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable. In the toner, since a polyester resin subjected to a crosslinking reaction and an extension reaction coexists, the toner exhibits good storage stability even when the glass transition temperature is lower than that of a conventional polyester toner.
When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.

  The glass transition temperature can be measured by, for example, the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. can do.

Specific examples of the adhesive substrate are not particularly limited and may be appropriately selected depending on the intended purpose. Particularly preferred examples include polyester resins.
There is no restriction | limiting in particular as said polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are mentioned especially suitably.
The urea-modified polyester resin comprises an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. Obtained by reacting in phase.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond, and in this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.

  Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophorone diamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, and (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol A polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene. Mixture of oxide 2 mol adduct and polycondensate of terephthalic acid, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A A polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid (9) Bisphenol A ethylene, a mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate and uread with hexamethylene diamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and toluene diisocyanate with urea diisocyanate with hexamethylenediamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

---- Binder resin ---
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, although a polyester resin etc. are mentioned, Unmodified polyester resin (unmodified polyester resin) is especially preferable.
When the unmodified polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of a polyol (PO) and a polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure that is compatible with each other. It is preferable in terms of resistance to hot offset.

The weight average molecular weight (Mw) of the unmodified polyester resin is preferably 1,000 to 30,000, preferably 1,500 to 15, in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). 1,000 is more preferable. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Therefore, the content of the component having the weight average molecular weight (Mw) of less than 1,000 as described above. Is required to be 8 to 28% by mass. On the other hand, when the weight average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the unmodified polyester resin is preferably 35 to 70 ° C. When the glass transition temperature is less than 35 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is usually 1.0 to 50.0 mgKOH / g, and preferably 5.0 to 20.0 mgKOH / g.
When the unmodified polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the unmodified polyester resin (PE) is 5/95. -25/75 is preferable, and 10 / 90-25 / 75 is more preferable.
If the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance may be deteriorated, and if it is less than 75, the low-temperature fixability and the glossiness of the image may be deteriorated. .

  As content of the said unmodified polyester resin in the said binder resin, 50-100 mass% is preferable, for example, and 55-95 mass% is more preferable. When the content is less than 50% by mass, low-temperature fixability, fixed image strength, gloss, and the like may be deteriorated.

-Crystalline polyester resin-
The crystalline polyester resin has crystallinity and exhibits a heat-melting characteristic that causes a sudden decrease in viscosity near the fixing start temperature. In other words, until the melting start temperature, the heat resistant storage stability is good due to crystallinity, and at the melting starting temperature, a sharp viscosity drop (sharp melt property) occurs and fixing is performed. A compatible toner can be produced. In addition, the mold release width (the difference between the low temperature fixing lower limit temperature and the hot offset occurrence temperature) is also excellent.

  The crystalline polyester is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diol compounds having 2 to 6 carbon atoms as alcohol components, particularly 1,4-butanediol and 1,6. Synthesis using hexanediol and those containing 80 mol% or more, preferably 85 to 100 mol%, and at least maleic acid, fumaric acid, succinic acid and derivatives thereof as acidic components Preferred examples thereof include crystalline polyester resins represented by the following general formula (1).

However, in the above general formula (1), n and m represent the number of repeat units, L is an integer of 1 to 3, R ¹ and R ² may be the same as each other, or different And may represent a hydrogen atom or a hydrocarbon group.

In order to control the crystallinity and softening point of the crystalline polyester resin, when the crystalline polyester is synthesized, a trihydric or higher polyhydric alcohol such as glycerin is used as the alcohol component, trimellitic anhydride is used as the acid component, etc. Non-linear polyesters obtained by condensation polymerization by adding a trivalent or higher polyvalent carboxylic acid may be used. The molecular structure of the crystalline polyester can be confirmed by solid NMR.
The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 1,000 to 30,000, more preferably 1,000 to 6,500 in terms of molecular weight distribution by GPC of the soluble portion of orthodichlorobenzene. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.
The number average molecular weight (Mn) of the crystalline polyester resin is preferably 500 to 6,000, more preferably 500 to 2,000 in terms of molecular weight distribution by GPC of the soluble part of orthodichlorobenzene. Moreover, as (Mw / Mn), 2-8 are preferable and 2-5 are more preferable.
In the molecular weight distribution by GPC, the peak position of the molecular weight distribution diagram in which the horizontal axis represents log (M) and the vertical axis represents mass% is in the range of 3.5 to 4.0, and the peak half-value width is 1 .5 or less is preferable.

The melting temperature and F1 _{/ 2} temperature of the crystalline polyester resin are preferably low so long as the heat resistant storage stability does not deteriorate. For example, the DSC endothermic peak temperature is preferably 50 to 150 ° C. When the melting temperature and the F _1/2 temperature are less than 50 ° C., the heat-resistant storage stability is deteriorated, and blocking tends to occur at the temperature inside the developing device, and when it exceeds 150 ° C., the lower limit fixing temperature is increased. Therefore, the low temperature fixability may be deteriorated.

The crystalline polyester resin preferably has an absorption based on at least the olefin to any of the infrared absorption spectrum at 965 ± 10 cm ^-1 and 990 ± 10cm ^-1 δCH (out-of-plane bending vibration). When absorption based on δCH of the olefin is present at the position, the low-temperature fixability is improved.

The acid value of the crystalline polyester is preferably 8 mgKOH / g or more, and more preferably 20 mgKOH / g or more in order to achieve low temperature fixability from the viewpoint of the affinity between paper and resin. On the other hand, in order to improve hot offset property, 45 mgKOH / g or less is preferable.
The hydroxyl value of the crystalline polyester resin is preferably from 0 to 50 mgKOH / g, more preferably from 5 to 50 mgKOH / g, from the viewpoint of improving low-temperature fixability and charging characteristics.

  When the non-modified polyester resin (b) and the crystalline polyester resin (c) are contained in the toner, the urea bond-forming group-containing polyester resin (a), the unmodified polyester resin (b), and the crystalline The mixing mass ratio with the polyester resin (c) is usually (a) / (b) + (c) of 5/95 to 25/75, preferably 10/90 to 25/75, and 12/88 to 25/75 is more preferable, 12/88 to 22/78 is still more preferable, and the mass ratio of (b) to (c) is 99/1 to 50/50, and 95/5 to 60/40. Is preferable, and 90/10 to 65/35 is more preferable. When the mass ratio is out of the numerical range, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat resistant storage stability and low temperature fixability.

  The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). The oil phase is emulsified or dispersed in the aqueous phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form the oil droplets, and both are subjected to elongation reaction or crosslinking in the aqueous phase. (2) The oil phase is emulsified or dispersed in the aqueous phase to which the active hydrogen group-containing compound has been added in advance to form the oil droplets. It may be produced by extending or cross-linking both, or (3) the oil phase is added and mixed in the aqueous phase, and then the active hydrogen group-containing compound is added to the oil droplets. Form the It may be generated by elongation reaction or crosslinking reaction from particle interfaces in phase medium. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive base material by the emulsification or dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

  Examples of a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)) in the aqueous phase include, for example, the water In the phase, a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, the release agent, the charge control agent, and the unmodified polyester resin For example, a method of adding the oil phase prepared by dissolving or dispersing the toner material in the organic solvent and dispersing it by a shearing force may be used.

