JP2007079144A - Toner, and developer, toner-filled container, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner with which peeling and embedding of an external additive over time hardly occur, the fluidity of the toner is stable despite environmental change of temperature and humidity, and a high quality image can be formed, and a developer, a toner-filled container, a process cartridge, a image forming method, and an image forming apparatus. <P>SOLUTION: The toner includes toner mother particles containing at least a binder resin and a colorant and at least one kind of inorganic particles, in which at least one kind of the inorganic particles are porous inorganic particles. The embodiment that the inorganic particles are subjected to hydrophobing treatment, the embodiment that the porous inorganic particles are ≥50 nm in volume average grain size of the primary particles, and the embodiment that the pore size of the pores in the porous inorganic particles is ≥10 nm, are more preferable. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a toner suitably used for a laser beam printer, a facsimile, a digital copy, and the like, and a developer, a toner-containing container, a process cartridge, an image forming apparatus, and an image forming method using the toner.

  In recent years, copying machines and laser printers using electrophotography have made remarkable progress in various respects such as improvement in image quality, printing speed, and reduction in machine size. Such an electrophotographic system uses a photoconductive substance and is on an electrostatic latent image carrier (hereinafter also referred to as “photosensitive member”, “electrophotographic photosensitive member”, or “latent image carrier”). Forming a latent image on the substrate, a developing step for developing the latent image using toner, a transfer step for transferring the toner image to a recording medium such as paper, and heating using a fixing roller. And a fixing step for fixing the toner image. Among these processes, the development process directly related to image formation is very important for enhancing the functions of copying machines and laser printers.

In general, development methods in electrophotography include a one-component development method using only toner as a developer and a two-component development method using a developer composed of toner and a carrier.
In the one-component developing method, the toner is moved to the developing roller and conveyed, and the toner is frictionally charged by the toner layer regulating member, and at the same time, the thickness of the toner layer is regulated, and the toner in the thin layer state on the developing roller is electrically It develops with strong force. In the developing region where the developing roller and the latent image carrier are opposed to each other, the electrostatic latent image formed on the latent image carrier is visualized with toner. In this case, in order to form a high-quality visible image having a predetermined density, it is necessary to transport a large amount of sufficiently charged toner to the development area and make the latent image visible with such toner.

  On the other hand, in the two-component development system, the toner and the carrier are agitated to develop the toner by giving the toner an appropriate charge amount. This method is a method of developing a latent image by transporting a developer to a latent image carrier by a developing roller provided with a rotatable non-magnetic sleeve outside the magnet roller. In the two-component development method, it is known that the carrier plays a role of charging and transporting the toner, and their mixing ratio and stirring state are greatly related to image formation.

  As described above, in both the one-component development system and the two-component development system, in the development process, it is required to impart a desired charge amount to the toner by frictional charging and to efficiently transport the toner to the development area.

The characteristics of the toner itself are important in order to sufficiently achieve the functions of these development processes, that is, charging and transporting of the toner. In particular, the fluidity of the toner not only relates to toner conveyance but also greatly affects the uniformity of stirring and the frictional charging performed in these processes. In the future, in order to increase the speed or miniaturization of copying machines and laser printers, this fluidity is required at a very high level.
For example, in order to achieve high speed, the toner must be stirred and charged in a short time. When the fluidity of the toner is low, frictional charging is difficult to proceed, so that the toner with a low charge amount is carried to the development area, leading to toner scattering and background smearing. In addition, if the toner is not uniformly stirred, in the two-component development method, the mixing ratio of the carrier and the toner becomes unstable, and in this case, the toner charge amount may be unstable. Furthermore, even in the one-component development method, if the toner fluidity is low, a thin toner layer cannot be uniformly formed on the developing roller that rotates at high speed. For example, the toner is deposited on the developing roller in an aggregated state. As a result, there is a problem that these toners are not sufficiently charged by the toner regulating member, leading to toner scattering and background contamination.

  In order to achieve a reduction in the size of the image forming apparatus, it is most effective to reduce the developer capacity in the developing device. However, if the developer capacity is reduced, the toner in the developing device is reduced when the toner is replenished. It becomes difficult to mix newly supplied toner in a short time. In the two-component development method, a screw for stirring must be downsized, and the stirring ability of the screw is reduced. In any case, it is clear that the fluidity of the toner is required more than ever.

In general, there are two methods for improving toner characteristics: (1) a method in which a material suitable for the purpose is mixed into a toner constituent material, and (2) a method in which fine particles are adhered to the toner surface.
As the method (1), for example, there is a method in which a charge control agent such as a nigrosine dye or a modified product thereof, a triphenylmethane compound, or an imidazole derivative is added to the inside of the toner for the purpose of controlling the chargeability of the toner ( For example, see Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6, and the like).

On the other hand, as the method (2), a method is known in which inorganic oxide particles having a diameter of several to several hundreds of nanometers are attached to the surface of toner base particles (see Non-Patent Document 1). Examples thereof include metal oxides such as silica, alumina, titania and the like produced by a dry production method or a wet production method. In some cases, they are used after the surface thereof is hydrophobized. Examples of the hydrophobizing agent include hexamethyldisilazane and silicone oil. This method has a great effect on improving the fluidity of the toner.
Further, as a method for attaching fine particles to the surface of toner base particles, a method of adding a fatty acid metal salt such as zinc stearate or calcium stearate is known. Originally, in the electrophotographic process, the fatty acid metal salt is often used for reducing the friction between the cleaning blade and the photosensitive member or for improving the transfer rate of the toner from the photosensitive member to the intermediate transfer belt. For the purpose of applying a toner to a photoreceptor or the like without using a member, a fatty acid metal salt has been adhered to the toner surface. Recently, however, it has become clear that the fatty acid metal salt improves the toner characteristics itself in addition to such effects. For example, the fatty acid metal salt prevents aggregation between the toners or increases the chargeability of the toner particles. It is also known that there is an effect (see Patent Document 7 and Patent Document 8).

In addition to speeding up and downsizing, as a technical issue for copiers and printers, more stable image output is required. Especially, stability over time and stability against changes in temperature and humidity environment are more than ever. It has been demanded.
Specifically, the fluidity of the toner changes when external additives such as inorganic particles are peeled off from the toner surface or embedded in the toner by rubbing when the toner is stirred and charged. There are challenges. In particular, as the speed of development and miniaturization of the developing device progresses, a desired charge amount must be imparted to the toner in a short time, and the stress applied to the toner increases. It is easy to happen. As a result, it becomes difficult to control the fluidity of the toner and also the charge amount of the toner, and problems such as background contamination and toner scattering are likely to occur.

  In addition, since the amount of water adsorbed on the toner surface varies greatly, the change in chargeability is expanded by changing the use environment, resulting in image density variation and fogging problems. This problem has been pointed out for a long time, and various countermeasures have been proposed, but the current copiers and printers that are progressing in image quality are required to have a higher level of stability. It is.

  In recent years, polymerized toners having a uniform particle size distribution have been developed, and have greatly contributed to improving the image quality of copying machines and printers. On the other hand, it has been pointed out that the polymerized toner has a difficult cleaning process in which the polymerized toner remaining on the photoreceptor after the transfer process is removed by a rubber blade (cleaning blade). In order to stably remove such polymerized toner from the photoreceptor, it is necessary to design the friction coefficient of the photoreceptor and the toner and the cleaning blade and the toner with high accuracy. If the external additive peels off over time due to agitation and charging in the developing unit, or if the moisture content on the toner surface changes due to the temperature and humidity environment, friction between the photoconductor and the toner, and between the cleaning blade and the toner. Since the coefficient changes from the initial value, there is a problem that it is difficult to remove all the toner remaining on the photosensitive member by the cleaning blade.