In the emulsification or dispersion, the use amount of the aqueous phase is preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner material.
When the amount used is less than 50 parts by mass, the toner material may be poorly dispersed and toner particles having a predetermined particle size may not be obtained. When the amount used exceeds 2,000 parts by mass, the production cost is high. May be.

In the emulsification or dispersion, if necessary, it is preferable to use a dispersant from the viewpoint of stabilizing the oil droplets and sharpening the particle size distribution while obtaining a desired shape.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used alone or in combination of two or more. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nippon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M); F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In the preparation of the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

-Oil drops-
The oil droplets are obtained by emulsifying or dispersing the oil phase in the aqueous phase.
The oil droplets are formed by emulsifying or dispersing the oil phase in the aqueous phase, and the composition of the oil droplets is the same as the composition of the oil phase. That is, the oil droplets include, for example, any of the monomer, the polymer, and a polymer that can react with the active hydrogen group-containing compound, and if necessary, the colorant, the release agent, The toner material containing the other components such as a charge control agent is contained, preferably the organic solvent is contained, and the toner material is dissolved in the organic solvent.

The viscosity of the oil droplet can be measured, for example, by dynamic viscoelasticity measurement, and the fluidity of the oil droplet can be measured, for example, by measuring a Casson yield value.
There is no restriction | limiting in particular as the method of the said dynamic viscoelasticity measurement, According to the objective, it can select suitably, For example, the flow curve ("AR2000"; TA Instruments company make) measured using the high shear viscometer (TA Instruments company make). (Hysteresis curve).

The oil droplets at the time of the convergence and the removal of the organic solvent preferably have a Casson yield value at 25 ° C. of greater than 0.5 Pa and less than 10,000 Pa, for example.
If the Casson yield value is 0.5 Pa or less, a deformed toner may not be obtained, and if it exceeds 10,000 Pa, the fluidity and viscosity of the oil droplets are increased and productivity is deteriorated. There is.
In addition, when the Casson yield value is 0.5 Pa or less, even if the oil droplet has the structural viscosity, the structural viscosity is weak and the state is close to the Newtonian viscosity.

The Casson yield value is described, for example, in books such as “Rheology for chemists” (Shigeharu Onoki, Kagaku Dojinsha, p. 205), and is based on Casson's approximate expression represented by Equation 1 below. Can be sought. That is, the Casson yield value indicates the value of the shear stress when the shear rate is 0, as shown in FIG.
In Equation 1, τ is the shear stress, τ ₀ is the yield value, Eta is the plastic viscosity, and D is the shear rate.
The Casson yield value can be measured using, for example, a high shear viscometer ("AR2000", manufactured by TA Instruments).

  The contents of the water phase and the oil phase in the oil droplets are not particularly limited and may be appropriately selected depending on the purpose. For example, the oil phase contains 90 to 10% by mass, and the oil phase It is preferable that 10-90 mass% is included. When the content of the water phase and the oil phase is within the numerical range, an oil-in-water emulsion or suspension in which the oil phase is dispersed in the water phase is formed.

<Convergence>
The convergence is performed by associating the oil droplets present in the vicinity with each other in oil droplets formed by emulsifying or dispersing the oil phase in the aqueous phase. Due to the convergence, one particle is formed from the oil droplets existing in the vicinity.
The convergence is obtained by producing a toner by granulating the toner in an aqueous phase, that is, a known suspension polymerization method, emulsion polymerization method, dissolution suspension method, and forming an adhesive substrate described later in the form of particles. This is performed when the toner is manufactured by a manufacturing method of the toner to be manufactured.

When emulsifying or dispersing the oil phase in the aqueous phase, when emulsifying or dispersing by applying a high shear force, the oil phase exhibits not only a Newtonian viscosity but also a non-Newtonian viscosity Even so, the structural viscosity is broken by the high shear force, the viscosity is close to that of a Newtonian fluid, and spherical oil droplets are formed according to the difference in interfacial tension between the oil phase and the water phase.
When a low shearing force is applied to the oil droplets so as to stir slowly, or when the convergence is performed in a stationary state, a toner having a narrow particle size distribution can be obtained. This is considered to be because, even when the particle size distribution of the oil droplets is wide, the small oil droplets are associated with the large oil droplets, thereby reducing the fine powder region and narrowing the entire particle size distribution.

In order to obtain a deformed toner, it is necessary to prevent fluid from flowing in the oil droplets at the time of convergence.
In the convergence, the oil droplets are released from a high shearing force. Therefore, when the oil droplets have the non-Newtonian viscosity and have a structural viscosity, the structural viscosity is recovered or recovered. However, the oil droplets are associated with each other. At this time, since the associated oil droplets have the structural viscosity, the oil droplets do not flow in the oil droplets, and each oil droplet in the formed particle maintains its shape. To form deformed particles. For example, as shown in FIG. 3a, the oil droplet having a large particle diameter maintains the shape of the oil droplet having a large particle diameter within the formed particle after the convergence. Further, as shown in FIG. 3b, the oil droplets having a small particle diameter maintain the shape of the oil droplets having a small particle diameter while associating with the oil droplets having a large particle diameter after the convergence.
Therefore, even if the oil droplets have a large particle size or a small particle size, the oil droplet interfaces are associated with each other, but the shape of each oil droplet is relatively maintained to form a deformed toner.

<Removal of organic solvent>
The removal of the organic solvent removes the organic solvent from oil droplets formed by emulsifying or dispersing an oil phase containing the organic solvent in the aqueous phase.
The removal of the organic solvent is performed, for example, when the toner is produced by a known dissolution suspension method or the toner production method of the preferred embodiment of the present invention.

In order to obtain a deformed toner, it is necessary to prevent the fluid from flowing in the oil droplet when the organic solvent is removed.
When the oil droplet has the non-Newtonian viscosity and has a structural viscosity, even if the structural viscosity is destroyed by the emulsification or dispersion, the viscosity of the oil droplet recovers with time. As shown in FIG. 4, for example, the structural viscosity does not recover during the convergence, and even when large spherical or substantially spherical oil droplets are obtained, the structural viscosity is recovered over time, and the organic solvent is removed. When the organic solvent is removed, no flow occurs in the oil droplets when the organic solvent is removed, so that the surface area shrinkage cannot follow the uniform volume shrinkage, and deformed particles are formed.

  In the removal of the organic solvent, as long as the oil droplets exhibit a non-Newtonian viscosity at the time of the removal, a deformed toner can be obtained, which includes converging the oil droplets, Removing the organic solvent from the oil droplets, wherein the oil droplets during the convergence show a non-Newtonian viscosity, and the oil droplets during the removal of the organic solvent show a non-Newtonian viscosity preferable. When the oil droplets exhibit non-Newtonian viscosity at the time of the convergence and the removal of the organic solvent, a toner having a smaller particle size and a more irregular shape can be obtained.

  The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed into a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board, etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries Ltd.), automatic mortar, and the like.

  The toner of the present invention has the following average circularity, volume average particle diameter (Dv), volume average particle diameter (Dv) / number average particle diameter (Dn), penetration, low temperature fixability, and no offset. It preferably has temperature, thermal characteristics, glass transition temperature, acid value, image density, and the like.

The average circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected area as the toner shape by the perimeter of the actual particles, and is preferably 0.900 to 0.980, for example, 0.900 to 0 .970 is more preferred. The particles having an average circularity of 0.970 or more are preferably 10% or less.
When the average circularity exceeds 0.980, in an image forming system employing blade cleaning or the like, poor cleaning occurs on the photoreceptor or the transfer belt, and stains on the image, such as photographic images, etc. In the case of image formation with a high image area ratio, the toner on which an untransferred image has been formed due to poor paper feed or the like may become a transfer residual toner on the photosensitive member, resulting in background smearing of the accumulated image. Or, it may contaminate the charging roller for charging the photoreceptor in contact with the photosensitive member, and the original charging ability may not be exhibited.

The average circularity is measured by, for example, an optical detection band method in which a suspension containing toner is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured as follows using a flow type particle image analyzer ("FPIA-2100"; manufactured by Sysmex Corporation).
First, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance. Add ~ 0.5g. Next, the suspension in which the sample is dispersed is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the dispersion concentration is set to 3,000 to 10,000 / μl. Can be measured in shape and distribution.

The volume average particle diameter (Dv) of the toner is preferably, for example, 3 to 8 μm, and more preferably 4 to 7.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When the thickness exceeds 8 μm, the resolution is high and high. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is, for example, preferably 1.05 to 1.25, more preferably 1.05 to 1.20. preferable.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is less than 1.05, in the two-component developer, the toner is fused to the surface of the carrier during long-term stirring in the developing device, The chargeability of the carrier may be reduced, and the cleaning property may be deteriorated. In the case of a one-component developer, the filming of the toner on the developing roller and the thinning of the toner are performed. Toner fusion may easily occur, and if it exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and toner particles in the case where the balance of the toner in the developer is performed Variation in diameter may be large.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.05 to 1.20, the heat resistant storage stability, the low temperature fixability, and the hot offset resistance are all excellent. In particular, when used in a full-color copying machine, the glossiness of the image is excellent. With two-component developers, there is little fluctuation in the toner particle diameter in the developer even if the toner balance for a long period of time is achieved, and good and stable developability can be obtained even with long-term stirring in the developing device. Even if the balance of the toner is carried out with the agent, fluctuations in the particle diameter of the toner are reduced, and there is no filming of the toner on the developing roller and no fusion of the toner to the member to the blade for thinning the toner. Even in the long-term use (stirring) of the developing device, good and stable developability can be obtained, so that a high-quality image can be obtained.

  The volume average particle diameter and the ratio (Dv / Dn) between the volume average particle diameter and the number average particle diameter are measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can do.

As said penetration, the penetration measured by the penetration test (JIS K2235-1991) needs to be 15 mm or more, for example, and 20-30 mm is more preferable.
When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated.
The penetration can be measured according to JIS K2235-1991. Specifically, a 50 ml glass container is filled with toner and left in a thermostatic bath at 50 ° C. for 20 hours. The penetration can be measured by cooling the toner to room temperature and performing a penetration test. In addition, it has shown that the said heat-resistant preservation | save property is excellent, so that the said penetration value is large.

As the low temperature fixability, from the viewpoint of achieving both a reduction in the fixing temperature and the occurrence of no offset, it is preferable that the lower limit temperature for fixing is lower, and more preferable that the temperature at which no offset is generated is higher. As a temperature range in which both can be achieved, the minimum fixing temperature is less than 140 ° C., and the non-offset temperature is 200 ° C. or more.
The fixing minimum temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the obtained fixed image is rubbed with a pad. The fixing member temperature is the lower limit fixing temperature.
The non-offset temperature is adjusted such that, for example, the toner to be evaluated is developed with a predetermined amount using an image forming apparatus, and is adjusted so that the temperature of the fixing member is variable. Can be determined by measuring.

The thermal characteristics are also called flow tester characteristics, and are evaluated as, for example, a softening temperature (Ts), an outflow start temperature (Tfb), a 1/2 method softening point (T1 / 2), and the like.
These thermal characteristics can be measured by an appropriately selected method. For example, the thermal characteristics can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
There is no restriction | limiting in particular as said softening temperature (Ts), According to the objective, it can select suitably, For example, 30 degreeC or more is preferable and 50-90 degreeC is more preferable. When the softening temperature (Ts) is less than 30 ° C., the heat resistant storage stability may be deteriorated.
There is no restriction | limiting in particular as said outflow start temperature (Tfb), According to the objective, it can select suitably, For example, 60 degreeC or more is preferable and 80-120 degreeC is more preferable. When the outflow start temperature (Tfb) is less than 60 ° C., at least one of heat resistant storage stability and offset resistance may be deteriorated.
The 1/2 method softening point (T1 / 2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 ° C. or higher is preferable, and 100 to 170 ° C. is more preferable. When the 1/2 method softening point (T1 / 2) is less than 90 ° C., the offset resistance may be deteriorated.

There is no restriction | limiting in particular as said glass transition temperature, Although it can select suitably according to the objective, For example, 40-70 degreeC is preferable and 45-65 degreeC is more preferable. When the glass transition temperature (Tg) is less than 40 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.
The glass transition temperature can be measured using, for example, a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation).

  The acid value of the toner is preferably, for example, 1.0 to 50.0 (KOH mg / g), and more preferably 3 to 35 (KOH mg / g). By giving the toner an acid value, it becomes easy to be negatively charged.

The image density is, for example, preferably 1.40 or more, more preferably 1.45 or more, and 1.50 or more, as measured by a spectrometer (X-Light, 938 Spectrodensitometer). Is more preferable.
If the image density is less than 1.40, the image density may be low and high image quality may not be obtained.
The image density can be determined by, for example, using a tandem color electrophotographic apparatus (“Imagio Neo 450”; manufactured by Ricoh Co., Ltd.) and a developer adhesion amount of 1 on copy paper (“Type 6200”; manufactured by Ricoh Co., Ltd.). A solid image of .00 ± 0.1 mg / cm ² was formed at a surface temperature of the fixing roller of 160 ± 2 ° C., and the image density at any five positions in the obtained solid image was measured by a spectrometer (manufactured by X-Light Corporation). 938 (spectrodensitometer) and the average value can be calculated.

  The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.

The method for producing a toner of the present invention includes at least the step of emulsifying or dispersing the oil phase in the aqueous phase to form oil droplets and converging the oil droplets, and the oil droplets during the convergence are non-condensed. Since it exhibits a Newtonian viscosity, even if the oil droplets are associated with each other in the convergence, the fluid does not flow in the oil droplets, and deformed particles are obtained.
The toner production method of the present invention includes at least the step of emulsifying or dispersing the oil phase containing the organic solvent in the aqueous phase to form oil droplets, and removing the organic solvent from the oil droplets. Since the oil droplets during the removal of the organic solvent exhibit non-Newtonian viscosity, no flow occurs in the oil droplets during removal of the organic solvent, and surface area shrinkage cannot follow volume shrinkage. For this reason, deformed particles are obtained.
Therefore, it is possible to efficiently produce a toner having a potato shape formed by combining a plurality of spherical particles with a small particle size, which is excellent in cleaning property and high image quality, excellent in cleaning property and high image quality. can do.

  Since the toner of the present invention has a potato shape formed by coalescing a plurality of spherical particles with a small particle diameter, it has excellent cleaning properties and can form a high-quality image. When the toner of the present invention includes the adhesive base obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous phase, Excellent characteristics such as chargeability, fluidity, releasability, and fixability, especially low temperature fixability. Therefore, the toner of the present invention can be suitably used in various fields, and can be more suitably used for image formation by electrophotography. The following toner-containing container, developer, and process of the present invention are described below. It can be particularly suitably used for a cartridge, an image forming apparatus, and an image forming method.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components appropriately selected such as the carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and image can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and high magnetization materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The core material has a volume average particle diameter of preferably 10 to 150 μm, more preferably 40 to 100 μm.
When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like, if necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.