In order to solve this problem, for example, Patent Document 9 proposes a capsule toner having porous silica attached thereto. According to this proposal, it is said that aggregation of toner can be prevented by absorbing the oily solvent exuded from the toner surface in a high temperature and high humidity environment through the silica pores.
However, in the above proposal, the effect of reducing the frictional force to the external additive and the effect of reducing the amount of moisture adsorbed on the toner surface cannot be obtained, and the effect of improving the cleaning property in the toner having high sphericity is not sufficient. Is the current situation.

Japanese Patent Publication No. 1-54694 Japanese Patent Publication No. 1-54695 JP-A-51-455 Japanese Examined Patent Publication No. 63-57787 JP-A-3-11964 Japanese Patent Laid-Open No. 3-202856 JP 2003-29446 A JP-A-9-251214 Japanese Patent Publication No. 8-3654 "Basics of Electrophotographic Technology and Applied Electrophotographic Society" (Corona)

  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 relates to a toner capable of forming a high-quality image, in which the external additive is less likely to be peeled off and buried with time, and the fluidity of the toner is stable against changes in the temperature and humidity environment. An object of the present invention is to provide a developer, a container containing toner, a process cartridge, an image forming method, and an image forming apparatus.

Means for solving the problems are as follows. That is,
<1> In a toner comprising toner base particles containing at least a binder resin and a colorant, and at least one kind of inorganic particles,
The toner is characterized in that at least one of the inorganic particles is porous inorganic particles.
<2> The toner according to <1>, wherein the inorganic particles are a plurality of types of inorganic particles having different particle diameters.
<3> The toner according to any one of <1> to <2>, wherein the inorganic particles are hydrophobized.
<4> The toner according to any one of <1> to <3>, wherein the porous inorganic particles have a volume average particle diameter of primary particles of 50 nm or more.
<5> The toner according to any one of <1> to <4>, wherein the pore diameter of the porous inorganic particles is 10 nm or more.
<6> The toner according to any one of <1> to <5>, wherein the total addition amount of the inorganic particles is 0.05 to 10.0 parts by mass with respect to 100 parts by mass of the toner base particles.
<7> The toner according to any one of <1> to <6>, further including a fatty acid metal compound.
<8> The toner according to any one of <1> to <7>, wherein the toner has a volume average particle diameter of 10 μm or less.
<9> The toner according to any one of <1> to <8>, wherein the toner has an average circularity of 0.96 or more.
<10> A developer comprising the toner according to any one of <1> to <9>.
<11> The developer according to <10>, which is one of a one-component developer and a two-component developer.
<12> A toner-containing container filled with the toner according to any one of <1> to <9>.
<13> 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 <9> to be a visible image And a developing means for forming the process cartridge.
<14> 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 <1> to <9> Development means for forming a visible image by developing using any of the toners, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium The image forming apparatus is characterized by having at least.
<15> The developing means carries toner on the peripheral surface, rotates in contact with the electrostatic latent image carrier, and supplies the toner to the electrostatic latent image formed on the latent image carrier for development. The image forming apparatus according to <14>, further including: a developing roller that performs a toner image; and a thin layer forming member that contacts the peripheral surface of the developing roller and thins the toner on the developing roller.
<16> The developing means includes a developer accommodating portion that accommodates a two-component developer composed of toner and a carrier, and a rotatable nonmagnetic sleeve that includes a plurality of fixed magnetic field generating means. The magnetic field generating means A developer carrying member that carries the two-component developer in the developer containing portion on the surface and conveys it to a developing region facing the electrostatic latent image carrying member;
The image forming apparatus according to <14>, further comprising a developer regulating member that regulates a layer thickness of the developer on the developer carrying member.
<17> An image forming apparatus includes an intermediate transfer member to which a visible image formed on an electrostatic latent image carrier is primarily transferred, and a visible image carried on the intermediate transfer member to a recording medium as a secondary The image forming apparatus according to any one of <14> to <16>, further including a transfer unit that transfers the image.
<18> 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 <9> 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.

The toner of the present invention comprises toner base particles containing at least a binder resin and a colorant, and at least one kind of inorganic particles, and at least one kind of the inorganic particles is porous inorganic particles.
In the toner of the present invention, since the contact area between the inorganic fine particles and the photoreceptor is reduced, the adhesive force and frictional force applied to the inorganic fine particles are reduced, and the external additive is less likely to be peeled off and buried over time. . In addition, the pores of the porous inorganic fine particles have a hygroscopic effect, the fluidity of the toner is stable against changes in the temperature and humidity environment, and high-quality images can be formed over a long period of time.

  The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, the chargeability is good and a good visible image is obtained.

  Since the toner-containing container of the present invention contains the toner of the present invention in the container, image formation by electrophotography using the toner stored in the toner-containing container results in temperature and humidity. The toner fluidity is stable against environmental changes, and a good visible image can be obtained.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge is attachable to and detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that the toner fluidity is stable against changes in the temperature and humidity environment, and the image quality is high. An image can be formed.

  An image forming apparatus according to the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using toner. The toner includes at least developing means for forming a visible image by development, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transfer image transferred to the recording medium. As described above, since the toner of the present invention is used, it is stable against changes in the temperature and humidity environment, and an image with high durability and high image quality can be obtained over a long period of time.

  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 developing the electrostatic latent image with toner to form a visible image. At least a development step, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. An electrostatic latent image carrier. In the image forming method of the present invention, since the toner of the present invention is used as the toner, the toner fluidity is stable against changes in the temperature and humidity environment, high durability and high image quality over a long period of time. Images can be obtained.

  According to the present invention, conventional problems can be solved, the external additive is less likely to be peeled off and buried over time, and the fluidity of the toner is stable against changes in the temperature and humidity environment. A toner capable of forming an image, a developer using the toner, a toner-containing container, a process cartridge, an image forming method, and an image forming apparatus can be provided.

(toner)
The toner of the present invention comprises toner base particles containing at least a binder resin and a colorant, and at least one inorganic particle, and further contains other components as necessary.

<Inorganic particles>
The said inorganic particle is at least 1 type, Preferably, it is multiple types (preferably 2-5 types) from which a particle size differs, At least 1 type of these is a porous inorganic particle.
The pore diameter of the porous inorganic particles is preferably 10 nm or more, and more preferably 10 to 30 nm. If the pore diameter is less than 10 nm, the amount of moisture adsorbed in the pores is reduced in a high humidity environment, and the humidity range in which the amount of moisture adsorption on the toner surface can be controlled may be limited.
This is because, in recent toners for electrophotography, a plurality of types of inorganic particles are often adhered for the purpose of multifunctionalization, and only one type of inorganic particles to be adhered to the toner is made porous. However, the effect can be fully expected.
Here, the pore diameter of the pores of the porous inorganic particles can be measured, for example, by observing the surface of the inorganic particles with an electron microscope.
In recent years, various methods have been studied for the porous inorganic particles. In the present invention, the method for producing the porous inorganic particles is not particularly limited, and can be appropriately selected according to the purpose.

The porous inorganic particles preferably have a volume average particle size of primary particles of 50 nm or more, and more preferably 50 to 300 nm. When the volume average particle size is less than 50 nm, the primary particle size is too small with respect to the pore size, so that it may not serve as a spacer between the toner and the fluidity may not be improved. .
In the present invention, as shown in FIG. 1A, since the inorganic particles 102 as the external additive having a large particle size have a large surface area, the friction force F1 of the toner 200 is larger than that of the external additive 101 having a small particle size. It has been pointed out that it is easy to apply and easily peels off from the toner surface. As shown in FIG. 1B, by forming the inorganic fine particles into the porous body 103, the rubbing force F2 can be reduced even when the particle size is large, and peeling from the surface of the toner 200 can be reduced. In FIG. 1A and FIG. 1B, reference numeral 104 denotes a base material (photoconductor).
Here, the volume average particle diameter of the inorganic particles can be measured, for example, by observation with an electron microscope.