Since the developer of the present invention contains the toner of the present invention having a potato shape formed by coalescing a plurality of spherical particles with a small particle diameter, the developer is excellent in cleaning properties and stable high-quality images. Can be formed.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention is formed by filling the container of the toner of the present invention or the developer.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably.
The size, shape, structure, material, etc. of the container body containing toner is not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. The spiral surface irregularities are formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.
The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. And at least developing means for forming the film, and other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably provided detachably in the electrophotographic apparatus of the present invention described later.

Here, for example, as shown in FIG. 5, the process cartridge includes a photosensitive member 101, and further includes a charging unit 102, a developing unit 104, and a cleaning unit 107, and further includes other members as necessary. Do it.
As the photoreceptor 101, the above-described one can be used.
A light source capable of writing with high resolution is used for the exposure means 103.
An arbitrary charging member is used for the charging unit 102.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon or the like is preferable in terms of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

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

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the electrostatic latent image carrier (photoconductor) with the transfer charger using the visible image, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose, but a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 6 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 6, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 7 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 6, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and the like around the photoconductor 10. Except for the fact that the cyan developing unit 45C is disposed directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 7, the same components as those in FIG. 6 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 8 is a tandem color image forming apparatus. The tandem image forming apparatus 100 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 8. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus 100, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image-corresponding image (L in FIG. 9), and an exposure device for forming an electrostatic latent image corresponding to each color image on the photosensitive member, A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image of each color toner, and the toner image is transferred to the intermediate transfer member 5. The image forming apparatus includes a transfer charger 62 for transferring the image on the surface, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta image) based on image information of each color. And cyan images) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotated by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 150 is rotated to feed out the sheets (recording paper) on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming apparatus and the image forming method of the present invention, the toner of the present invention having a potato shape formed by coalescing a plurality of spherical particles having a small particle diameter, which has excellent cleaning properties and high image quality, is used. Therefore, a high-quality image can be formed efficiently.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Production Example 1)
-Preparation of oil phase-
The oil phase of Production Example 1 was prepared as follows.

--- Synthesis of unmodified polyester (low molecular weight polyester)-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 529 parts by mass of bisphenol A propion oxide 3 mol adduct, 208 parts by mass of terephthalic acid, 46 masses of adipic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. A modified polyester was synthesized.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,600, a weight average molecular weight (Mw) of 5,800, a glass transition temperature (Tg) of 45 ° C., and an acid value of 24.

-Preparation of master batch (MB)-
1200 parts by mass of water, 540 parts by mass of carbon black (“PB-k7: Printex 60”, manufactured by Degussa, DBP oil absorption = 114 ml / 100 g, pH = 7) and 1200 parts by mass of polyester resin were added to Henschel mixer (Mitsui Mine Co., Ltd.). Mixed). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

--Synthesis of prepolymer--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.74% by mass.

--Synthesis of ketimine (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen machine-containing compound) was 418.

  In a reaction vessel equipped with a stir bar and a thermometer, 300 parts by mass of the unmodified polyester, 90 parts by mass of carnauba wax, 10 parts by mass of rice wax, and 1000 parts by mass of ethyl acetate were charged, and the temperature was raised to 79 ° C. with stirring. After warming and dissolving, it was rapidly cooled to 4 ° C. Using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.), three passes were performed under conditions where the liquid feed speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 80% by volume of 0.5 mm zirconia beads were filled. A wax dispersion having a volume average particle size of 0.6 μm was obtained. Next, 500 parts by mass of the master batch and 640 parts by mass of a 70% by mass ethyl acetate solution of the unmodified polyester were added to the wax dispersion, mixed for 10 hours, and then passed through a bead mill under the same conditions as above. Then, ethyl acetate was added to obtain a raw material solution having a solid content (130 ° C., 30 minutes) of 50 mass%.

  Into a reaction vessel, 73.2 parts by mass of the raw material solution, 6.6 parts by mass of the prepolymer, and 0.48 parts by mass of the ketimine compound were charged and mixed well to prepare an oil phase.

-Oil phase viscosity-
About the obtained oil phase, Casson yield value and structural viscosity were measured as follows. The results are shown in Table 1.

<Measurement of Casson yield value>
The Casson yield value of the oil phase was measured with a high shear viscometer ("AR2000", manufactured by TA Instruments). The measurement conditions were obtained by measuring a flow curve at 25 ° C. with a 40 mm parallel plate and a gap of 1.000 mm, and calculating using the Casson approximation represented by the following Equation 1.
In Equation 1, τ is the shear stress, τ ₀ is the yield value, Eta is the plastic viscosity, and D is the shear rate.
As a result, the Casson yield value of the oil phase was 10.5 Pa.

<Measurement of structural viscosity>
The structural viscosity of the oil phase was measured with a high shear viscometer (“AR2000”, manufactured by TA Instruments). The measurement conditions were 30 ° C., 40 mm parallel plate, gap 0.500 mm, and shear rate was measured from 0 to 1,800 (1 / s) in 2 minutes, and then from 1,800 to 0 (1 / s). The measurement was performed over a period of minutes, and the structural viscosity was determined from the flow curve (hysteresis curve). As a result, non-Newtonian viscosity having structural viscosity was exhibited, and the structural viscosity was thixotropy.

(Production Examples 2 to 4)
-Preparation of oil phase-
In Production Example 1, a master batch in which carbon black and resin in the master batch were replaced with the pigment and resin shown in Table 1 was used, and the solid content concentration in the raw material solution was adjusted to the solid content concentration shown in Table 1. Prepared oil phases of Production Examples 2 to 4 in the same manner as in Production Example 1. The Casson yield value and structural viscosity of the obtained oil phase were measured by the same method as in Production Example 1. The results are shown in Table 1.

(Production Example 5)
-Preparation of oil phase-
In Production Example 3, the oil phase of Production Example 5 was produced in the same manner as in Production Example 3, except that the amount of the master batch used was changed to 2500 parts by mass and the solid content concentration in the raw material solution was changed to 70% by mass. Was prepared. The Casson yield value and structural viscosity of the obtained oil phase were measured by the same method as in Production Example 1. The results are shown in Table 1.

Example 1
-Formation of oil droplets-
Using the oil phase prepared in Production Example 1, oil droplets were formed as follows to produce a toner.

-Preparation of aqueous phase-
--- Preparation of fine particle dispersion ---
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30", manufactured by Sanyo Chemical Industries, Ltd.), styrene 83 Part by weight, 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours. Vinyl resin particles (styrene salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) An aqueous dispersion (fine particle dispersion) was prepared.
The volume average particle size of the fine particles contained in the obtained fine particle dispersion was measured with a particle size distribution measuring apparatus (“LA-920”, manufactured by Horiba, Ltd.) using a laser light scattering method, and found to be 105 nm. Further, when a part of the fine particle dispersion was dried to isolate the resin, and the glass transition temperature (Tg) of the resin was measured, it was 59 ° C. and the weight average molecular weight (Mw) was measured. 000.

  990 parts by weight of water, 83 parts by weight of the fine particle dispersion, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”, manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts by weight of ethyl acetate Were mixed and stirred to obtain a milky white liquid (aqueous phase).

--Emulsification or dispersion--
120 parts by mass of the aqueous phase is added to 80.48 parts by mass of the oil phase obtained in Production Example 1, and the mixture is mixed for 1 minute at a rotational speed of 13,000 rpm with a TK homomixer (made by Special Machine). An emulsified slurry containing oil droplets was prepared.

<Convergence>
The resulting emulsified slurry was slowly stirred at room temperature and converged for 1 hour. The Casson yield value and structural viscosity after 1 hour of the emulsified slurry (oil droplets) were measured. The results are shown in Table 2.

<Removal of organic solvent>
The emulsified slurry after convergence was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 1 hour, aging was performed at 60 ° C. for 5 hours to obtain a dispersed slurry.

-Cleaning and drying-
After filtering 100 parts by mass of the dispersion slurry under reduced pressure, adding 300 parts by mass of ion exchange water to the filter cake, mixing with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtering three times. And a final filter cake was obtained.
The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh of 75 μm to obtain toner base particles of Example 1.

-External additive treatment-
Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) contains 0.7 parts by mass of hydrophobic silica as an external additive and 0.3 parts by mass of hydrophobized titanium oxide with respect to 100 parts by mass of the obtained toner base particles of Example 1. The toner of Example 1 was manufactured by mixing with the toner.
The obtained toner was observed with a scanning electron microscope (SEM) FE-SEM (“S-4200”, manufactured by Hitachi, Ltd.). The SEM photograph at this time is shown in FIG. 1A. From the SEM photograph, the toner of Example 1 has a potato shape, and the diameter R (μm) of the spherical particles and the length L (μm) in the depth direction of the joining portion of the spherical particles are shown. As a result of the determination, all satisfied 0.1R ≦ L <1.0R.

  For the obtained toner, the volume average particle size (Dv), number average particle size (Dn), particle size distribution (volume average particle size (Dv) / number average particle size (Dn)), and average circularity are determined by the following methods. It was measured. The results are shown in Table 3.

<Toner particle size>
The volume average particle diameter (Dv) of the toner and the number average particle diameter (Dn) of the toner were measured using a particle size measuring device (“Multisizer II”; manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm. From these results, the particle size distribution (volume average particle diameter (Dv) / number average particle diameter (Dn)) was calculated. As a result, the volume average particle size was 5.5 μm, the number average particle size was 4.9 μm, and the particle size distribution (Dv / Dn) was 1.12.

<Average circularity>
The average circularity of the toner was measured using a flow type particle image analyzer (“FPIA-1000”, manufactured by Toa Medical Electronics Co., Ltd.). Specifically, 0.1 to 0.5 ml of a surfactant (alkylbenzene sulfonate) as a dispersant is added to 100 to 150 ml of water from which impure solids have been removed in advance, and each toner is further added. 0.1 to 0.5 g was added and dispersed. The obtained dispersion is dispersed for about 1 to 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.), so that the concentration of the dispersion is 3,000 to 10,000 / μl, and the shape and distribution of the toner. Was measured. The average circularity was calculated from these measurement results. As a result, the average circularity was 0.978.

(Examples 2 to 5)
In Example 1, toner base particles of Examples 2 to 5 were produced in the same manner as in Example 1 except that the oil phase of Production Example 1 was replaced with the oil phase of Production Examples 2 to 5, respectively. Additive treatment was performed to produce toners of Examples 2-5. Further, various physical properties and the like were measured in the same manner as in Example 1. The results are shown in Tables 2 and 3.
Further, from the SEM photographs of the toners of Examples 2 to 5, the toners of Examples 2 to 5 have a potato shape, and the diameter R (μm) of the spherical particles and the depth of the coalescing portion between the spherical particles. As a result of obtaining the length L (μm) in the vertical direction, all satisfy 0.1R ≦ L <1.0R.

(Example 6)
-Formation of oil droplets-
In the following manner, an oil phase and an aqueous phase were prepared, oil droplets were formed, and a toner was manufactured.

-Preparation of oil phase-
--- Preparation of masterbatch (MB) ---
1200 parts by mass of water, 540 parts by mass of pigment (“PY155”; manufactured by Clariant) and 1200 parts by mass of polyester resin were mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

  In a reaction vessel equipped with a stirrer and a thermometer, 90 parts by weight of carnauba wax, 10 parts by weight of rice wax, and 300 parts by weight of toluene were charged, heated to 80 ° C. with stirring, dissolved, and then at once. Quenched to 4 ° C. Using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.), 5 passes were performed under the condition that the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / second, and 80% by volume of 0.5 mm zirconia beads were filled. A wax dispersion having a volume average particle size of 0.6 μm was obtained. Next, 600 parts by mass of the master batch was added to the wax dispersion, mixed for 10 hours, and then subjected to 5 passes with a bead mill under the same conditions as described above. 100 parts by mass of this in another container in which a stir bar and a thermometer are set, 70 parts by mass of styrene, 5 parts by mass of methacrylic acid, 25 parts by mass of n-butyl acrylate, and a metal compound of dialkyl salicylate (the charge control agent) ) 5 parts by mass was added and dissolved or dispersed uniformly at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). In this, 5 parts by mass of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare an oil phase of the polymerizable monomer composition.

--- Oil phase viscosity-
The obtained oil phase was measured for Casson yield value and structural viscosity. The Casson yield value was 1.0 Pa and had structural viscosity. The structural viscosity was thixotropy.

-Preparation of aqueous phase-
350 parts by mass of ion-exchanged water and 230 parts by mass of a 0.1 M Na ₃ PO ₄ aqueous solution were heated to 60 ° C. and then stirred at 12,000 rpm using a TK homomixer. To this, 34 parts by mass of a 1.0 M CaCl ₂ aqueous solution was gradually added to prepare an aqueous phase of an aqueous dispersion containing Ca ₃ (PO ₄ ) ₂ .

  The oil phase is added to the obtained aqueous phase, and stirred at 11,000 rpm for 3 minutes with a TK homomixer at 60 ° C. in a nitrogen atmosphere to produce a polymerizable monomer composition (the oil droplets). Grained.

<Convergence>
The resulting polymerizable monomer composition was converged for 1 hour while being slowly stirred with a paddle stirring blade. Casson yield value and structural viscosity after 1 hour of the polymerizable monomer composition (oil droplets) were measured. The results are shown in Table 3.

  After the convergence, the polymerizable monomer composition was heated to 80 ° C. and reacted for 10 hours, and then the residual monomer was distilled off under reduced pressure. After cooling, hydrochloric acid was added to dissolve calcium phosphate, Filtration, washing and drying were performed to obtain yellow toner base particles.

-External additive treatment-
The obtained toner base particles of Example 6 were subjected to an external additive treatment in the same manner as in Example 1 to produce the toner of Example 6.

For the obtained toner, the volume average particle diameter (Dv), the number average particle diameter (Dn), the particle size distribution (volume average particle diameter (Dv) / number average particle diameter (Dn)), and average circularity are shown in Examples. It was measured by the same method as in 1. The results are shown in Table 3.
Further, from the SEM photograph of the toner of Example 6, the toner of Example 6 has a potato shape, and the diameter R (μm) of the spherical particles and the length in the depth direction of the joining portion of the spherical particles. As a result of obtaining the thickness L (μm), all satisfied 0.1R ≦ L <1.0R.