  There is no restriction | limiting in particular as said inorganic particle, Although it can select suitably according to the objective, For example, a silica, titanium oxide, an alumina, or these hydrophobization processed materials etc. are mentioned. Of these, hydrophobized silica is particularly preferable. Such a hydrophobizing agent performs surface treatment to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. Especially in one-component development, the toner thin layer on the developing roller Becomes uniform. Examples of the hydrophobizing agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. Is mentioned.

  The total addition amount of the inorganic particles depends on the particle size and the like and cannot be generally defined, but is preferably 0.05 to 10.0 parts by mass with respect to 100 parts by mass of the toner base particles, and 0.3 -3.0 mass parts is more preferable. If the total addition amount is less than 0.05 parts by mass, the effect of improving fluidity may not be expected. If the total addition amount exceeds 10.0 parts by mass, the inorganic particles are not sufficiently adhered to the toner surface. As a result, the inorganic particles may adhere to the surface of the photoconductor and become contaminated, or the photoconductor surface may be scraped off. There is.

  For the addition of the inorganic particles, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

Further, the flow characteristics can be further improved by attaching a fatty acid metal compound such as zinc stearate to the surface of the toner base particles together with the inorganic particles as described above.
The zinc stearate is a typical lamellar crystal powder, but the lamellar crystal has a layered structure in which amphiphilic molecules are self-organized, and when shearing force is applied, the crystal breaks along the layers and is slippery. . This action is effective in reducing the friction coefficient, and can uniformly cover the toner surface under shearing force. When the zinc stearate is applied, the lubricity can be sufficiently exhibited when the film thickness is about 10 nm. At this time, considering that the molecular chain length of zinc stearate is about 5 nm, the optimum coating condition is that the lubricating layer thickness is about 10 nm. That is, two molecules are oriented with respect to the toner. Sometimes it shows that the effect is sufficient. That is, it is shown that zinc stearate exhibits sufficient lubricity due to the deviation between the two molecular layers. As other fatty acid metal salts, for example, magnesium stearate, calcium stearate, etc. also show the same properties as zinc stearate, and the molecular chain length is almost the same, so that the zinc stearate film is always in the range of 10 nm in thickness. By forming it, it is considered that a sufficient lubricating effect is exhibited.
The method for adding these fatty acid metal compounds is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, the fatty acid metal compound can be added using a mixing means such as a Henschel mixer, a ball mill, or a coffee mill. .

<Toner base particles>
Although not limited to the type and manufacturing method of the toner base particles, a toner having a nearly spherical shape can exert a greater effect. There are mainly a pulverization method and a polymerization method as a method for producing the toner. A spherical toner having a high degree of circularity is produced by the polymerization method. Examples of the polymerization method include suspension polymerization method, dispersion polymerization method, emulsion polymerization method, microcapsule polymerization method, and spray drying. For example, in the case of suspension polymerization, the binder resin is produced by homogenizing an additive such as a colorant or a charge control agent, and adding a dispersion medium and a dispersant to polymerize the binder resin. Since the process of the polymerization method is simplified, the manufacturing cost is lower than that of the pulverization method. In addition, there is an advantage that the particle diameters are relatively well aligned, toners having large and small particle diameters can be selectively produced, and irregularly shaped particles are hardly produced (mostly spherical toners).

[Crushing toner]
The pulverization method is, for example, a method of obtaining toner base particles by melting and kneading a toner material containing at least a binder resin and a colorant, and pulverizing and classifying the toner material. In the case of the pulverization method, for the purpose of increasing the average circularity of the toner, the shape may be controlled by applying a mechanical impact force to the obtained toner base particles. In this case, the mechanical impact force can be applied to the toner base particles using a device such as a hybridizer or mechanofusion.

  The above toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikekai Tekko Co., Ltd. Preferably used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature is performed with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed by removing the fine particle portion by, for example, a cyclone, a decanter, centrifugation, or the like.
After the pulverization and classification are completed, the pulverized product is classified in an air stream by centrifugal force or the like to produce a toner having a predetermined particle size.

  Further, in order to improve the fluidity, storage stability, developability and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner base particles produced as described above. For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

The toner material contains at least a binder resin, a colorant, and a release agent, and further contains other components as necessary.
-Binder resin-
The binder resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and a single substitution product thereof. Polymer: Styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-di Chloromethyl methacrylate copolymer, starene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene -Isoprene copolymer, styrene-acrylonitrile Styrene copolymers such as ru-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic resin, acrylic resin, methacrylic resin, polyacetic acid Vinyl, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, rosin, modified rosin, terpene resin, coumaroindene resin, aliphatic or aliphatic hydrocarbon resin, aromatic petroleum resin Chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, polyester resins are particularly preferable from the viewpoint of color developability and image strength.

The polyester resin is usually obtained by a polycondensation reaction between a polyhydric alcohol compound and a polycarboxylic acid compound.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO), trihydric or higher polyhydric alcohol (TO), and among these, (DIO) alone or (DIO) and a small amount. A mixture with (TO) of is preferred.

Examples of the dihydric alcohol (DIO) include alkylene glycol (eg, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); Alkylene ether glycol (eg, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol (eg, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.) Bisphenols (eg, bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxides of the above alicyclic diols (eg, ethylene oxide, propylene oxide) Side, butylene oxide, etc.) adducts; alkylene oxide (ethylene oxide of the bisphenols, propylene oxide, and the like butylene oxide, etc.) adducts.
Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferred. Combinations of alkylene oxide adducts of bisphenols and alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Is particularly preferred.

  Examples of the trihydric or higher polyhydric alcohol (TO) include 3 to 8 or higher polyhydric aliphatic alcohols (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); 3 And higher phenols (for example, trisphenol PA, phenol novolac, cresol novolak, etc.); alkylene oxide adducts of the above trivalent polyphenols and the like.

Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC), trivalent or higher polyvalent carboxylic acid (TC), (DIC) alone, and (DIC) and a small amount of (TC). And mixtures thereof are preferred.
Examples of the divalent carboxylic acid (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid). , Terephthalic acid, naphthalenedicarboxylic acid, etc.).
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polyvalent carboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid, pyromellitic acid, etc.). The polyvalent carboxylic acid (PC) may be reacted with polyhydric alcohol (PO) using the above acid anhydrides or lower alkyl esters (eg, methyl ester, ethyl ester, isopropyl ester, etc.). Good.

  The ratio of the polyhydric alcohol (PO) to the polyvalent carboxylic acid (PC) is preferably an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH] of 2/1 to 1/1. 1.5 / 1 to 1/1 are more preferable, and 1.3 / 1 to 1.02 / 1 are particularly preferable.

  The polycondensation reaction between the polyhydric alcohol (PO) and the polycarboxylic acid (PC) is heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the pressure is reduced as necessary. The produced water is distilled off to obtain a polyester resin having a hydroxyl group. The hydroxyl value of the polyester resin is preferably 5 or more. The acid value of the polyester resin is usually preferably from 1 to 30, and more preferably from 5 to 20. By giving an acid value as described above, it becomes easy to be negatively charged, and furthermore, at the time of fixing onto a recording paper, the affinity between the recording paper and the toner is good and the low-temperature fixability is improved. However, when the acid value exceeds 30, there is a tendency to deteriorate with respect to the stability of charging, particularly the environmental fluctuation.