(Comparative Example 1)
In Example 5, toner base particles were prepared by the same method as in Example 5 except that the solid content concentration of the oil phase obtained in Production Example 5 was changed to 50% by mass, and external additive treatment was performed. A toner of Comparative Example 1 was produced. Further, various physical properties and the like were measured in the same manner as in Example 1. The results are shown in Table 3.
The obtained toner was observed with a scanning electron microscope (SEM) FE-SEM (“S-4200”; manufactured by Hitachi, Ltd.). The SEM photograph at this time is shown in FIG. From the SEM photograph, it was confirmed that the toner of Comparative Example 1 had a true spherical shape.

(Comparative Example 2)
A toner of Comparative Example 2 was prepared in the same manner as Example 1 of JP-A-2001-66820.
The obtained toner was observed with a scanning electron microscope (SEM) FE-SEM (“S-4200”; manufactured by Hitachi, Ltd.). From this SEM photograph, it was confirmed that the toner of Comparative Example 2 had a true spherical shape.

  Next, a conventional method is performed from 5% by mass of each of the toners of Examples 1 to 6 and Comparative Examples 1 and 2 that have been treated with external additives and 95% by mass of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin. Thus, developers of Examples 1 to 6 and Comparative Examples 1 to 2 were produced.

  Using the obtained developers, (a) cleaning properties, (b) fixing properties, (c) image density, and (d) crack resistance were evaluated as follows. The results are shown in Table 4.

(A) Cleaning property The transfer residual toner on the photosensitive member that has passed the cleaning step is transferred to a white paper using a scotch tape (manufactured by Sumitomo 3M Limited), and this is measured with a Macbeth reflection densitometer (RD514 type). The cleaning property was evaluated based on the standard.
〔Evaluation criteria〕
○ (Good): The difference from the blank is 0.01 or less.
X (defect): The difference with a blank exceeds 0.01.

(B) Fixability (offset generation temperature and fixing lower limit temperature)
Tandem-type color image forming apparatus (image Neo Neo 450, manufactured by Ricoh Co., Ltd.), plain paper (“TYPE 6200”; manufactured by Ricoh Co., Ltd.), and cardboard transfer paper (“copy printing paper <135>”; manufactured by NBS Ricoh) Were used to evaluate fixability (offset non-occurrence temperature and fixing lower limit temperature). Note that the tandem color image forming apparatus can continuously print A4 size paper every 45 minutes.

<Offset generation temperature>
Image formation is performed using the tandem-type color image forming apparatus, and each of the plain paper has a single color of yellow, magenta, cyan, and black, and a solid image of red, blue, and green as each intermediate color. 0.0 ± 0.1 mg / cm ² of toner was adjusted to be developed. The obtained image was fixed by changing the temperature of the fixing belt (heating roller), and the lower limit value (offset generation temperature) of the fixing temperature at which the offset occurred was measured.

<Fixing temperature limit>
For the image, the tandem color image forming apparatus was used to set the cardboard and perform a copy test. The fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more was determined as the minimum fixing temperature.

(C) Image Density Using a tandem type color image forming apparatus (“Imagio Neo 450”; manufactured by Ricoh Co., Ltd.), the amount of each developer adhered to transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) is 1. A solid image of 00 ± 0.1 mg / cm ² was formed at a surface temperature of the fixing roller of 160 ± 2 ° C. The image density at any five positions in the obtained solid image was measured using a spectrometer (“938 Spectrodensitometer, manufactured by X-Rite”. The image density value is an average value of the image densities at the five positions. It means that the higher the obtained image density value, the higher the image density and the higher density image can be formed, and when the image density is 1.4 or more, it is a practical level. Is recognized.

(D) Crack resistance test 50 g of each developer was placed in a 100 ml bottle (manufactured by Nidec Rika Co., Ltd.) and stirred using a paint conditioner at 50 Hz for 30 minutes, followed by separation of the toner by electric field separation and scanning. An electron microscope (SEM) observation was performed. In this SEM observation, the cracking property was evaluated by the ratio (%) of the number of broken or broken toners in 1000 toners. In addition, it shows that crack resistance is inferior, so that a number is large.

From the results of Tables 2 to 4, the following is clear. That is, in Examples 1 to 6, toners having a small particle size and an irregular shape were obtained. It was also found that the toner has excellent cleaning properties, good low-temperature fixability, good image density evaluation results, and high image quality.
On the other hand, it was found that the toners obtained in Comparative Examples 1 and 2 were spherical and had poor cleaning properties. Further, it is recognized that the toner of Comparative Example 2 is inferior in crack resistance.

(Synthesis Example 1)
-Synthesis of crystalline polyester resin (1)-
Into a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, 2070 g of 1,4-butanediol, 2535 g of fumaric acid, 291 g of trimellitic anhydride, and 4.9 g of hydroquinone are placed. The mixture was reacted at 160 ° C. for 5 hours, then heated to 200 ° C. and reacted for 1 hour. Furthermore, it was made to react at 8.3 kPa for 1 hour, and the crystalline polyester resin (1) was synthesize | combined.
The DSC endothermic peak temperature of the obtained crystalline polyester resin is 123 ° C., and the molecular weight distribution by GPC of the soluble portion of orthodichlorobenzene is 2,100 in terms of weight average molecular weight (Mw), 710 in terms of number average molecular weight (Mn), The Mw / Mn was 2.96. Moreover, in the infrared absorption spectrum, when the absorption based on δCH (out-of-plane variable vibration) of olefin was measured, it was 970 cm ⁻¹ .

(Synthesis Examples 2 to 7)
-Synthesis of crystalline polyester resins (2) to (7)-
In the synthesis example 1, except having changed the kind and usage-amount of an alcohol component and an acidic component as shown in Table 4, it is the same method as the synthesis example 1, and the crystalline polyester resin (2)-of the synthesis examples 2-7. (7) was synthesized. Table 5 shows the characteristics of the obtained crystalline polyester resin.

(Preparation Example 1)
-Preparation of crystalline polyester resin dispersion (1)-
100 g of the crystalline polyester resin (5) synthesized in Synthesis Example 5 and 400 g of ethyl acetate were taken in a metal 2 L container, heated and dissolved at 79 ° C., and then cooled in an ice-water bath. 500 ml of glass beads (diameter 3 mm) were added to this, and the mixture was pulverized for 10 hours with a batch type sand mill (made by Campehapio). Then, part of ethyl acetate was distilled off, the volume average particle size was 0.4 μm, solid A crystalline polyester resin dispersion (1) having a partial concentration of 50% by mass was obtained.

(Preparation Examples 2 to 6)
-Preparation of crystalline polyester resin dispersions (2) to (6)-
In Preparation Example 1, the crystalline polyester resin dispersions (2) to (6) of Preparation Examples 2 to 6 were prepared by the same method as Preparation Example 1 except that the dispersion conditions were changed as shown in Table 6. .

(Production Example 6)
-Preparation of oil phase-
--- Synthesis of unmodified polyester (low molecular weight polyester)-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 229 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 529 parts by mass of bisphenol A propion oxide 3 mol adduct, 208 parts by mass of terephthalic acid, 46 adipic acid 46 Part by mass and 2 parts by mass of dibutyltin oxide were added, and a condensation reaction was performed at 230 ° C. for 8 hours under a normal pressure nitrogen stream. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, and then 44 parts by mass of trimellitic anhydride was added and reacted at 180 ° C. for 2 hours under normal pressure to obtain an unmodified polyester.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25.