The weight average molecular weight (Mw) of the polyester resin is preferably 10,000 to 400,000, and more preferably 20,000 to 200,000. When the weight average molecular weight is less than 10,000, the offset resistance may be deteriorated, and when it exceeds 400,000, the low-temperature fixability may be deteriorated.
Here, the weight average molecular weight of the polyester resin is measured by, for example, gel permeation chromatography (GPC).

-Release agent-
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.
The waxes are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include animal and plant waxes such as rice wax, candelilla wax, carnauba wax, lanolin; paraffin wax, microcrystalline wax, Petroleum and other petroleum wax; low density polyethylene, high density polyethylene, polyethylene copolymer, polypropylene, polypropylene copolymer, acid value-modified polyethylene, acid-modified polyethylene, graft-modified polyethylene with aromatic monomers, pyrolysis-type low Examples thereof include olefinic waxes such as density polyethylene and pyrolytic polypropylene. These may be used individually by 1 type and may use 2 or more types together.

  Moreover, as said wax, a commercial item can be used, for example, HNP (product number: 1, 3, 9, 10, 11, 12), SP (product number: 0145, 1035, 3040, 3035, 0110), Hi. -Mic (part number: 2095, 1080, 3080, 1070, 2065, 1045, 2045), POLYCOAT (part number: 1025, 1455, 2255, 3030, 3155), NEOPALAX (part number: 2545, 3240), PALVAX (part number: 1230, 1335, 1430), CARTOWAX-3025, BONTEX (part numbers: 0011, 2266), S-0750, OX (part numbers: 261BN, 0550, 2251, 1949), NSP-8070, NPS (part numbers: L-70, 6010, 9210) ), HAD (Part No .: 5080, 670), WEISSEN-0453, JP-1500, LUVAX (part number: 1266, 2191, 1151, 0321), EMUSTAR (part number: 0001, 042X, 0135, 0136, 0164, 358) (manufactured by Nippon Wax Co., Ltd.), High wax (Part No .: 800P, 400P, 200p, 100P, 720P, 410P, 420P, 320P, 210P, 220P, 110P, 405MP, 310MP, 320MP, 210MP, 220MP, 4051E, 4052E, 4202E, 1105A, 2203A, 1120H, 1140H 1160H, NL100, NL200, NL500, NL800, NP055, NP105, NP505, NP805) (manufactured by Mitsui Petrochemical Co., Ltd.) and the like can be used.

  The addition amount of the wax as the release agent is preferably 2 to 7 parts by mass with respect to 100 parts by mass of the binder resin. If the addition amount is less than 2 parts by mass, sufficient releasability cannot be exhibited, and hot offset may occur at the time of toner fixing, and if it exceeds 7 parts by mass, too much wax will come out on the toner surface. As a result, the wax content in the toner fine powder increases, and as a result, the variation in glossiness of the visible image (toner image) may increase. Moreover, when there is too much content of wax, hot offset may generate | occur | produce.

-Colorant-
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, Pigment 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 individually by 1 type and may use 2 or more types together.
The content of the colorant in the toner is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.

  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, styrene copolymer, polymethyl methacrylate resin, polybutyl Methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polypropylene resin, polyester resin, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic hydrocarbon resin, alicyclic 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.

-Charge control agent-
The charge control agent is not particularly limited, and a positive or negative charge control agent can be appropriately selected and used depending on whether the charge charged on the photoconductor is positive or negative.
As the negative charge control agent, for example, a resin or compound having an electron donating functional group, an azo dye, a metal complex of an organic acid, or the like can be used. Specifically, Bontron (product numbers: S-31, S-32, S-34, S-36, S-37, S-39, S-40, S-44, E-81, E-82, E -84, E-86, E-88, A, 1-A, 2-A, 3-A) (above, manufactured by Orient Chemical Industry Co., Ltd.)), Kaya Charge (part numbers: N-1, N-2), Kaya Set Black (Part No .: T-2, 004) (Nippon Kayaku Co., Ltd.), Eisenspiron Black (T-37, T-77, T-95, TRH, TNS-2) FCA-1001-N, FCA-1001-NB, FCA-1001-NZ (manufactured by Fujikura Kasei Co., Ltd.), and the like.
Examples of the positive charge control agent include basic compounds such as nigrosine dyes, cationic compounds such as quaternary ammonium salts, and metal salts of higher fatty acids. Specifically, Bontron (part numbers: N-01, N-02, N-03, N-04, N-05, N-07, N-09, N-10, N-11, N-13, P -51, P-52, AFP-B) (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415, TP-4040 (above, manufactured by Hodogaya Chemical Co., Ltd.), Copy Blue PR, Copy Charge ( Product number: PX-VP-435, NX-VP-434) (manufactured by Hoechst), FCA (Product number: 201, 201-B-1, 201-B-2, 201-B-3, 201-PB, 201-PZ, 301) (above, manufactured by Fujikura Kasei Co., Ltd.), PLZ (product numbers: 1001, 2001, 6001, 7001) (above, manufactured by Shikoku Kasei Kogyo Co., Ltd.), and the like.
These may be used individually by 1 type and may use 2 or more types together.

  The addition amount of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited. However, with respect to 100 parts by mass of the binder resin. 0.1-10 mass parts is preferable and 0.2-5 mass parts is more preferable. When the addition amount exceeds 10 parts by mass, the chargeability of the toner is too large, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is reduced, and the image density is increased. If the amount is less than 0.1 parts by mass, the charge rise and charge amount are insufficient, and the toner image may be easily affected.

  In addition to the binder resin, the release agent, the colorant, and the charge control agent, the toner material includes inorganic fine particles, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, and the like as necessary. Can be added.

[Polymerized toner]
The polymerized toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner produced by a suspension polymerization method, an emulsion polymerization method, a polymer suspension method or the like is preferable.
The suspension polymerization method is an oil-soluble polymerization initiator, emulsification described later in an aqueous medium in which a colorant, a release agent, and the like are dispersed in a polymerizable monomer and a surfactant and other solid dispersant are contained. Emulsified and dispersed by the method. Thereafter, a polymerization reaction is performed to form particles, and then wet processing for attaching inorganic fine particles to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.
Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and other acids, acrylamide, Surface of toner particles by using methacrylamide, diacetone acrylamide or their methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, acrylates with methacrylates such as dimethylaminoethyl methacrylate, methacrylates, etc. in part Functional groups can be introduced into
Further, by selecting a dispersant having an acid group or a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

  As the emulsion polymerization method, a water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by a usual emulsion polymerization method. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, wet processing of inorganic fine particles described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer that can be used in the suspension polymerization method.

  In the present invention, among these, since the selectivity of the resin is high, the low-temperature fixability is high, the granulation property is excellent, and the particle size, the particle size distribution, and the shape can be easily controlled. The toner is preferably obtained by emulsifying or dispersing a toner material dissolved or dispersed in an aqueous medium and granulating the toner.

The toner material solution is obtained by dissolving the toner material in a solvent, and the toner material dispersion liquid is obtained by dispersing the toner material in a solvent.
The toner material includes at least an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, a binder resin, and an adhesive base material obtained by reacting a colorant. Furthermore, other components such as a release agent, resin fine particles, and a charge control agent are included as necessary.

-Adhesive substrate-
The adhesive base material 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 medium. 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, 1,000 or more are preferable and 2,000-10,000,000 are more preferable. 3,000 to 1,000,000 are particularly preferred.
When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

The storage elastic modulus of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10,000 dyne / cm ² , Usually, it is 100 ° C. or higher, and preferably 110 to 200 ° C. When the (TG ′) is less than 100 ° C., the hot offset resistance may be deteriorated.
The viscosity of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (Tη) at which a measurement frequency of 20 Hz is 1,000 poise is usually 180 ° C. or lower. Yes, 90-160 degreeC is preferable. When the (Tη) exceeds 180 ° C., the low-temperature fixability may be deteriorated.
Therefore, from the viewpoint of achieving both hot offset resistance and low-temperature fixability, the (TG ′) is preferably higher than the (Tη). That is, the difference (TG′−Tη) between (TG ′) and (Tη) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. The larger the difference, the better.
Further, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability, the (TG′−Tη) is preferably 0 to 100 ° C., more preferably 10 to 90 ° C., and still more preferably 20 to 80 ° C.

Specific examples of the adhesive substrate are not particularly limited and may be appropriately selected depending on the intended purpose. Particularly preferred are 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-based resin includes 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. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. 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.

-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 medium.
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 individually by 1 type and may use 2 or more types together. 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 individually by 1 type and may use 2 or more types together. 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.
When the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be lowered. When the mixing equivalent ratio exceeds 3/1, the molecular weight of the urea-modified polyester resin becomes 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 individually by 1 type and may use 2 or more types together. 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 heating medium for fixing. 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-forming group in the urea bond-forming 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 glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, 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. Mixtures are particularly preferred.

The trihydric or higher polyol (TO) is preferably a trihydric or higher polyhydric alcohol, for example, a trihydric or higher polyhydric aliphatic alcohol, a trihydric or higher polyphenol, or a trihydric 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 trivalent or higher polyphenols alkylene oxide adducts include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trivalent 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: 0.01-100: 10 are preferable and 100: 0.01-100: 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 tricarboxylic or higher polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. 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, sebacic acid, and the like. 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, 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 3 to 8 or higher, 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: 0.01-100: 10 are preferable and 100: 0.01-100: 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 and diphenyl ether-4,4′-diisocyanate. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, and the like.
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 group 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 4/1 to 1.2 / 1. Is more preferable, and 3/1 to 1.5 / 1 is particularly preferable.
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.

The average number of isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A) is preferably 1 or more, more preferably 1.2 to 5, and more preferably 1.5 to 4.
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 1,000 to 30,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 1,500-15,000 are more preferable. 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 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 the molecular weights made by Toyo Soda Industry Co., Ltd. are 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8. It is preferable to use 6 × 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.

--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, Undenatured 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, as described above, the content of the component having the weight average molecular weight (Mw) of less than 1,000. 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 usually preferably 50 to 70 ° C. When the glass transition temperature is less than 50 ° 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 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 35.0 mgKOH / g, and more preferably 10 to 35.0 mgKOH / g. Generally, it becomes easy to be negatively charged by giving the toner an acid value.
When the unmodified polyester resin is contained in the toner material, a mixing mass ratio of a polymer (for example, a urea bond-forming group-containing polyester resin) capable of reacting with an active hydrogen group-containing compound and the unmodified polyester resin ( The polymer / unmodified polyester resin) is preferably 5/95 to 80/20, more preferably 10/90 to 25/75.
When the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Glossiness may deteriorate.
As content of the said non-modified polyester resin in the said binder resin, 50-100 mass% is preferable, for example, 70-95 mass% is more preferable, 80-90 mass% is still more preferable. When the content is less than 50% by mass, the low-temperature fixability and the glossiness of the image may be deteriorated.

  In addition, the same colorant, release agent, charge control agent and the like in the polymerization toner can be used as in the pulverization toner.

The toner has a volume average particle size of preferably 10 μm or less, more preferably 4 to 8 μm.
When the volume average particle diameter exceeds 10 μm, the cohesive force between the powders becomes strong, and it may be difficult to control the fluidity of the toner.
The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) of the toner is preferably 1.00 to 1.40, more preferably 1.10 to 1.25. preferable.
The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are, for example, a particle size measuring instrument ““ Coulter Counter TAII ”manufactured by Coulter Electronics Co., Ltd. Can be measured.

The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected area as the shape of the toner by the circumference of the actual particles, and is preferably 0.96 or more, for example, 0.96 to 0.99. More preferred.
If the average circularity is less than 0.96, the toner becomes an irregular shape separated from the spherical shape, and a satisfactory high transferability and a high-quality image without dust may not be obtained.
The average circularity is measured, for example, by 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 using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).

  The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. The developer may be a one-component developer or a two-component developer.
In the one-component developer, after the toner is transported onto the developer carrier, the toner is thinned by the layer thickness regulating member and developed, but the toner and the developer carrier, the layer thickness regulating member, etc. The contact / friction charging time with the friction charging member is very short. Therefore, in order to obtain a toner having a desired charge amount, the pressure between the layer thickness regulating member and the developer carrier must be set high, and the stress applied to the toner increases, and the external additive peels off. Is likely to occur. As a result, the toner is not supported on the developing roller and becomes scattered toner, which contaminates the inside of the image forming apparatus, or the toner is developed in a non-image area of the photoreceptor, causing fogging. Has the effect of reducing peeling of the external additive, and is therefore sufficiently effective in the one-component development system.
On the other hand, in the two-component developer, the magnetic carrier is used to convey the toner to a region close to the electrostatic latent image carrier, so that the magnetic carrier or the magnetic brush of the two-component developer is applied to the electrostatic latent image carrier. Under the influence of the hit state, a phenomenon in which development unevenness occurs without being faithful to the electrostatic latent image, that is, a so-called magnetic brush mark occurs. For this reason, the two-component developing device is inherently inferior in the reproducibility of high-definition images compared to the one-component developing device, and if the toner characteristics change over time or the environment, the effect is even greater. Will appear. Since the present invention has the effect of achieving stabilization of toner characteristics with respect to time and environment, it is sufficiently effective in a two-component development system.

  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 highly magnetized 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 particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D50)) of 10 to 200 μm, and more preferably 40 to 100 μm.
When the average particle size (volume average particle size (D50)) is less than 10 μm, in the distribution of carrier particles, there are many fine powder systems, and the magnetization per particle may be lowered, causing carrier scattering, If it exceeds 200 μm, the specific surface area may decrease and toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be particularly poor.

  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, fluorine And a copolymer of vinylidene fluoride and 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, polyacrylonitrile 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 as 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 application method include an immersion 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.
In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

Since the developer of the present invention contains the toner of the present invention, it is possible to prevent the occurrence of photoconductor filming, and to stably form excellent clear high-quality images without fluctuations in image unevenness. Can do.
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 comprises the toner or the developer of the present invention contained in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a toner container main body and a cap etc. are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral unevenness is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Particularly preferred.
The material of the toner container main body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable. Among them, for example, a polyester resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, a polychlorinated resin is preferable. Preferred examples include vinyl 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 toner to produce a visible image. A developing unit to be formed, and further includes other units such as a charging unit, a developing unit, a transfer unit, a cleaning unit, and a discharging unit, which are 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 mounted on various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably mounted on the image forming apparatus of the present invention described later.

Here, for example, as shown in FIG. 2, the process cartridge includes a photosensitive member 201, and includes a charging unit 202, a developing unit 204, a transfer unit 208, and a cleaning unit 207, and other units as necessary. It has. In FIG. 2, reference numeral 203 denotes exposure by exposure means, and 205 denotes a recording medium.
As the photosensitive member 201, the same one as an image forming apparatus described later can be used. An arbitrary charging member is used for the charging means 202.
Next, the image forming process using the process cartridge shown in FIG. 2 will be described. The photosensitive member 201 is rotated on the surface by charging by the charging unit 202 and exposure 203 by the exposure unit (not shown) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the exposure image is formed. The electrostatic latent image is developed with toner by the developing unit 204, and the toner development is transferred to the recording medium 205 by the transfer unit 208 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 207, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  The image forming apparatus of the present invention is constructed by integrally combining the electrostatic latent image carrier and the components such as a developing device and a cleaning device as a process cartridge, and this unit can be attached to and detached from the apparatus main body. It may be configured. Further, at least one of a charger, an image exposure device, a developing device, a transfer or separation device, and a cleaning device is integrally supported together with an electrostatic latent image carrier to form a process cartridge, and is detachably attached to the apparatus main body. One unit may be detachable using guide means such as a rail of the apparatus main body.