-Preparation of master batch (MB)-
540 parts by mass of carbon black (“PBk-7 Printex”, manufactured by Degussa) as a colorant (DBP oil absorption 114 ml / 100 g, pH 10), polyester resin (“RS801”, manufactured by Sanyo Chemical Industries, Ltd., acid value = 10) , 1200 parts by mass of weight average molecular weight (Mw) = 20,000, glass transition temperature (Tg) = 64 ° C.) and 1200 parts by mass of water were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded at 150 ° C. for 30 minutes with two rolls, rolled and cooled, and pulverized to a size of 1 mm in diameter using a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

In a reaction vessel in which a stir bar and a thermometer were set, 378 parts by mass of the unmodified polyester, 92 parts by mass of carnauba wax, 22 parts by mass of CCA (“salicylic acid metal complex E-84”, manufactured by Orient Chemical Industry Co., Ltd.), and 947 parts by mass of ethyl acetate was added, the temperature was raised to 80 ° C. with stirring, the temperature was maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts by mass of the master batch and 500 parts by mass of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution.
1324 parts by mass of the obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia. The carbon black and carnauba wax were dispersed by three passes under the condition of 80% by volume of beads. Next, 1042.3 parts by mass of a 65% by mass ethyl acetate solution of the unmodified polyester was added to the dispersion. One pass was performed in a bead mill under the same conditions as described above, and the mixture was dispersed to prepare an oil phase. The solid content concentration of the obtained oil phase (130 ° C., 30 minutes) was 50% by mass.

(Production Example 7)
-Preparation of oil phase-
In Production Example 6, 200 parts by mass of the crystalline polyester resin dispersion (1) was added together with 1042.3 parts by mass of the 65% by mass ethyl acetate solution of the unmodified polyester resin, and a part of ethyl acetate was further evaporated. Prepared the oil phase of Production Example 7 by the same method as Production Example 6.

(Production Examples 8-12)
-Preparation of oil phase-
In Production Example 7, the crystalline polyester resin dispersion (1) was replaced with the crystalline polyester resin dispersions (2) to (6) shown in Table 7, respectively, and the solid content concentration shown in Table 7 was further prepared. Prepared oil phases of Production Examples 8 to 12 in the same manner as in Production Example 7.

(Example 7)
-Manufacture of toner-
Using the oil phase obtained in Production Example 6, a toner was produced as follows.

--Preparation of fine particle dispersion--
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30", manufactured by Sanyo Chemical Industries, Ltd.), styrene 83 Part by weight, 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, so that vinyl resin particles (copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) An aqueous dispersion of polymer) (fine particle dispersion) was prepared.
The volume average particle size of the fine particles contained in the obtained fine particle dispersion was measured with a particle size distribution measuring apparatus (“LA-920”, manufactured by Horiba, Ltd.) using a laser light scattering method, and found to be 105 nm. Further, when a part of the fine particle dispersion was dried to isolate the resin, and the glass transition temperature (Tg) of the resin was measured, it was 59 ° C. and the weight average molecular weight (Mw) was measured. 000.

-Preparation of aqueous phase (aqueous medium)-
990 parts by weight of water, 83 parts by weight of the fine particle dispersion, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”, manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts by weight of ethyl acetate Were mixed and stirred to obtain a milky white liquid (aqueous phase).

--Synthesis of prepolymer--
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, 22 parts by mass of merit acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.53% by mass.

--Synthesis of ketimine (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen machine-containing compound) was 418.

--Emulsification / dispersion (formation of oil droplets)-
In a reaction vessel, 664 parts by mass of the oil phase, 109.4 parts by mass of the prepolymer, and 4.6 parts by mass of the ketimine compound are charged, and 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika). For 1 minute to obtain an emulsified oil phase (the oil droplets). To the emulsified oil phase, 1200 parts by mass of the aqueous phase was added, and the mixture was mixed for 20 minutes at a peripheral speed of 18.4 m / s with a stirring blade using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an emulsion slurry.
Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 1 hour, aging was performed at 45 ° C. for 4 hours to obtain a dispersed slurry.
The solid content concentration of the emulsified oil phase was 50% by mass. Further, the viscosity of the emulsified oil phase was measured by the following method. The results are shown in Table 8.

<Measurement of viscosity>
The viscosity of the emulsified oil phase was measured using a Brookfield rotary viscometer (DV-E VISCOMETER: HADVE115 type). Measurement conditions were measured at 25 ° C. at a rotation speed of 5 rpm, and the viscosity ratio was obtained by measuring the viscosity at a rotation speed of 50 rpm using the same emulsified oil phase and calculating using the following formula. It was. As a result, the emulsified oil phase had a viscosity of 3.5 Pa · s and a viscosity ratio of 3.2.
<Viscosity ratio formula>
Viscosity ratio = viscosity (5 rpm) / viscosity (50 rpm)

--- Washing and drying--
After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed and then filtered. To the filter cake, 100 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed and then filtered. 100 parts by mass of 10% by mass hydrochloric acid was added to the filter cake, mixed, and then filtered. Further, 300 parts by mass of ion-exchanged water was added to the filter cake, mixed and then filtered twice to obtain a final filter cake.

Here, the obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh having an opening of 75 μm to obtain a toner of Example 7. The toner was observed with a scanning electron microscope (SEM) FE-SEM (“S-4200”, manufactured by Hitachi, Ltd.). The SEM photograph at this time is shown in FIGS. 11A and 11B. From the SEM photograph, the obtained toner has a potato shape, and the diameter R (μm) of the spherical particles and the length L (μm) in the depth direction of the joining portion of the spherical particles are obtained. As a result, all satisfied 0.1R ≦ L <1.0R.
The magnifications of the SEM photographs in FIGS. 11A and 11B are 1500 times and 3000 times, respectively.
Further, the volume average particle diameter (Dv), number average particle diameter (Dn), (Dv / Dn), and average circularity of the toner were measured in the same manner as in Example 1. The results are shown in Table 8.

(Examples 8 to 13)
-Manufacture of toner-
In Example 7, the oil phase of Production Example 6 is replaced with the oil phase of Production Examples 7 to 12 shown in Table 8, respectively, and the viscosity of the emulsified oil phase (oil droplets), the solid content concentration, and the peripheral speed of the stirring blade are shown. A toner was produced in the same manner as in Example 7 except that the change was made as shown in FIG. The volume average particle diameter (Dv), number average particle diameter (Dn), (Dv / Dn), and average circularity of the obtained toner were measured. The results are shown in Table 8.
Further, the obtained toners of Examples 8 to 13 were observed by SEM photographs. As a result, the toners of Examples 8 to 13 have a potato shape, and the diameter R (μm) of the spherical particles and the length L (μm) in the depth direction of the joining portion of the spherical particles are obtained. As a result, all satisfied 0.1R ≦ L <1.0R.

(Comparative Example 3)
-Manufacture of toner-
In Example 7, ethyl acetate was added to the emulsified oil phase (oil droplets), the solid content concentration was 25% by mass, and when the emulsified oil phase viscosity was 0.5 Pa · s, dispersion was performed at a peripheral speed of 4.8 m / s. A toner was manufactured in the same manner as in Example 7 except that this was done. The volume average particle diameter (Dv), number average particle diameter (Dn), (Dv / Dn), and average circularity of the obtained toner were measured. The results are shown in Table 8. Further, the toner of Comparative Example 3 was observed from an SEM photograph. As a result, it was found that the toner was spherical.

  Next, with respect to 100 parts by mass of the toners (toner base particles) of Examples 7 to 13 and Comparative Example 3 thus obtained, 0.7 part by mass of hydrophobic silica as an external additive and 0.3% of hydrophobized titanium oxide were obtained. Part by mass was mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain a toner subjected to external additive treatment. Various physical property values of the obtained toner are shown in Tables 9 to 11.

-Preparation of developer-
Next, it was carried out in a conventional manner from 5% by mass of each of the toners of Examples 7 to 13 and Comparative Example 3 treated with external additives and 95% by mass of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin. Each developer of Examples 7 to 13 and Comparative Example 3 was produced.

  Using each of the toners and the obtained developers, (a) charge amount, (b) thermal properties of the toner, (c) fixability (offset non-occurrence temperature and fixing lower limit temperature), (D) Image density, (e) background stain, (f) cleanability, (g) filming, (h) heat resistant storage stability, and (i) crack resistance were measured. The results are shown in Tables 9-11.

(A) Charge amount 6 g of the developer was weighed, charged in a metal cylinder that can be sealed, and blown to obtain the charge amount. The toner concentration was adjusted to 4.5 to 5.5% by mass.

(B) Thermal characteristics of toner (flow tester characteristics)
The thermal characteristics were obtained from a flow curve (see FIGS. 12A to 12B) measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation). Here, in FIGS. 12A to 12B, Ts represents the softening temperature, Tfb represents the outflow start temperature, and the melting temperature in the 1/2 method represents the 1/2 method softening point (F _1/2 ). The measurement conditions were a load of 10 kg / cm ² , a temperature increase rate of 3.0 ° C./min, a die diameter of 0.50 mm, and a die length of 10.0 mm.

(C) Fixability (offset non-occurrence temperature and fixing lower limit temperature)
Using a tandem type color image forming apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.), plain paper (“TYPE 6200”, manufactured by Ricoh Co., Ltd.) and cardboard transfer paper (“copy printing paper <135>”, Inc.) Fixability (offset non-occurrence temperature and fixing lower limit temperature) was evaluated using NBS Ricoh. Note that the tandem color image forming apparatus can continuously print A4 size paper every 45 minutes.

<Temperature without offset>
Image formation is performed using the tandem-type color image forming apparatus, and each of the plain paper has a single color of yellow, magenta, cyan, and black, and a solid image of red, blue, and green as each intermediate color. 0.0 ± 0.1 mg / cm ² of toner was adjusted to be developed. The obtained image was fixed by changing the temperature of the fixing belt (heating roller), and the fixing temperature at which no offset occurred (temperature at which no offset occurred) was measured.

<Fixing temperature limit>
For the image, using the tandem color image forming apparatus, the cardboard was set and a copy test was performed. The fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more was determined as the minimum fixing temperature.

(D) Image density Using the tandem color image forming apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.), the amount of each developer adhered to plain paper (TYPE 6200, manufactured by Ricoh Co., Ltd.) is 1.00 ± 0.00. A solid image of 1 mg / cm ² was formed at a surface temperature of the fixing roller of 160 ± 2 ° C. The image density of arbitrary five places in the obtained solid image was measured using a spectrometer (938 Spectrodensitometer, manufactured by X-Rite). The image density value is shown as an average value of image densities at five locations. Note that the higher the obtained image density value, the higher the image density and the higher the density image can be formed.

(E) Stain on the background Using an image forming apparatus (“Imagio Neo450”, manufactured by Ricoh Co., Ltd.), the blank image is stopped during development, the developer on the photoconductor after development is transferred to tape, and the untransferred tape The difference from the image density was measured with a spectrometer (“938 Spectrodensitometer”, manufactured by X-Light).

(F) Cleaning property The transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to a white paper using a scotch tape (manufactured by Sumitomo 3M Limited), and measured with a Macbeth reflection densitometer (RD514 type). The cleaning property was evaluated based on the standard.
〔Evaluation criteria〕
○ (Good): The difference from the blank is 0.01 or less.
X (defect): The difference with a blank exceeds 0.01.

(G) Filming The presence or absence of toner filming on the developing roller or the photoreceptor was visually observed and evaluated based on the following criteria.
〔Evaluation criteria〕
○: Filming is not observed.
Δ: Streaky filming is observed.
X: Filming is observed as a whole.

(H) Heat-resistant storage stability Each toner was filled in a 50 ml glass container and left in a constant temperature bath at 50 ° C. for 20 hours. The toner was cooled to room temperature, and the penetration (%) was measured by a penetration test (JIS K2235-1991). The heat-resistant storage stability was evaluated based on the following criteria from the penetration (%) with respect to the toner after being solidified.
〔Evaluation criteria〕
○: The penetration is 60% or more.
X: The penetration is less than 60%.

(J) Crack resistance test 50 g of each developer is placed in a 100 ml bottle (manufactured by Nidec Rika Glass Co., Ltd.), stirred using a paint conditioner at 50 Hz for 30 minutes, and then the toner is separated by electric field separation. Observation with a scanning electron microscope (SEM) was performed. In this SEM observation, the cracking property was evaluated by the ratio (%) of the number of broken or broken toners in 1000 toners. In addition, it shows that crack resistance is inferior, so that a number is large.

  Since the toner of the present invention has a potato shape formed by coalescing a plurality of spherical particles with a small particle diameter, it has excellent cleaning properties and is suitably used for high-quality image formation. The developer, toner-containing container, process cartridge, image forming apparatus and image forming method of the present invention using the toner of the present invention are suitably used for high-quality image formation.

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Constant current source 55 Switching claw 56 Discharging roller 57 Discharging tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 101 Photoconductor 102 Charging means 103 Exposure means 104 Developing means 107 Cleaning means 110 Belt type fixing device 120 Tandem type developing device 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Conveyance roller 148 Paper Feed Path 150 Copier Main Body 200 Paper Feed Table 300 Scanner 400 Automatic Document Feeder (ADF)

Claims (9)

A toner granulated in an aqueous medium,
Containing at least an amorphous resin and a crystalline resin,
A toner having an outer shape in which at least two spherical particles are connected via a coalesced portion.   When the diameter of the virtual circle drawn along the arc of the spherical particles is R (μm) and the length in the depth direction of the joining portion between the spherical particles is L (μm), The toner according to claim 1, wherein ≦ L <1.0R is satisfied.   30 to 100 toner particles satisfying a shape of 0.1R ≦ L <1.0R out of 100 toner particles observed by electron micrographs having a shape in which 2 to 20 spherical particles are fused. The toner according to claim 1, comprising a number%.   The toner according to claim 2, wherein the number average of the diameters R is 0.5 to 7 μm.   Of the 1000 toner particles observed by scanning electron micrograph after stirring 50 g of developer consisting of 2.5 g of toner and 47.5 g of carrier in a 100 ml bottle after stirring at 50 Hz for 30 minutes using a paint conditioner, The toner according to any one of claims 1 to 4, wherein the ratio of the number of the broken or broken toner is 10% or less.   The toner according to claim 1, comprising a crystalline polyester resin as the crystalline resin.   The toner according to claim 1, comprising a polyester resin as the non-crystalline resin.   A developer comprising a carrier and the toner according to claim 1. An electrostatic latent image carrier, development means for developing a visible image on the electrostatic latent image carrier using the toner according to claim 1, and the visible image An image forming apparatus comprising: a transfer unit that transfers to a recording medium; and a fixing unit that fixes a transfer image transferred to the recording medium.