(Image forming apparatus and image forming method)
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.
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. A recycling process, a control process, and the like.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-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.
The electrostatic latent image bearing member (sometimes referred to as “electrophotographic photosensitive member” or “photosensitive member”) is not particularly limited in terms of material, shape, structure, size, etc. Although it can be selected as appropriate, the shape is preferably a drum shape, and examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. . Among these, amorphous silicon and the like are preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method, or the like is applied on the support. A photoconductor having a photoconductive layer made of a-Si (hereinafter sometimes referred to as “a-Si-based photoconductor”) can be used. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

The electrostatic latent image can be formed, for example, by charging the surface of the electrostatic latent image carrier and then exposing it like an image, and by the electrostatic latent image forming means. .
The electrostatic latent image forming unit includes, for example, at least a charger that charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise.

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 roller, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. In the case of using a magnetic brush, the magnetic brush is composed of various ferrite particles such as Zn—Cu ferrite as a charging member, a non-magnetic conductive sleeve for supporting it, and a magnet roll included therein. Or, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound or attached to a metal or other conductive core. To make a charger.
The charger is not limited to the contact charger as described above. However, since an image forming apparatus in which ozone generated from the charger is reduced is obtained, a contact charger is used. preferable.

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 latent electrostatic image bearing member 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 means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developing unit capable of contacting or non-contacting the toner or the developer with the electrostatic latent image is provided, and includes the toner container according to the present invention. More preferred is a developing device.
As the developing means, a toner is carried on the peripheral surface, rotated in contact with the electrostatic latent image carrier, and supplied to the electrostatic latent image formed on the electrostatic latent image carrier. An embodiment having a developing roller that performs development and a thin layer forming member that contacts the peripheral surface of the developing roller and thins the toner on the developing roller is preferable.
The developing means comprises a developer containing portion for containing a two-component developer comprising toner and carrier, and a rotatable nonmagnetic sleeve containing a plurality of fixed magnetic field generating means. A developer carrier that carries the two-component developer in the developer container on the surface and conveys it to a development region facing the electrostatic latent image carrier;
An embodiment having a developer regulating member that regulates the layer thickness of the developer on the developer carrying member is preferable.

  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 latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, 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. The number of the transfer means may be one, or two or more.
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 typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

-Fixing Step and Fixing Unit The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium. Alternatively, the toners of the respective colors may be simultaneously formed in a state where they are laminated.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 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 toner removed by 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.

  Here, FIG. 3 is a schematic view showing an example of the image forming apparatus of the present invention. In FIG. 3, the image forming apparatus includes a photosensitive body 2 that is driven to rotate in a clockwise direction in FIG. 3 in a main body housing (not shown), and a charging unit 3 around the photosensitive body 2. , A writing unit 4, a developing unit 5, a transfer unit 7, a paper separating unit, a cleaning unit 13, a photoreceptor charge eliminating unit 8, a control device 15, and a voltage applying unit 16.

  The image forming apparatus includes a paper feeding cassette (not shown) that stores a plurality of recording papers. The recording paper in the paper feeding cassette is formed by a pair of registration rollers (not shown) one by one by a paper feeding roller (not shown). After the timing adjustment, the paper is transferred between the paper transfer unit 7 and the photosensitive member 2.

  The image forming apparatus rotates the photosensitive member 2 in the clockwise direction in FIG. 3, uniformly charges the photosensitive member 2 with the charging unit 3, and then irradiates a laser modulated with image data by the writing unit 4. An electrostatic latent image is formed on the photosensitive member 2, and toner is attached to the photosensitive member 2 on which the electrostatic latent image is formed by the developing unit 5 and developed. In the image forming apparatus, the photosensitive member 2 on which the toner image is formed by attaching the toner in the developing unit 5 is transferred to the recording paper conveyed between the photosensitive member 2 and the paper transfer unit 7 by the paper transfer unit 7. Then, the recording paper on which the toner image is transferred is conveyed to the fixing unit.

  The fixing unit includes a fixing roller that is heated to a predetermined fixing temperature by a built-in heater and a pressure roller that is pressed against the fixing roller with a predetermined pressure, and heats and applies the recording paper conveyed from the paper transfer unit 7. After the toner image on the recording paper is fixed to the recording paper, the paper is discharged onto a paper discharge tray (not shown).

  On the other hand, the image forming apparatus further rotates the photosensitive member 2 on which the toner image is transferred to the recording paper by the paper transfer unit 7, and scrapes and removes the toner remaining on the surface of the photosensitive member by the cleaning unit 13 with a blade. The photosensitive member neutralizing unit 8 neutralizes the charge. In the image forming apparatus, after the photosensitive member 2 that has been neutralized by the photosensitive member neutralizing unit 8 is uniformly charged by the charging unit 3, the next image formation is performed in the same manner as described above. The cleaning unit 13 is not limited to the one that scrapes the residual toner on the photoconductor 2 with a blade, and may be one that scrapes the residual toner on the photoconductor 2 with a fur brush 502, for example.

FIG. 4 is a schematic diagram showing an example of an image forming apparatus to which the present invention is applied. FIG. 4 shows a tandem type full-color image forming apparatus.
In FIG. 4, the image forming apparatus stores an electrostatic latent image carrier 2 that is driven to rotate clockwise in FIG. 4 in a main body housing (not shown). A charging unit 3, a writing unit 4, a developing unit 5, an intermediate transfer unit 6, a paper transfer unit 7 and the like are arranged.
Although not shown, the image forming apparatus includes a paper feeding cassette that stores a plurality of recording papers. The recording paper P in the paper feeding cassette is timed by a pair of registration rollers (not shown) one by one by a paper feeding roller (not shown). After the adjustment, the sheet is sent out between the intermediate transfer unit 6 and the electrostatic latent image carrier 2.
The image forming apparatus rotates the electrostatic latent image carrier 2 in the clockwise direction in FIG. 4 to uniformly charge the electrostatic latent image carrier 2 with the charging unit 3, and then writes the image data with the writing unit 4. An electrostatic latent image is formed on the electrostatic latent image carrier 2 by irradiating the modulated laser, and the developing unit 5 attaches toner to the electrostatic latent image carrier 2 on which the electrostatic latent image has been formed. To do. In the image forming apparatus, toner is attached by the developing unit 5 and the toner image is transferred from the electrostatic latent image carrier 2 to the intermediate transfer member by the intermediate transfer unit 6. This is performed for each of the four colors CMYK to form a full-color toner image.

  FIG. 5 is a schematic diagram illustrating an example of a revolver type full-color image forming apparatus. In this image forming apparatus, a plurality of colors of toner are sequentially developed on one electrostatic latent image carrier by switching the operation of the developing device. Then, the color toner image on the intermediate transfer member is transferred to the recording paper P by the paper transfer unit 7, and the recording paper P on which the toner image is transferred is conveyed to the fixing unit 10 to obtain a fixed image.

  On the other hand, the image forming apparatus further rotates the electrostatic latent image carrier 2 on which the toner image is transferred to the recording paper by the intermediate transfer unit 6, and removes the toner remaining on the surface of the electrostatic latent image carrier by the cleaning unit 13. Then, the charge is removed by the charge removing unit 8. The image forming apparatus uniformly charges the electrostatic latent image carrier 2 neutralized by the neutralization unit 8 by the charging unit 3, and then performs the next image formation as described above. The cleaning unit 13 is not limited to scraping off the residual toner on the electrostatic latent image carrier 2 with a blade. For example, the cleaning unit 13 scrapes off residual toner on the electrostatic latent image carrier 2 with a fur brush. There may be.

  FIG. 6 is a cross-sectional view showing an example of the developing unit 5 of the one-component developing system to which the present invention is applied together with the vicinity of the photoreceptor 2. In this apparatus example, the toner in the toner hopper 20 is supplied onto the developing roller 22 by the replenishing roller 21. The toner supplied onto the developing roller 22 is charged by friction between the developing roller 22 and the thin layer forming member 23. The toner that has not been consumed for development is peeled off from the developing roller 22 by the replenishing roller 21 and returns to the toner hopper. Further, the inside of the hopper is stirred by the agitator 24 and kept in a uniform state.

FIG. 7 is a cross-sectional view showing the configuration of an example of the developing unit 5 of the two-component developing system to which the present invention is applied, together with the vicinity of the photoreceptor 2. In the developing device 110, a developing sleeve 111 is disposed so as to be close to the photosensitive member 100, and a developing region is formed in a portion facing both. In the developing sleeve 111, a developing sleeve 111 formed of a nonmagnetic material such as aluminum, brass, stainless steel, or conductive resin in a cylindrical shape is rotated in a clockwise direction by a rotation driving mechanism (not shown). . In the area of the developing sleeve 111 opposite to the photosensitive member 100, the toner fed from the toner bottle 115 and the first conveying screw 112 for pumping the developer in the developing casing to the developing sleeve 111 while stirring is developed. A second conveying screw 113 that mixes and conveys the agent is provided. The toner in the developer is frictionally charged by mixing and stirring by the first conveying screw 112 and the second conveying screw 113.
Inside the developing sleeve 111, a magnet roller body that forms a magnetic field is provided in a fixed state so as to cause the developer to stand up on the peripheral surface of the developing sleeve 111. The magnet roller body includes a plurality of magnets. Development main magnet P1 for causing the developer to spike in the development area, magnet P3 for pumping the developer onto the developing sleeve 111, magnets P4 and P5 for transporting the pumped developer to the development area, developer in the developed area Is provided with a magnet P2. These magnets P1, P3, P4, P5 and P2 are arranged in the radial direction of the developing sleeve 111 and have a magnetic force line distribution as shown in FIG. Here, a magnet P3 for pumping up the developer onto the developing sleeve 111, a magnet P5 for transporting the pumped developer to the development area, and a magnet P2 for transporting the developer in the developed area form an N pole. The developing main magnet P1 and the magnet P4 that conveys the pumped developer form an S pole. The downstream magnet P2 that forms the developer carrying magnet has a function of assisting the formation of the developing main magnet magnetic force, and if it is too small, carrier adhesion occurs.
The magnetic carrier of the developer forms spikes on the developing sleeve 111 so as to follow the normal magnetic field lines emitted from the magnet roller body, and the charged toner adheres to the magnetic carrier forming the spikes, so that the magnetic brush Composed. The magnetic brush is conveyed in the same direction as the developing sleeve 111 by the rotation of the developing sleeve 111. The linear velocity of the developing sleeve 111 is preferably different from the linear velocity of the photoconductor 100. By providing the linear velocity difference, it is possible to satisfactorily supply toner to the electrostatic latent image formed on the surface of the photoconductor 100.
In the upstream portion of the development area in the developer transport direction (clockwise direction in the figure), the height of the magnetic brush formed by the magnetic carrier, that is, the thickness of the developer layer on the development sleeve 111 is regulated. A doctor blade 114 as a layer thickness regulating member is provided. The doctor gap DG, which is the distance between the doctor blade 114 and the developing sleeve 111, needs to be set so that the developer magnetic brush formed on the developing sleeve 111 sufficiently rubs the surface of the photoreceptor 100.

  In the image forming method and the image forming apparatus of the present invention, the toner of the present invention is capable of forming a high-quality image that is resistant to peeling and burying of external additives over time and that is stable against changes in the temperature and humidity environment. Therefore, high-quality images can be obtained efficiently over a long period of time.

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

Example 1
-Production of magenta base toner A1 by pulverization-
First, the raw materials of the following formulation are mixed with a Henschel mixer, melt kneaded with a busconyder (Bus) set at 120 ° C., the kneaded product is cooled, and then finely pulverized with a pulverizer using a turbo mill (Turbo Industries). Crushing and classification using an air classifier produced magenta toner base particles A having a volume average particle size of 6.72 μm, an average circularity of 0.91, and a specific surface area of 2.34 m ² / g.
<Toner prescription>
Polyester resin (softening point 103 ° C., glass transition temperature (Tg) = 65 ° C.) 100 parts by mass Quinacridone-based magenta pigment 4 parts by mass Zinc compound of salicylic acid 1.5 parts by mass

  Next, 2.0 parts by mass of porous silica having a volume average particle diameter of 50 nm and a pore diameter of 10 nm of primary particles was added to 100 parts by mass of the obtained magenta toner base particles A, and a Henschel mixer (Mitsui Miike Co., Ltd.) was added. Were sufficiently mixed to produce magenta toner A1.

(Example 2)
-Production of magenta toner A2 by pulverization-
To 100 parts by mass of toner base particle A of Example 1, 1.0 part by mass of hydrophobic silica having a primary particle volume average particle size of 10 nm, hydrophobic having a primary particle volume average particle size of 100 nm and pore size of 10 nm. 1.4 parts by mass of porous silica and 0.8 parts by mass of titania having a volume average particle diameter of 20 nm of primary particles are added and mixed thoroughly with a Henschel mixer (manufactured by Mitsui Miike) to prepare magenta toner A2. did.

(Example 3)
-Production of magenta toner A3 by pulverization-
To 100 parts by mass of toner base particle A of Example 1, 1.0 part by mass of hydrophobic silica having a primary particle volume average particle size of 10 nm, hydrophobic having a primary particle volume average particle size of 100 nm and pore size of 10 nm. 1.0 part by mass of porous silica and 0.8 part by mass of titania having a volume average particle diameter of 20 nm of primary particles were added. Next, 0.1 part by mass of zinc stearate was added and mixed well with a Henschel mixer (Mitsui Miike) to prepare magenta toner A3.

(Comparative Example 1)
-Production of magenta toner A4 by pulverization-
To 100 parts by mass of toner base particle A of Example 1, 1.5 parts by mass of hydrophobic silica having a volume average particle diameter of 10 nm of primary particles and 0.8% of titania having a volume average particle diameter of 20 nm of primary particles are used. A magenta toner A4 was prepared by adding parts by mass and thoroughly mixing with a Henschel mixer (Mitsui Miike).

Example 4
-Production of Toner B1 by Polymerization Method-
In the same manner as described in Examples in Japanese Patent Application Laid-Open No. 2004-18453, toner base particles B using a polyester resin were produced.
The obtained toner base particles B had a volume average particle size of 5.8 μm and an average circularity of 0.97.
Next, with respect to 100 parts by mass of the toner base particle B, 1.0 part by mass of hydrophobic silica having a volume average particle diameter of 10 nm of primary particles, a hydrophobic porous having a volume average particle diameter of 100 nm of primary particles, and a pore diameter of 10 nm. 1.0 part by mass of silica and 0.8 part by mass of titania having a volume average particle diameter of 20 nm of primary particles are added, and further 0.1 part by mass of zinc stearate is added, and a Henschel mixer (Mitsui Miike Co., Ltd.) is added. The toner was sufficiently mixed to prepare polymerization toner B1.

(Comparative Example 2)
-Production of toner B2 by polymerization method-
For 100 parts by mass of toner base particle B of Example 4, 1.5 parts by mass of hydrophobic silica having a primary particle volume average particle size of 10 nm and 0.8% of titania having a primary particle volume average particle size of 20 nm are 0.8. The polymer toner B2 was prepared by adding part by mass and thoroughly mixing with a Henschel mixer (Mitsui Miike).

Using the obtained toners of Examples 1 to 4 and Comparative Examples 1 to 2, various properties were evaluated as follows. The results are shown in Table 1.
All the evaluations were performed after continuously printing 100,000 sheets of black solid 5% chart paper using an image forming apparatus (Ricoh Co., Ltd., Ipsio Color 8150).

<Evaluation method of exfoliation and embedding of external additives over time>
The external additive peeling and burying over time was evaluated by observing the surface of the toner with an electron microscope, for example. Specifically, 0.1 g of toner was sampled from the developing unit, and the toner was fixed on a sample stage of an electron microscope using a conductive carbon tape. Thereafter, the observation magnification was set from 10,000 times to 50,000 times, 30 toners were sampled and observed, ranked according to the adhesion state of the external additives, and evaluated according to the following criteria.
〔Evaluation criteria〕
○: External additive is not peeled or buried, and is good ×: External additive is peeled, buried, or is poor

<Toner fluidity>
Using a known powder tester (manufactured by Hosokawa Micron Corporation), the measurement was carried out by the following method. First, 5.0 g of toner was accurately weighed. A sieve of 100 mesh (aperture 150 μm), 200 mesh (aperture 75 μm), and 400 mesh (aperture 38 μm) was stacked and set on the shaking table. A weighed amount of 5.0 g of toner was gently placed on a 100-mesh sieve, and was vibrated for 15 seconds with an amplitude of 1 mm. Thereafter, the amount of toner remaining on each sieve is precisely weighed. The following calculations were performed based on the measurement results.
(Toner amount on 100 mesh / 5.0) × 100 = A
(Toner amount on 200 mesh / 5.0) × 100 × (3/5) = B
(Amount of toner on 400 mesh / 5.0) × 100 × (1/5) = C
Toner fluidity (aggregation degree) [%] = A + B + C
The toner fluidity derived as described above was evaluated according to the following criteria.
〔Evaluation criteria〕
○: Fluidity (cohesion) 5% or less △: Fluidity (cohesion) 5% to 10%
X: Fluidity (cohesion) 20% to 50% or more

<Image density>
The image density of the solid image after continuous copying was measured by X-Rite 938, and the difference from the image density at the same position in the initial image was evaluated in three stages.
〔Evaluation criteria〕
○: No difference in image density Δ: Difference in image density is 0.1 to 0.3
×: Image density difference is 0.5 or more

<Chargeability>
1 g of developer was weighed and the change in charge amount was determined by the blow-off method. When the change in the charge amount was 5 μc / g or less, it was evaluated as ◯, when it was 10 μc / g or less, Δ when it exceeded 10 μc / g.

<Cleanability>
The evaluation of the cleaning property was performed by visually evaluating the degree of toner remaining in a portion corresponding to the solid image on the photoreceptor after continuous copying in three stages.
〔Evaluation criteria〕
○: There is no residual toner on the photoconductor, and it is good Δ: There is a little residual toner on the photoconductor ×: There is a lot of residual toner on the photoconductor, and it is defective

<Image quality>
As the image evaluation, the presence / absence of an abnormal image in a 5% chart, a blank paper image, and a 16 gradation image and the black portion image density were visually evaluated in 3 stages.
〔Evaluation criteria〕
○: Image density is high and good △: Image density is slightly low, but at a practically usable level ×: Image density is low and poor

The toner of the present invention is suitable for electrophotographic image formation because the external additive is less likely to peel off or be buried over time, is stable against changes in the temperature and humidity environment, and can form high-quality images. Used for.
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.

FIG. 1A is a schematic diagram showing the effect of the rubbing force when non-porous inorganic particles are present on the surface of the toner. FIG. 1B is a schematic diagram showing the effect of the rubbing force when the toner surface has porous inorganic particles. FIG. 2 is a schematic view showing an example of the process cartridge of the present invention. FIG. 3 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 4 is a schematic view showing an example of the tandem type full-color image forming apparatus of the present invention. FIG. 5 is a schematic view showing an example of a revolver type full color image forming apparatus of the present invention. FIG. 6 is a schematic view showing an example of a developing unit of the one-component developing system in the image forming apparatus of the present invention. FIG. 7 is a schematic view showing an example of a developing unit of a two-component developing system in the image forming apparatus of the present invention.

Explanation of symbols

2 Photoconductor (electrostatic latent image carrier)
DESCRIPTION OF SYMBOLS 3 Charging part 4 Writing part 5 Developing part 6 Intermediate transfer part 7 Transfer part 8 Electric discharge part 10 Fixing part 13 Cleaning part 15 Control device 16 Voltage application part 20 Toner hopper 21 Supply roller 22 Developing roller 23 Thin layer forming member 24 Agitator 201 Photosensitive Body 202 charging means 203 exposure means 204 developing means 205 recording medium 207 cleaning means 208 transfer means P recording paper

Claims (18)

In a toner comprising toner base particles containing at least a binder resin and a colorant, and at least one inorganic particle,
A toner, wherein at least one of the inorganic particles is porous inorganic particles.   The toner according to claim 1, wherein the inorganic particles are a plurality of types of inorganic particles having different particle diameters.   The toner according to claim 1, wherein the inorganic particles are hydrophobized.   The toner according to claim 1, wherein the porous inorganic particles have a primary particle volume average particle diameter of 50 nm or more.   The toner according to claim 1, wherein the pore diameter of the porous inorganic particles is 10 nm or more.   The toner according to claim 1, wherein the total amount of inorganic particles added is 0.05 to 10.0 parts by mass with respect to 100 parts by mass of the toner base particles.   The toner according to claim 1, further comprising a fatty acid metal compound.   The toner according to claim 1, wherein the toner has a volume average particle size of 10 μm or less.   The toner according to claim 1, wherein the toner has an average circularity of 0.96 or more.   A developer comprising the toner according to claim 1.   The developer according to claim 10, which is either a one-component developer or a two-component developer.   A toner-containing container filled with the toner according to claim 1.   An electrostatic latent image carrier and development means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to claim 1 to form a visible image. A process cartridge having at least   An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of claims 1 to 9 At least developing means for forming a visible image by developing the toner, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. An image forming apparatus.   Development in which the developing means carries toner on the peripheral surface, rotates in contact with the electrostatic latent image carrier, and supplies the toner to the electrostatic latent image formed on the latent image carrier for development The image forming apparatus according to claim 14, further comprising: a roller; and a thin layer forming member that is in contact with a peripheral surface of the developing roller and thins the toner on the developing roller. The developing means comprises a developer containing portion for containing a two-component developer comprising toner and a carrier, and a rotatable non-magnetic sleeve containing a plurality of fixed magnetic field generating means. The developer containing means is accommodated by the magnetic field generating means. A developer carrying member that carries the two-component developer in the unit on the surface and conveys it to a development area facing the electrostatic latent image carrier,
The image forming apparatus according to claim 14, further comprising a developer regulating member that regulates a layer thickness of the developer on the developer carrying member.   An image forming apparatus performs an intermediate transfer body on which a visible image formed on an electrostatic latent image carrier is primarily transferred, and a transfer for secondary transfer of the visible image carried on the intermediate transfer body to a recording medium. The image forming apparatus according to claim 14, further comprising: An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to any one of claims 1 to 9 to form a visible image An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium.