JP2011191725A - Toner for developing electrostatic image, image forming device using the toner, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: toner excellent in small dot reproducibility, cleaning property, low-temperature fixing property, blocking resistance, transfer efficiency and OHP transparency; an image forming device; and an image forming method. <P>SOLUTION: The toner can be obtained through a process to emulsify or disperse a toner material solution containing a solution containing materials constituting the toner in an aqueous medium. The toner material solution contains at least a precursor of a binder resin (A) and/or a binder resin (B), a wax, a layered inorganic mineral and tertiary amine. The wax is a petroleum wax of which weight reduction is 10 mass% or less at 165°C and its melting point is 60-95°C. The layered inorganic mineral is provided by modifying at least some of inter-layer ions with organic ions. The toner has an average circularity of 0.955-0.975 and the tertiary amine remaining in the toner is 0.1 wt.% or less. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a toner suitably used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, an image forming apparatus using the toner, and an image forming method.

  Image formation by electrophotography generally forms an electrostatic image on a photoreceptor (electrostatic image carrier), develops the electrostatic image with a developer to form a visible image (toner image), The visible image is transferred to a recording medium such as paper and fixed on the transfer medium by heat, pressure, solvent gas, or the like, and a series of processes are performed to obtain a fixed image (see Patent Document 1).

As the developer, a one-component developer using a magnetic toner or a non-magnetic toner alone and a two-component developer composed of a toner and a carrier are known. The one-component development method is classified into a magnetic one-component development method and a non-magnetic one-component development method depending on whether or not magnetic force is used to hold toner particles on the developing roller. In general, a toner produced by a kneading and pulverizing method in which a thermoplastic resin is melt-kneaded with a colorant or the like, then finely pulverized, and further classified is used. If necessary, inorganic fine particles or organic fine particles may be added to the surface of the toner particles for the purpose of improving fluidity and cleaning properties.

The toner obtained by the kneading and pulverizing method is generally fixed by heating and melting using a hot roll. At that time, if the hot roll temperature is too high, the toner is excessively melted and fused to the hot roll. An offset phenomenon may occur. Conversely, if the heat roll temperature is too low, the toner may not be sufficiently melted and fixing may be insufficient. In recent years, from the viewpoint of energy saving and downsizing of devices such as copying machines, a toner having both hot offset resistance and low temperature fixability, which has a higher hot offset generation temperature and a lower fixing temperature, has been demanded. In particular, in full-color copiers, full-color printers, and the like, glossiness and color mixing of the image are important, so a toner having a lower melting point is desired. However, a toner having a lower melting point has a hot offset phenomenon. Since it tends to occur and is inferior in heat-resistant storage stability under high temperature and high humidity, a method for imparting releasability by applying silicone oil or the like to a hot roll has been conventionally employed in full-color equipment.

However, this method requires an oil tank, an oil application device, and the like, resulting in a complicated and large image forming apparatus. Further, since the heat roll is likely to be deteriorated, maintenance is required every certain period. Furthermore, there is a problem that oil adheres to copy paper, OHP film, etc., and the color tone of the image deteriorates due to the adhered oil.

Therefore, a method of adding a release agent such as wax to the toner is generally used in order to impart releasability without applying oil to the heat roll and prevent the problem of toner fusion. Here, the state of dispersion of the wax in the toner greatly affects the releasability. When the wax is compatible with the binder in the toner, the releasability cannot be expressed, and the releasability is expressed only when the wax is present as incompatible domain particles. At this time, if the dispersion diameter of the domain particles is too large, the ratio of the wax existing in the vicinity of the toner particle surface is relatively increased, so that the agglomeration is exhibited and the fluidity is deteriorated. There is a case where filming occurs due to transfer to a photoreceptor or the like, and good image quality cannot be obtained. On the other hand, if the dispersion diameter of the domain particles is too small, the wax may be excessively finely dispersed and sufficient releasability may not be obtained.

In the pulverization and kneading method, it is difficult to control the dispersion diameter of the domain particles of the wax, and the wax is likely to be present on the fracture surface, so that more wax is exposed on the toner surface, resulting in poor fluidity and filming. The above-mentioned problems of generation of the above-mentioned may occur. Furthermore, the toner obtained by the pulverization and kneading method generally has a wide particle size distribution, unevenness in the triboelectric chargeability of the toner, and the occurrence of fog and the like. In addition, the volume average particle diameter is 2 to 2 in terms of production efficiency. There is a problem that it is difficult to obtain a toner having a small particle diameter of 8 μm and it is impossible to meet the demand for high image quality.

Thus, attention has been drawn to toner obtained by granulation in an aqueous phase. The toner has a narrow particle size distribution, can be easily reduced in size, can obtain a high-quality and high-definition image, has an offset resistance due to high dispersion of a release agent such as wax, and low-temperature fixability. Also excellent. In addition, the transfer uniformity is excellent due to the uniformity of charging, and the fluidity is good, and the design of the developing device is advantageous in that the design of the hopper and the torque for rotating the developing roll can be reduced. .

As a toner obtained by granulating in the aqueous phase, a toner obtained by a suspension polymerization method or an emulsion polymerization aggregation method (hereinafter referred to as a chemical toner) has been developed.

In the suspension polymerization method, a monomer, a polymerization initiator, a colorant, a release agent, and the like are added to an aqueous phase containing a dispersion stabilizer while stirring to form oil droplets, and then the temperature is raised to cause a polymerization reaction. In this method, toner particles are obtained. According to the suspension polymerization method, although it is possible to reduce the toner particle size, it is necessary to use a dispersion stabilizer that lowers the chargeability when it remains, and if no dispersion stabilizer is used, There is a problem that it is difficult for the release agent to easily enter the oil droplets at the time of formation, and to be appropriately present on the surface of the toner particles. Furthermore, only a spherical shape can be obtained, which is problematic for cleaning.

In the emulsion polymerization aggregation method, for example, a polyester resin is used as a binder resin, and after emulsifying and dispersing in an aqueous phase, fine particles obtained by solvent removal, a colorant, a release agent (wax), and the like are mixed with water. This is a method for producing toner particles by agglomerating a dispersion formed by dispersing in a phase and heat-sealing (see Patent Documents 2 and 3). In this method, the shape can be controlled by controlling the heating and fusing temperature and time. According to these production methods, since there is no generation of ultrafine particles, it is possible to produce a classification-free toner having no emulsification loss and a sharp particle size distribution. If they are agglomerated, the coalescence becomes insufficient, and cracks at the interface after the coalescence occur. For this reason, the heating process which advances coalescence between particles with heat is essential. However, when heated, the wax component is finely dispersed in the toner particles (surface precipitation), spheroidized, aggregated between the finely dispersed wax particles, etc., and the wax is sufficiently finely dispersed. Can not maintain the state. In particular, when a wax having a low melting point (release agent) is used, there is a problem that it is easy to dissolve in the heating step, the releasability cannot be ensured, and the suitability for oilless heat roll fixing is lacking.

Further, a release agent fine particle coated with or impregnated with a vinyl polymer by adding a polymerizable vinyl monomer and a water-soluble polymerization initiator to the release agent emulsion for polymerization is added at the time of emulsification of the toner composition. A method of uniformly and firmly adhering to the toner surface has been proposed (see Patent Document 4). However, in this method, it is essential to polymerize the release agent emulsion and the polymerizable vinyl monomer, and since the glass transition temperature (Tg) of the resin constituting the release agent fine particles is high, There exists a problem that it is inferior to releasability, low temperature fixability, etc.

Patent Document 5 discloses a low melting point wax that cannot be used in a pulverized toner by producing a toner by suspension polymerization of a polymerizable monomer system containing a substance having a polar group and a release agent in water. It is described that can be contained. Contrary to the polar component, the nonpolar component such as wax does not exist in the vicinity of the surface of the toner particles, and has a pseudo capsule structure covered with the polar component on the surface. However, the wax distribution inside the toner particles has not been analyzed and is unknown.

Patent Document 6 describes a toner in which the wax content is 0.1 to 40% by mass and the ratio of the wax exposed on the toner surface is 1 to 10% by mass of the constituent compound exposed on the surface. . The ratio of the wax exposed on the toner surface is measured and defined by ESCA. However, since the analysis by ESCA is limited to a depth of about 0.1 μm from the outermost surface of the toner, it is necessary to know the dispersion state of the wax which exists further inside and is suitable for exhibiting releasability in the fixing process. Absent.

Patent Document 7 describes a toner in which wax is encapsulated in toner particles and localized on the particle surface. However, the detailed dispersion state of the wax near the toner surface is unknown.

Patent Document 8 defines the ratio of the wax exposed on the toner surface measured by FTIR-ATR. However, toner blocking and hot offset properties, filming and paper wrapping are in a completely trade-off relationship, and it is difficult to improve toner by further improving toner and controlling wax dispersion. It is in.
Therefore, while maintaining the advantages of a chemical toner that has a small particle size and narrow particle size distribution and excellent fluidity, it has excellent releasability at low temperatures, less filming, low temperature fixability and heat resistant storage stability. However, there is a strong demand for a method that can stably and efficiently obtain a toner capable of obtaining a high-quality image at the same time, but this method has not yet been provided.

  As an attempt to control the shape, a method is known in which a filler is added to an organic solvent together with a toner composition to make particles indefinite (see Patent Document 9). However, when a filler is added to the toner, the viscoelasticity of the toner increases, and the lower limit of fixing is observed. In addition, when the filler is present on the toner surface, there is almost no increase in the viscoelasticity of the toner. However, if a substance such as a filler is present on the toner surface layer, it inhibits the exudation of wax or the binder resin dissolves. Inhibition of constant temperature fixing property and hot offset property is also observed.

  Furthermore, a charge control agent has been developed in which ions such as metal cations existing between layers of the layered inorganic mineral are modified with ions such as organic cations, and it has been proposed to add this to the toner particles after granulation (Cited Document 10). 11, 12, and 13), and toners with low circularity using layered inorganic minerals have been proposed in Patent Document 14, but these toners have not yet been sufficiently low-temperature fixability and heat-resistant storage stability.

  In addition, the image forming apparatus needs to transfer and supply toner to the developing device according to the amount of toner consumed. Since the suction type powder pump that transfers toner transfers the toner as an air-fuel mixture, there is a load on the toner particles. The toner is less deteriorated, but the toner powder agglomerates also with the suction type powder pump, and an abnormal image (firefly) that forms a light color gamut around the dark color point is likely to occur. Even when the above conventional toner is used, the occurrence of abnormal images cannot be prevented.

(1) Provided are a toner capable of obtaining a high-quality image having excellent reproducibility of fine dots, an image forming apparatus and an image forming method using the toner.
(2) To provide a toner that can obtain high reliability especially in cleaning, an image forming apparatus using the toner, and an image forming method.
(3) Toner having excellent low-temperature fixability and blocking resistance, and an image forming apparatus and an image forming method using the toner are provided.
(4) Toner that can simultaneously achieve the problems (1) to (3), an image forming apparatus using the toner, and an image forming method are provided.
(5) Provided are a dry toner that is excellent in transfer efficiency and has a low transfer residual toner to obtain a high-quality image, and an image forming apparatus and an image forming method using the toner.
(6) To provide an oilless dry toner having both charge stability and low-temperature fixability.
(7) To provide a novel toner that consumes less power and has both high transferability and OHP transparency required for color images at a high level.
(8) To prevent the occurrence of abnormal images in the image forming apparatus having a toner transfer step of transferring toner from the toner cartridge to the development step by a suction type powder pump according to the consumed amount.

The present inventors have completed the present invention to solve the above-described problems.
That is, according to the present invention, the following toner and image forming method and apparatus are provided.
(1) A toner obtained through a step of emulsifying or dispersing a toner material liquid containing a liquid containing a material constituting the toner in an aqueous medium, wherein the toner material liquid contains at least a binder resin (A) And / or a binder resin (B) precursor, a wax, a layered inorganic mineral, and a tertiary amine, and the wax has a melting point of 60 mass% at 165 ° C. of 10% by mass or less. It is a petroleum wax of ˜95 ° C., and the layered inorganic mineral is obtained by modifying at least part of ions between layers with organic ions, and the toner has an average circularity of 0.955 to 0.975. And a tertiary amine compound remaining in the toner is 0.1 wt% or less.
(2) The toner according to (1), wherein the toner material liquid contains a tertiary amine compound in an amount of 0.05 wt% to 1.5 wt% based on the solid content of the toner.
(3) The toner according to (1) or (2), wherein the wax is at least a microcrystalline wax.
(4) The binder resin (B) precursor contains an active hydrogen group-containing compound and a polymer having reactivity with the active hydrogen group, and the binder resin (B) is the aqueous medium. (1) to (1), wherein the active hydrogen group-containing compound and a polymer having reactivity with the active hydrogen group are reacted in the emulsifying or dispersing step. The toner according to any one of 3).
(5) The toner according to (4), wherein the polymer having reactivity with the active hydrogen group contains a modified polyester resin.
(6) The toner according to (5), wherein the modified polyester resin has a weight average molecular weight of 3,000 to 45,000.
(7) The toner according to any one of (1) to (6), wherein the binder resin (A) is an unmodified polyester.
(8) The toner according to (7), wherein the acid value of the unmodified polyester is 12 to 30 (mgKOH / g).
(9) The toner according to any one of (1) to (8) above, wherein the glass transition point of the unmodified polyester is 30 to 70 ° C.
(10) The above-mentioned (1), wherein the binder resin containing the binder resin (A) and the binder resin (B) has a weight average molecular weight of 3,000 to 30,000 in a THF soluble portion The toner according to any one of (9) to (9).
(11) The toner according to (10), wherein the binder resin has a glass transition point of 35 ° C. to 65 ° C.
(12) The toner according to any one of (1) to (11) above, wherein an insoluble content of tetrahydrofuran (THF) contained in the toner is 5 to 25% by mass.
(13) The toner according to any one of (1) to (12), wherein the toner contains 10 to 300% by mass of a wax dispersant with respect to the wax.
(14) The toner according to any one of (1) to (13) above, wherein the volume average particle diameter of the dispersed particles of the wax in the toner material liquid is 0.1 to 2 μm.
(15) The toner according to any one of (1) to (14) above, wherein the toner particles have a volume average particle diameter / number average particle diameter of 1.00 to 1.25.
(16) The toner according to any one of (1) to (15), wherein the toner particles have a volume average particle diameter of 1 to 7 μm.
(17) A developer comprising the toner according to any one of (1) to (16) and a carrier.
(18) A toner-containing container comprising the toner according to any one of (1) to (16).
(19) In a process cartridge that integrally supports an electrostatic latent image carrier, a developing unit, a charging unit and / or a cleaning unit and is detachable from the main body of the image forming apparatus, the developing unit holds toner. The toner is the toner according to any one of (1) to (16).
(20) By an image forming apparatus having a toner transfer step of supplying toner to the development step according to the amount of toner consumed from the toner cartridge, a development step of developing the developer containing the toner, a transfer step, and a fixing step An image forming method for forming an image, wherein the toner is the toner according to any one of (1) to (16), and a toner having a diameter of 0.2 mm or more in the developer after the toner transfer step. An image forming method, wherein the amount of aggregates is less than two.
(21) An image forming apparatus having a toner transfer process for supplying toner to a development process according to the amount of toner consumed from the toner cartridge, a development process for developing a developer containing the toner, a transfer process, and a fixing process. The toner is the toner according to any one of (1) to (16), and the amount of toner aggregates having a diameter of 0.2 mm or more in the developer after the toner transfer step is less than two. An image forming apparatus, comprising:

(1) According to the present invention, it is possible to provide a toner capable of obtaining a high-quality image having excellent small dot reproducibility, an image forming apparatus and an image forming method using the toner.
(2) According to the present invention, it is possible to provide a toner that can obtain high reliability particularly in cleaning, an image forming apparatus and an image forming method using the toner.
(3) According to the present invention, it is possible to provide a toner excellent in low-temperature fixability and blocking resistance, an image forming apparatus and an image forming method using the toner.
(4) According to the present invention, it is possible to provide a toner that can simultaneously achieve the problems (1) to (3), an image forming apparatus using the toner, and an image forming method.
(5) According to the present invention, it is possible to provide a dry toner capable of obtaining a high-quality image with excellent transfer efficiency and a small amount of residual toner, and an image forming apparatus and an image forming method using the toner.
(6) According to the present invention, an oilless dry toner having both charge stability and low-temperature fixability can be provided.
(7) According to the present invention, it is possible to provide a novel toner that consumes less power and has both high transferability and OHP transparency required for color images at a high level.

It is the schematic of a transfer apparatus. It is a figure which shows an example of a powder pump means. 1 is an overall configuration diagram illustrating an image forming apparatus according to an embodiment of the present invention. FIG. 4 is a cross-sectional view showing the vicinity of an image forming unit in the image forming apparatus of FIG. 3. FIG. 4 is a cross-sectional view illustrating a toner conveyance path in the image forming apparatus of FIG. 3. It is a figure which shows a process cartridge. FIG. 3 is a diagram illustrating an example of a fixing device.

First, the toner of the present invention will be described. The toner of the present invention is a toner obtained through a step of emulsifying or dispersing a toner material liquid containing a liquid containing a material constituting the toner in an aqueous medium, and the toner material liquid includes at least a binder resin (A) and / or binder resin (B) precursor, wax, layered inorganic mineral, and tertiary amine, and the wax has a weight loss at 165 ° C. of 10% by mass or less. It is petroleum wax having a melting point of 60 to 95 ° C., and the layered inorganic mineral is obtained by modifying at least a part of ions between layers with organic ions, and the toner has an average circularity of 0.955 to 0.00. The toner is 975, and the tertiary amine compound remaining in the toner is 0.1 wt% or less.

The toner obtained through the step of emulsifying or dispersing the toner material liquid containing the toner material of the present invention in an aqueous medium usually has a spherical shape due to the interfacial tension and has a high average circularity. By adding a layered inorganic mineral in which at least a part of ions between layers of the layered inorganic mineral is modified with organic ions, it is possible to deform the layered mineral.

The reason for this is not clear, but when a layered inorganic mineral in which at least part of ions between layers of the layered inorganic mineral is modified with organic ions is added, the viscosity of the liquid containing the material constituting the toner has thixotropy, During stirring, the viscosity is low, the particle size distribution becomes narrow and uniform, and the viscosity immediately increases when the stirring is stopped. Therefore, it is considered that spheroidization due to interfacial tension can be prevented and the shape during stirring can be maintained.
Further, the layered inorganic mineral becomes moderately hydrophobic by modifying at least a part thereof with organic ions, and the oil phase containing the toner composition and / or the toner composition precursor has a non-Newtonian viscosity. The toner particles can be deformed, and the toner particles are finely distributed near the surface of the toner particles, so that the charge adjusting function is sufficiently exhibited.

However, in order to achieve both low-temperature fixability and heat-resistant storage stability, it is difficult to sufficiently deform it by simply adding the layered inorganic mineral when using petroleum wax, especially microcrystalline wax, which has a large viscosity change with respect to temperature change. Turned out to be.

The inventors of the present invention added a tertiary amine to a liquid containing a material constituting the toner in an amount of 0.1 wt% to 1.5 wt% based on the solid content of the toner in the toner material liquid. It has been found that the use of the toner promotes the deforming and can easily produce a toner having an average circularity of 0.955 to 0.975.

Although it is not clear why the modification is promoted by adding a tertiary amine, a layered inorganic mineral in which at least a part of ions between layers of the tertiary amine and the layered inorganic mineral is modified with organic ions is provided. It is thought that some kind of interaction is brought about.

The toner material liquid will be described.
The toner material liquid is obtained by dissolving or dispersing a material constituting the toner in an oil-based medium.
The material constituting the toner contains at least a binder resin (A) and / or a binder resin (B) precursor, a wax, a layered inorganic mineral, and a tertiary amine. Accordingly, it contains other components such as a colorant and a charge control agent.
In the method for producing a toner according to a preferred embodiment of the present invention, the toner material liquid is prepared in an oil-based medium by an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, wax, coloring It is possible to carry out by dissolving or dispersing a toner material such as an agent or a charge control agent. Among the materials constituting the toner, other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound. The components may be added and mixed in the aqueous medium in the preparation of the aqueous medium described later, or may be added to the aqueous medium together with the toner material liquid when the toner material liquid is added to the aqueous medium. .

The layered inorganic mineral refers to an inorganic mineral formed by superimposing layers having a thickness of several nanometers, and modifying with organic ions refers to introducing organic ions into ions existing between the layers. This is called intercalation in a broad sense.
As the layered inorganic mineral obtained by modifying at least part of the metal cations of the layered inorganic mineral used in the toner of the present invention with an organic cation, those having a smectite basic crystal structure modified with an organic cation are desirable.
Examples of the layered inorganic mineral modified with an organic cation include montmorillonite or bentonite, beidellite, nontronite, saponite, hectorite attapulgite, sepiolite, magadiite, and a mixture of two or more.
Of these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted with a small addition amount without affecting the toner characteristics.

Examples of the layered inorganic mineral obtained by modifying at least a part of the metal ions of the layered inorganic mineral with an organic cation include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like. A quaternary alkyl ammonium salt is desirable.
Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.
The content of the layered inorganic mineral obtained by partially modifying the toner material with an organic cation is preferably 0.05 to 2% by weight.

Commercially available layered inorganic minerals partially modified with organic ions include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite, such as (manufactured by Southern Clay), and stearalkonium bentonite, such as Bentone 27 (manufactured by Leox), Thixogel LG (manufactured by United catalyst), Clayton AF, Clayton APA (manufactured by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA.
In the present invention, organically modified hydrotalcite (organic anion modified hydrotalcite) is also preferably used.
For example, the layered double hydroxide salt contains monovalent and / or divalent and further trivalent metal cations and is modified with one or more organic anions of the compound represented by formula (1) Organically modified hydrotalcite.

X-R-Y Formula (1)
Wherein X is hydroxyl, carboxyl, sulfate or sulfo, Y is carboxyl, sulfate or sulfo, and R is a total of at least 8 carbon atoms, for example 8-50 carbon atoms, Aliphatic, cycloaliphatic, heterocyclic aliphatic, olefin, cycloolefin, heterocyclic olefin, aromatic, heterocyclic, especially having 10 to 44 carbon atoms, more preferably 10 to 32 carbon atoms An aromatic, araliphatic or heterocyclic araliphatic group, hydroxyl, amino, halogen, C1-C22-alkyl, C1-C22-alkoxy, -C1-C22-alkylene- (CO) -O- ( CH ₂ CH ₂ O) 0~50- alkyl, -C1～C22- alkylene _{- (CO) -O- (CH 2} CH 2 O) 0~50- haloalkyl, carboxy, sulfo One or more from the group of nitro or cyano, preferably, can also be present 1, 2, 3 or 4 kinds of substituents.)
Furthermore, you may use the organic modified hydrotalcite modified | denatured using the organic anion of Japanese translations of PCT publication No. 2006-503313.
In the double hydroxide salt, the number of hydroxyl groups is about 1.8 to 2.2 times, preferably about twice the total of all metal cations. The molar ratio of monovalent and / or divalent metal cation to trivalent metal cation can be 10 ⁴ to 10 ⁻⁴ , preferably 10 to 0.1, in particular 5 to 0.2.
The ratio of the monovalent metal cation to the divalent metal cation can be arbitrary, but in addition to the trivalent metal cation, only a divalent metal cation or a mixture of a monovalent metal cation and a divalent metal cation can be used. It is preferable to exist as a double hydroxide salt.
The organic anion can be a monovalent or polyvalent charged organic anion of formula (1). The amount of anion is determined by the positive and negative charge stoichiometry in the double hydroxide salt so that the sum of all charges is zero.
However, some anions of formula (1), for example 0.1-99 mol%, in particular 1-90 mol%, can be replaced with other anions, such as inorganic anions, such as halides, bicarbonates. , Carbonate, sulfate, nitrate, phosphate or borate or acetate can be substituted.
The organically modified layered inorganic mineral used in the present invention may be a double hydroxide salt containing water molecules in the form of water crystallized or inserted between individual layers.
Monovalent metal cations include in particular alkali metal cations such as Li +, Na + or K +.
The divalent metal cations, in ^{particular, Mg 2 +, Ca 2 +} , Zn 2 +, Co 2 +, Ni 2 +, Fe 2 +, Cu 2 + or Mn ² + and the like.
The trivalent metal cations, in ^{particular, Al 3 +, Fe 3 +} , Co 3 +, Mn 3 +, Ni 3 +, Cr 3 + and ^{B 3} + and the like.
Particularly preferred double hydroxide salts are those containing Mg ² + and Al ³ +, in particular in a molar ratio of 3.1: 1 to 1: 2.
The organic anion is preferably benzylic acid, naphthalene disulfonic acid such as naphthalene-1,5-disulfonic acid, naphthalene dicarboxylic acid, hydroxynaphthoic acid such as 1-hydroxy-2-naphthoic acid, 2-hydroxy-1 -Naphthoic acid, 3-hydroxy-2-naphthoic acid, octanedicarboxylic acid, decanedicarboxylic acid (sebacic acid), dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, naphthalenetetracarboxylic acid, sulfosuccinic acid (C ₆ -C ₂₂₎ - alkyl monoesters, sulfosuccinic acid _(C 6 ~C ₂₂₎ - include anions from the group of fluoroalkyl monoesters.
However, it is also possible to replace part of the organic anion A, for example 0.1-99.9 mol%, preferably 0.2-99.8 mol%, with another organic anion. The organic anion corresponds to the formula H—R—Y, where R and Y have the same definition as described for formula (1), for example C ₁₂ -C ₄₄ fatty acids, Especially stearic acid.
Particularly preferred double hydroxide salts are those with a Mg: Al molar ratio of 3.1: 1 to 1: 2, with sebacic acid as the organic anion in each case and in its calcined form.
The layered inorganic mineral is preferably contained in the toner material in an amount of 0.05 to 5.0% by weight,
More preferably, it is 0.05-2 weight%.

The toner of the present invention uses petroleum wax as the wax.
Petroleum wax is a solid or semi-solid hydrocarbon present in crude oil at normal temperature, and examples thereof include paraffin wax, microcrystalline wax, and petrolatum.
Paraffin wax is a wax that is solid at room temperature and has a straight chain saturated hydrocarbon having about 20 to 36 carbon atoms as a main component, and microcrystalline wax is a saturated hydrocarbon having a large molecular weight and having side chains of about 30 to 55 carbon atoms. Is a wax that is solid at room temperature and contains a small amount of n-paraffin, naphthene, aromatic hydrocarbon and the like.
The higher the melting point of paraffin wax, the higher the viscosity. However, the microcrystalline wax has a side chain and thus exhibits high viscosity even at a low melting point. Paraffin wax and microcrystalline wax both decrease in viscosity with increasing temperature, but microcrystalline wax has a large viscosity change with respect to temperature change, and is preferable for achieving both low-temperature fixability and heat-resistant storage stability.

As the microcrystalline wax, those having a low melting point are preferable from the viewpoint of improving low-temperature fixability. The melting point is preferably 60 to 95 ° C, more preferably 65 to 90 ° C, and further preferably 85 to 90 ° C.
If the melting point is less than 60 ° C., the wax may adversely affect the heat resistant storage stability, and if it exceeds 95 ° C., a cold offset may easily occur during fixing at a low temperature.
Furthermore, when the wax is dispersed in the liquid, the dispersion is prepared by once melting and cooling the wax in the liquid. Need to be higher. When such a solvent is used, the temperature may be higher than the glass transition point of the toner when the solvent is removed, and the toner may cause aggregation and coarsening.

The microcrystalline wax preferably has a small volatile content at the time of fixing, and preferably has a weight loss at 165 ° C. of 10% by mass or less.

There is no restriction | limiting in particular as said tertiary amine compound, Although it can select suitably according to the objective, For example, the compound represented by following General formula (1) can be used conveniently. The tertiary amine compound not only functions as a urethane or urea catalyst, but also in the preparation of the oil-in-water dispersion, when the toner material is dissolved or dispersed in the aqueous medium, In combination with the inorganic mineral, it functions as an emulsification aid, and is preferably contained in an amount of 0.05 wt% to 1.5 wt% with respect to the toner solid content in the toner material liquid.

  When the tertiary amine remains in the toner particles, the blocking resistance of the toner particles is deteriorated. Particularly, when the tertiary amine is combined with the wax, the blocking resistance is remarkably deteriorated. It is necessary to make the residual amount of the amine compound 0.05 wt% to 0.1 wt%.

  The tertiary amine compound can be removed in the toner particle cleaning step. The tertiary amine compound is water-soluble and can be removed by washing. However, if it is insufficient, the surfactant is removed by washing, and then an acid is added to the aqueous dispersion containing the toner. By adjusting the pH to about 4, the tertiary amine compound is further removed.

<Binder resin>
The binder resin exhibits adhesiveness to a recording medium such as paper, and the binder resin (A) and / or the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound (binding agent). It is preferable that an adhesive polymer (binder resin B) obtained by reacting a (resin precursor) in an aqueous medium is included.
By including the binder resin (A) and / or the binder resin (B), it is possible to easily add a gel component to the toner. Furthermore, a binder resin appropriately selected from known binder resins may be included.
The weight average molecular weight of the THF-soluble component of the binder resin is preferably 3,000 or less, more preferably 4,000 to 30,000, and particularly preferably 4,000 to 20,000. Hot offset resistance may fall that a weight average molecular weight is 3,000 or less.
The tetrahydrofuran (THF) insoluble matter contained in the toner is preferably 5 to 25% by mass.

  The glass transition temperature of the binder resin is preferably 35 ° C to 65 ° C, and more preferably 45 ° C to 65 ° C. When the glass transition temperature is less than 35 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 65 ° C., the low-temperature fixability may not be sufficient. Note that a toner containing a polyester resin subjected to a crosslinking reaction or elongation reaction as a binder resin has good storage stability even when the glass transition temperature is low.

The binder resin preferably contains a binder resin (B) obtained by reacting an active hydrogen group-containing compound with a polymer having reactivity with the active hydrogen group.
The polymer having reactivity with the active hydrogen group is not particularly limited and may be appropriately selected depending on the intended purpose. A modified polyester resin capable of reacting with a compound having an active hydrogen group is preferably used.
The weight average molecular weight of the modified polyester resin is preferably 3,000 to 45,000.
The modified polyester resin capable of reacting with the compound having an active hydrogen group is preferably a polyester having an isocyanate group as a polymer having reactivity with the active hydrogen group.
In addition, you may form a urethane bond by adding alcohol when making the isocyanate group containing polyester resin and the compound which has an active hydrogen group react. The molar ratio of the urethane bond to the urea bond thus formed (to distinguish it from the urethane bond of the polyester prepolymer having an isocyanate group) is preferably from 0 to 9, and preferably from 1/4 to 4. Is more preferable, and 2/3 to 7/3 is particularly preferable. If this ratio is greater than 9, the hot offset resistance may decrease.

  Specific examples of the binder resin (B) include a polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate, and bisphenol A urea. Mixture of ethylene oxide 2-mole adduct and isophthalic acid polycondensate; Bisphenol A ethylene oxide 2-mole adduct and isophthalic acid polycondensate reacted with isophorone diisocyanate and uread with isophorone diamine And a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid Polyester prepolymer obtained by reacting polycondensate of formic acid with isophorone diisocyanate and uread with isophorone diamine, bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and polycondensate of terephthalic acid A mixture of bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid with isophorone diisocyanate and a urea prepolymerized with isophorone diamine, and bisphenol A Mixture of propylene oxide 2 mol adduct and polycondensate of terephthalic acid; bisphenol A ethylene oxide 2 mol adduct and polycondensate of terephthalic acid to isophorone diisocyanate A mixture of a polyester prepolymer that has been reacted with urethan with hexamethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid; bisphenol A ethylene oxide 2 mol adduct and terephthalic acid A polyester prepolymer obtained by reacting a polycondensate of bisphenol A with isophorone diisocyanate and uread with hexamethylenediamine, a bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct, and a polycondensate of terephthalic acid, A mixture of bisphenol A ethylene oxide 2 mol adduct and a polycondensate of terephthalic acid reacted with isophorone diisocyanate and uread with ethylenediamine, and bis Mixture of phenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate; polyester prepolymer obtained by reacting bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate with diphenylmethane diisocyanate in urea with hexamethylenediamine Of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride A polyester prepolymer obtained by reacting a polycondensate with diphenylmethane diisocyanate and uread with hexamethylenediamine, and a bisphenol A ethylene oxide 2-mole adduct / biphenyl Mixture of phenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate; polyester prepolymer obtained by reacting bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate with toluene diisocyanate with urea in hexamethylene diamine And a mixture of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate.

The compound having an active hydrogen group acts as an elongation agent, a crosslinking agent or the like when a polymer having reactivity to the active hydrogen group undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous medium.
Specific examples of the active hydrogen group include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group, mercapto group and the like. In addition, an active hydrogen group may be individual, and 2 or more types of mixtures may be sufficient as it.

  The compound having an active hydrogen group can be appropriately selected according to the purpose. However, when the polymer having reactivity to the active hydrogen group is a polyester prepolymer having an isocyanate group, the compound has an elongation with the polyester prepolymer. Amines are preferred because they can be increased in molecular weight by reaction, crosslinking reaction or the like.

  The amines are not particularly limited and may be appropriately selected depending on the intended purpose. Specifically, diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and these amino groups are blocked. Among them, diamine and a mixture of diamine and a small amount of trivalent or higher amine are preferable. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the diamine include aromatic diamines, alicyclic diamines, and aliphatic diamines. Specific examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, and the like. Specific examples of the alicyclic diamine include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminocyclohexane, isophorone diamine and the like. Specific examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, hexamethylene diamine and the like. Specific examples of the trivalent or higher amine include diethylenetriamine and triethylenetetramine. Specific examples of amino alcohols include ethanolamine and hydroxyethylaniline. Specific examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan. Specific examples of amino acids include aminopropionic acid and aminocaproic acid. Specific examples of those in which the amino group is blocked include ketimine compounds and oxazolidone compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

  In addition, a reaction terminator can be used in order to stop the elongation reaction, the crosslinking reaction, and the like of the compound having an active hydrogen group and a polymer having reactivity with the active hydrogen group. When a reaction terminator is used, the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Specific examples of the reaction terminator include monoamines such as diethylamine, dibutylamine, butylamine and laurylamine, and ketimine compounds in which these amino groups are blocked.

  The ratio of the equivalent of the isocyanate group of the polyester prepolymer to the equivalent of the amino group of the amine is preferably 1/3 to 3, more preferably 1/2 to 2, and particularly preferably 2/3 to 1.5. . If this ratio is less than 1/3, the low-temperature fixability may be lowered. If it exceeds 3, the molecular weight of the urea-modified polyester resin may be lowered, and the hot offset resistance may be lowered.

  The polymer having reactivity to active hydrogen groups (hereinafter sometimes referred to as “prepolymer”) can be appropriately selected from known resins and the like, and can be selected from polyol resins, polyacrylic resins, polyester resins, and epoxy resins. And derivatives thereof. Among them, it is preferable to use a polyester resin in terms of high fluidity and transparency at the time of melting. These may be used alone or in combination of two or more.

  Examples of the functional group capable of reacting with the active hydrogen group of the prepolymer include an isocyanate group, an epoxy group, a carboxyl group, and a functional group represented by the chemical structural formula -COC-, among which an isocyanate group is preferable. . The prepolymer may have one of such functional groups or two or more kinds.

  As a prepolymer, the molecular weight of the polymer component can be easily adjusted, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. Since it can ensure, it is preferable to use the polyester resin which has an isocyanate group etc. which can produce | generate a urea bond.

  The polyester prepolymer containing an isocyanate group can be appropriately selected depending on the purpose. Specific examples include a reaction product of a polyester resin having an active hydrogen group obtained by polycondensation of a polyol and a polycarboxylic acid, and a polyisocyanate.

  The polyol is not particularly limited and can be appropriately selected depending on the purpose. A diol, a trihydric or higher alcohol, a mixture of a diol and a trihydric or higher alcohol, and the like can be used. A trihydric or higher alcohol mixture is preferred. These may be used individually by 1 type and may use 2 or more types together.

  Specific examples of the diol include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol; diethylene glycol, triethylene glycol, dipropylene Diols having an oxyalkylene group such as glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols including ethylene oxide and propylene oxide , With addition of alkylene oxide such as butylene oxide; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols with ethyleneoxy , Propylene oxide, alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide. In addition, it is preferable that carbon number of alkylene glycol is 2-12. Among these, alkylene glycols having 2 to 12 carbon atoms or alkyne oxide adducts of bisphenols are preferable, alkylene oxide adducts of bisphenols or alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. The mixture of is particularly preferred.

  Examples of trihydric or higher alcohols include trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols. Specific examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Specific examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak and the like. Specific examples of adducts of trivalent or higher polyphenols with alkylene oxides include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.

When a diol and a trihydric or higher alcohol are mixed and used, the mass ratio of the trihydric or higher alcohol to the diol is preferably 0.01% by mass to 10% by mass, and 0.01% by mass to 1% by mass. Is more preferable.
The polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicarboxylic acids, trivalent or higher carboxylic acids, and mixtures of dicarboxylic acids and trivalent or higher carboxylic acids. A dicarboxylic acid or a mixture of a dicarboxylic acid and a small amount of a trivalent or higher polycarboxylic acid is preferred. These may be used alone or in combination of two or more.

  Specific examples of the dicarboxylic acid include divalent alkanoic acid, divalent alkenoic acid, and aromatic dicarboxylic acid. Specific examples of the divalent alkanoic acid include succinic acid, adipic acid, sebacic acid and the like. The number of carbon atoms of the divalent alkenoic acid is preferably 4 to 20, and specific examples include maleic acid and fumaric acid. The aromatic dicarboxylic acid preferably has 8 to 20 carbon atoms, and specific examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, a divalent alkenoic acid having 4 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable.

As the trivalent or higher carboxylic acid, trivalent or higher aromatic carboxylic acid or the like can be used. The carbon number of the trivalent or higher aromatic carboxylic acid is preferably 9 to 20, and specific examples thereof include trimellitic acid and pyromellitic acid.
As the polycarboxylic acid, an acid anhydride or lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid can be used. Specific examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

When the dicarboxylic acid and the trivalent or higher carboxylic acid are mixed and used, the mass ratio of the trivalent or higher carboxylic acid to the dicarboxylic acid is preferably 0.0% by mass to 10% by mass, and 0.01% by mass. % To 1% by mass is more preferable.
As for the mixing ratio at the time of polycondensation of the polyol and the polycarboxylic acid, the equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid is usually preferably 1 to 2, more preferably 1 to 1.5, 1.02-1.3 is particularly preferred.

  The content of the structural unit derived from the polyol in the polyester prepolymer having an isocyanate group is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and 2% by mass to 20%. Mass% is particularly preferred. When the content is less than 0.5% by mass, the hot offset resistance is lowered, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability of the toner, and exceeds 40% by mass. In this case, the low-temperature fixability may be lowered.

  The polyisocyanate can be appropriately selected depending on the purpose, but it is blocked with an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, an araliphatic diisocyanate, an isocyanurate, or the like, blocked with a phenol derivative, oxime, caprolactam, or the like. And the like.

Specific examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate. Specific examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Specific examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl. 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like. Specific examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Specific examples of the isocyanurates include tris (isocyanatoalkyl) isocyanurate, tris (isocyanatocycloalkyl) isocyanurate, and the like. These may be used individually by 1 type and may use 2 or more types together.

  When the polyisocyanate and the polyester resin having a hydroxyl group are reacted, the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is usually preferably 1 to 5, more preferably 1.2 to 4, more preferably 1 .5-3 are particularly preferred. When the equivalent ratio exceeds 5, the low-temperature fixability may decrease, and when it is less than 1, the offset resistance may decrease.

  The content of the structural unit derived from polyisocyanate in the polyester prepolymer containing an isocyanate group is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and 2% by mass. -20 mass% is still more preferable. When the content is less than 0.5% by mass, the hot offset resistance may be deteriorated, and when it exceeds 40% by mass, the low-temperature fixability may be deteriorated.

  The average number of isocyanate groups that the polyester prepolymer has per molecule is preferably 1 or more, more preferably 1.2 to 5, and still more preferably 1.5 to 4. When the average number is less than 1, the molecular weight of the urea-modified polyester resin is lowered, and the hot offset resistance may be lowered.

  1000-30000 are preferable and, as for the mass average molecular weight of the polymer which has the reactivity with respect to an active hydrogen group, 1500-15000 are more preferable. When the mass average molecular weight is less than 1000, the heat-resistant storage stability may be lowered, and when it exceeds 30000, the low-temperature fixability may be lowered.

The said mass mean molecular weight can be calculated | required by measuring a tetrahydrofuran soluble part, for example using a gel permeation chromatography (GPC).
Here, the GPC measurement can be performed as follows, for example. First, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran is used as a column solvent at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran solution adjusted to a sample concentration of 0.05% to 0.6% by mass is injected and measured. In measuring the molecular weight, the molecular weight is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of standard samples and the count number. As standard samples for preparing a calibration curve, the molecular weight is 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ and 4.48 × 10 ⁶ monodisperse polystyrene (manufactured by Pressure Chemical or Toyo Soda Industry Co., Ltd.) can be used. At this time, it is preferable to use about 10 kinds of standard samples. A refractive index detector can be used as the detector.

In addition, the binder resin of the present invention preferably contains an unmodified polyester resin (binder resin A) that is not modified in combination with the binder resin (B). Thereby, low temperature fixability and glossiness can be improved.
The acid value of the unmodified polyester resin is 12 to 30 mgKOH / g, and preferably 15 to 25 mgKOH / g. Generally, it becomes easy to be negatively charged by giving the toner an acid value.
Although the reason is not clear, when the acid value of the unmodified polyester resin is lower than 12 mgKOH / g, the reaction rate is increased, the viscosity of the toner material liquid is increased, and it is difficult to emulsify and disperse in an aqueous medium. become.
Moreover, when higher than 30 mgKOH / g, hot offset property deteriorates.

Examples of the unmodified polyester resin include a polycondensate of a polyol and a polycarboxylic acid. The unmodified polyester resin is partially compatible with the urea-modified polyester resin, that is, has a similar structure compatible with each other, in terms of low-temperature fixability and hot offset resistance. preferable.
The mass average molecular weight of the unmodified polyester resin is preferably 1,000 to 30,000, more preferably 1,500 to 15,000. When the mass average molecular weight is less than 1,000, the heat resistant storage stability may be lowered. For this reason, it is preferable that content of the component whose said mass mean molecular weight is less than 1,000 is 8 mass%-28 mass%. On the other hand, if the mass average molecular weight exceeds 30,000, the low-temperature fixability may deteriorate.

The glass transition temperature of the unmodified polyester resin is preferably 30C to 70C, more preferably 35C to 60C, and still more preferably 35C to 55C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g to 120 mgKOH / g, and still more preferably 20 mgKOH / g 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 mgKOH / g to 50.0 mgKOH / g, and more preferably 1.0 mgKOH / g to 30.0 mgKOH / g. Thereby, the toner is easily negatively charged.

  When the toner contains an unmodified polyester resin, the mass ratio of the polyester prepolymer having an isocyanate group to the unmodified polyester resin is preferably 5/95 to 25/75, more preferably 10/90 to 25/75. preferable. When the mass ratio is less than 5/95, the hot offset resistance may be lowered, and when it exceeds 25/75, the low-temperature fixability and the glossiness of the image may be lowered.

The oil-based medium is a solvent capable of dissolving or dispersing the material constituting the toner, and the solvent preferably contains an organic solvent. Further, the organic solvent is preferably removed when the toner base particles are formed or after the toner base particles are formed. From the viewpoint of ease of removal, a volatile solvent having a boiling point of less than 150 ° C. is preferred. When the boiling point is 150 ° C. or more, toner aggregation may occur when the solvent is removed. Examples of such solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate. , Methyl ethyl ketone, methyl isobutyl ketone, and the like. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of toner materials, and 60-140 mass parts is more. 80 to 120 parts by mass are more preferable.

  In addition to the above components, the toner of the present invention can further contain a release agent, a charge control agent, resin fine particles, inorganic fine particles, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, and the like.

  The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material is used. It is preferable to use it. Specifically, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts including fluorine-modified quaternary ammonium salts, alkylamides, phosphorus alone or compounds thereof, tungsten alone Or a compound thereof, a fluorosurfactant, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. These may be used individually by 1 type and may use 2 or more types together.

Commercially available products may be used as the charge control agent. Examples of commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, E-89 of phenol condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), copy charge of quaternary ammonium salt PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, boron complex LR-147 (manufactured by Nippon Carlit) , Quinacridone, azo pigments, other sulfonic acid groups, carboxyl groups, quaternary ammonia Polymer or the like having a functional group such as beam salts.
The charge control agent may be dissolved or dispersed after being melt-kneaded with the master batch, or may be dissolved or dispersed in a solvent together with each component of the toner, and may be fixed on the surface of the toner after the toner is produced. Also good.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence or absence of the additive, the dispersion method, and the like, and cannot be generally specified, but is 0.1% by mass to the binder resin. It is preferable that it is 10 mass%, and 0.2 mass%-5 mass% are more preferable. When the content is less than 0.1% by mass, the charge controllability may not be obtained. When the content exceeds 10% by mass, the chargeability of the toner becomes too large, and the electrostatic attractive force with the developing roller is low. May increase, resulting in a decrease in developer fluidity and a decrease in image density.

<Organic resin particles>
The organic resin particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin. Specific examples include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and the like. Among these, one or more resins selected from the group consisting of vinyl resins, polyurethane resins, epoxy resins, and polyester resins are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained. These may be used individually by 1 type and may use 2 or more types together.
The vinyl resin is a resin obtained by homopolymerizing or copolymerizing a vinyl monomer. Specifically, a styrene- (meth) acrylic acid ester copolymer, a styrene-butadiene copolymer, (meth) Acrylic acid-acrylic acid ester polymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

Moreover, as the organic resin particles, a copolymer obtained by polymerizing a monomer having a plurality of unsaturated groups can also be used. The monomer having a plurality of unsaturated groups can be appropriately selected according to the purpose. Specifically, sodium salt eleminol RS-30 of methacrylic acid ethylene oxide adduct sulfate (manufactured by Sanyo Chemical Industries), divinylbenzene 1,6-hexanediol diacrylate and the like.
The resin particles can be obtained by polymerization using a known method, but are preferably used as an aqueous dispersion of resin particles. As a method for preparing an aqueous dispersion of resin particles, in the case of a vinyl resin, an aqueous dispersion of resin particles is obtained by polymerizing a vinyl monomer using a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method. In the case of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins, a precursor such as a monomer or oligomer or a solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant. After that, heating or adding a curing agent to cure, a method for producing an aqueous dispersion of resin particles, a precursor such as a monomer or oligomer, or an appropriate emulsifier is dissolved in the solution, and then water is added. Method of phase inversion emulsification: Resin is pulverized and classified using a mechanical pulverizer or jet pulverizer to obtain resin particles, which are then dispersed in water in the presence of an appropriate dispersant. After obtaining resin particles by spraying a resin solution in the form of a mist, the resin particles are dispersed in water in the presence of an appropriate dispersant, a poor solvent is added to the resin solution, or the solvent is heated. By cooling the dissolved resin solution, the resin particles are precipitated, and after removing the solvent to obtain resin particles, a method of dispersing the resin particles in water in the presence of an appropriate dispersant, a resin solution, Disperse in an aqueous medium in the presence of an appropriate dispersant, then remove the solvent by heating, reduced pressure, etc., dissolve an appropriate emulsifier in the resin solution, and then add water to emulsify the phase. Methods and the like.

<Inorganic particles>
The inorganic particles are not particularly limited and can be appropriately selected from known materials according to the purpose. Specifically, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, Strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate , Silicon carbide, silicon nitride and the like. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method of an inorganic particle is 20 m <2> / g-500 m <2> / g.

The content of the inorganic particles in the toner is preferably 0.01% by mass to 5.0% by mass, and more preferably 0.01% by mass to 5.0% by mass.
When the surface treatment is performed using the fluidity improver, the hydrophobicity of the toner surface is improved, and the deterioration of the flow characteristics and charging characteristics can be suppressed even under high humidity. Specific examples of fluidity improvers include silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. Etc.
When the cleaning property improving agent is added to the toner, the transferred developer remaining on the photoreceptor or the primary transfer medium is easily removed. Specific examples of cleaning improvers include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, resin particles obtained using soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles. . The resin particles preferably have a narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 μm to 1 μm.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, and iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, a white magnetic material is preferable in terms of color tone.

<Toner production method>
As a method for producing the toner, an oil phase containing at least a binder resin and a colorant is suspended, emulsified and granulated in an aqueous medium.
As a method for producing a toner by the polymerization method, a method for forming toner base particles while producing an adhesive substrate is shown below. In such a method, preparation of an aqueous medium phase, preparation of a liquid containing a toner material, emulsification or dispersion of the toner material, formation of an adhesive substrate, removal of the solvent, a polymer having reactivity to active hydrogen groups And the synthesis of a compound having an active hydrogen group.

The aqueous medium can be prepared by dispersing the resin particles in the aqueous medium. The addition amount of the resin particles in the aqueous medium is preferably 0.5% by mass to 10% by mass.
Preparation of the liquid containing the toner material is carried out in a solvent such as a compound having an active hydrogen group, a polymer having reactivity with the active hydrogen group, a pigment, a release agent, a charge control agent, an unmodified polyester resin, etc. Can be dissolved or dispersed.
In the toner material, components other than the polymer having reactivity with the active hydrogen group may be added and mixed in the aqueous medium when the resin particles are dispersed in the aqueous medium, or the toner material contains the toner material. When the liquid is added to the aqueous medium, it may be added to the aqueous medium.

  The emulsification or dispersion of the toner material can be performed by dispersing a liquid containing the toner material in an aqueous medium. Then, when the toner material is emulsified or dispersed, an adhesive base is formed by subjecting a compound having an active hydrogen group and a polymer having reactivity to the active hydrogen group to an extension reaction and / or a crosslinking reaction.

  Adhesive substrates such as urea-modified polyester resins contain, for example, a liquid containing a polymer having reactivity with active hydrogen groups such as polyester prepolymers having isocyanate groups, and active hydrogen groups such as amines. It may be produced by emulsifying or dispersing together with a compound in an aqueous medium and subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium. It may be produced by emulsifying or dispersing in an added aqueous medium and by subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium, and after emulsifying or dispersing the liquid containing the toner material in the aqueous medium. Then, a compound having an active hydrogen group is added, and an extension reaction and / or a cross-linking reaction are performed on both from the particle interface in an aqueous medium. It may be. When both are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, a urea-modified polyester resin is preferentially formed on the surface of the toner to be produced, and a concentration gradient of the urea-modified polyester resin can be provided in the toner.

  The reaction conditions for producing the adhesive substrate can be appropriately selected according to the combination of the polymer having reactivity with active hydrogen groups and the compound having active hydrogen groups. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours. The reaction temperature is preferably 150 ° C. or lower, and more preferably 40 ° C. to 98 ° C.

  In a water-based medium, a method for stably forming a dispersion containing a polymer capable of reacting with an active hydrogen group such as a polyester prepolymer having an isocyanate group includes a reaction with an active hydrogen group in the aqueous medium phase. Examples include a method in which a liquid prepared by dissolving or dispersing a toner material such as a polymer, a pigment, a pigment dispersant, a release agent, a charge control agent, and an unmodified polyester resin in a solvent is added and dispersed by shearing force. It is done.

Dispersion can be performed using a known disperser, and examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, and an ultrasonic disperser. Although mentioned, since the particle diameter of a dispersion can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The number of rotations is preferably 1,000 to 30,000 rpm, and more preferably 5,000 to 20,000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 150 ° C. or less, more preferably 40 ° C. to 98 ° C. under pressure. The dispersion temperature is generally easier to disperse when the temperature is higher.

The amount of the aqueous medium used when emulsifying or dispersing the toner material is preferably 50 parts by mass to 2000 parts by mass, and more preferably 100 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the toner material. When the amount used is less than 50 parts by mass, the dispersion state of the toner material is deteriorated and toner base particles having a predetermined particle diameter may not be obtained. When the amount exceeds 2000 parts by mass, the production cost is high. May be.
In the step of emulsifying or dispersing the liquid containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets so as to obtain a desired shape and sharpening the particle size distribution.

The dispersant can be appropriately selected according to the purpose, and examples thereof include a surfactant, a sparingly water-soluble inorganic compound dispersant, a polymeric protective colloid, and the like, but a surfactant is preferable. These may be used individually by 1 type and may use 2 or more types together.
As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be used.

Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferably used. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, perfluorooctanesulfonyl glutamate disodium, 3- [ω-fluoroalkyl (C6 to C11). Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid Or a metal salt thereof, perfluoroalkylcarboxylic acid (C7 to C13) or a metal salt thereof, perfluoroalkyl (C4 to C12) sulfonic acid or a metal salt thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) perfluoroocta Sulfonamides, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salts, monoperfluoroalkyl (C6-C16) ethyl phosphate, and the like. It is done.
Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (above, manufactured by Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC. -129 (manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (above, manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products) 100, 150 (above, manufactured by Neos), and the like.

  Examples of the cationic surfactant include amine salt type surfactants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, Quaternary ammonium salt type surfactants such as pyridinium salts, alkylisoquinolinium salts, benzethonium chloride and the like can be mentioned. Among these, aliphatic primary, secondary or tertiary amino acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzalkonium salts, chlorides Benzethonium, pyridinium salts, imidazolinium salts and the like are preferable. Commercially available cationic surfactants include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M); Unidyne DS-202 (manufactured by Daikin Industries Ltd.), MegaFuck F-150, It is preferable to use F-824 (manufactured by Dainippon Ink); Xtop EF-132 (manufactured by Tochem Products);

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

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include, for example, a monomer having a carboxyl group, an alkyl (meth) acrylate having a hydroxyl group, a vinyl ether, a vinyl carboxylate, an amide monomer, an acid chloride monomer, a monomer having a nitrogen atom or a heterocyclic ring thereof, etc. Homopolymers or copolymers obtained by polymerizing styrene, polyoxyethylene resins, celluloses and the like. In addition, the homopolymer or copolymer obtained by polymerizing the above monomers includes those having a structural unit derived from vinyl alcohol.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-hydroxy acrylate. Propyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. It is done. Specific examples of the vinyl ether include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate and the like. Examples of the amide monomer include acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide, and the like. Examples of the acid chloride monomer include acrylic acid chloride and methacrylic acid chloride. Examples of the monomer having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethyleneimine. Examples of the polyoxyethylene resin include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples include ethylene lauryl phenyl ether, polyoxyethylene stearate phenyl, polyoxyethylene pelargonate phenyl, and the like. Examples of celluloses include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

  Examples of the dispersant include acids such as calcium phosphate salts and those soluble in alkali. When calcium phosphate is used as the dispersant, the calcium phosphate salt can be removed by dissolving the calcium salt with hydrochloric acid or the like and washing it with water or decomposing with an enzyme.

  A catalyst can be used for the elongation reaction and / or the crosslinking reaction in producing the adhesive substrate. Specific examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  As a method for removing the organic solvent from the dispersion liquid such as an emulsified slurry, the temperature of the entire reaction system is gradually raised to evaporate the organic solvent in the oil droplets, and the dispersion liquid is sprayed in a dry atmosphere to obtain the oil. Examples include a method of removing the organic solvent in the droplets.

  When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. Classification may be performed by removing fine particle portions by a cyclone, decanter, centrifugation, or the like in the liquid, or classification may be performed after drying.

The obtained toner base particles may be mixed with particles such as a colorant, a release agent, and a charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent particles such as a release agent from detaching from the surface of the toner base particles.
As a method of applying mechanical impact force, a method of applying impact force to a mixture using a blade rotating at a high speed, throwing the mixture into a high-speed air current, and accelerating the particles or particles to an appropriate collision plate The method of making it collide etc. is mentioned. As an apparatus used for this method, an ong mill (manufactured by Hosokawa Micron Corporation), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, a hybridization system (manufactured by Nara Machinery Co., Ltd.), Examples include a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), an automatic mortar, and the like.

  The toner of the present invention can be used in various fields, but can be suitably used for image formation by electrophotography.

The average circularity of the toner of the present invention is 0.955 to 0.975, preferably 0.960 to 0.970.
The content of particles having a circularity of less than 0.955 in the toner is preferably 15% or less. When the average circularity is less than 0.955, a satisfactory transferability and a high-quality image free from dust may not be obtained. When the average circularity exceeds 0.975, an image forming apparatus employing blade cleaning or the like may be used. In addition, poor cleaning of the photosensitive member and the transfer belt may occur, and stains on the image may occur.
For example, when forming an image with a high image area ratio, such as a photographic image, toner that has formed an untransferred image due to poor paper feed or the like accumulates on the photoconductor, causing image smudges or touching the photoconductor The charging roller or the like to be charged may be contaminated and the original charging ability may not be exhibited.
The circularity is a value obtained by dividing the circumference of a circle having an area equal to the projected area of the sample by the circumference of the sample.

  The volume average particle size of the toner of the present invention is preferably 3 μm to 8 μm, more preferably 4 μm to 7 μm. When the volume average particle diameter is less than 3 μm or more, in the two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In the case of a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may occur. On the other hand, if the volume average particle size exceeds 8 μm or less, it becomes difficult to obtain a high-resolution and high-quality image, and the toner balance in the developer becomes difficult. The particle size variation may increase.

  The ratio of the volume average particle diameter to the number average particle diameter of the toner of the present invention is preferably 1.00 to 1.25, and more preferably 1.05 to 1.25. As a result, in the two-component developer, even if the toner balance for a long period of time is performed, the toner particle diameter in the developer is little changed, and good and stable developability can be obtained even in the case of long-term stirring in the developing device. . In the case of a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner filming on the developing roller and the toner on a member such as a blade for thinning the toner Therefore, even when the developing device is used (stirred) for a long time, good and stable developability can be obtained, so that a high-quality image can be obtained. When this ratio exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle diameter may increase. is there.

  Here, the ratio of the volume average particle diameter to the volume average particle diameter and the number average particle diameter can be measured as follows using a particle size measuring device Multisizer III (manufactured by Beckman Coulter, Inc.). First, 0.1 to 5 ml of a surfactant such as an alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of an electrolyte aqueous solution such as an approximately 1% by mass sodium chloride aqueous solution. Next, about 2 to 20 mg of a measurement sample is added. The aqueous electrolyte solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and then the volume and number of toners are measured using a 100 μm aperture to determine the volume distribution and number distribution. calculate. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.

The penetration of toner is preferably 15 mm or more, and more preferably 20 mm to 30 mm. When the penetration is less than 15 mm, the heat resistant storage stability is deteriorated.
Here, the penetration can be measured by a penetration test (JIS K2235-1991). Specifically, the toner is filled in a 50 ml glass container and left in a thermostat at 50 ° C. for 20 hours, and then the toner is cooled to room temperature and a penetration test is performed. In addition, it has shown that heat resistance preservability is excellent, so that the value of penetration is large.

The toner of the present invention preferably has a low fixing minimum temperature and a high offset non-occurrence temperature from the viewpoint of achieving both low-temperature fixability and offset resistance. For this purpose, it is preferable that the lower limit fixing temperature is less than 140 ° C. and the temperature at which no offset occurs is 200 ° C. or more. Here, the lower limit fixing temperature is the lower limit of the fixing temperature at which the residual ratio of the image density after a copy test using an image forming apparatus and rubbing the obtained image with a pad is 70% or more. The offset non-occurrence temperature can be obtained by measuring a temperature at which no offset occurs using an image forming apparatus adjusted to be developed with a predetermined amount of toner.
The thermal characteristics of the toner, also called flow tester characteristics, are evaluated as a softening temperature, an outflow start temperature, a 1/2 method softening point, and the like. These thermal characteristics can be measured by an appropriately selected method, and can be measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).

The softening temperature of the toner is preferably 30 ° C. or higher, and more preferably 50 ° C. to 90 ° C. When the softening temperature is less than 30 ° C., the heat resistant storage stability may be deteriorated.
The outflow start temperature of the toner of the present invention is preferably 60 ° C. or higher, and more preferably 80 ° C. to 120 ° C. When the outflow start temperature is less than 60 ° C., at least one of heat resistant storage stability and offset resistance may be deteriorated.
The 1/2 method softening point of the toner of the present invention is preferably 90 ° C. or higher, and more preferably 100 ° C. to 170 ° C. When the 1/2 method softening point is less than 90 ° C., the offset resistance may be deteriorated.

The glass transition temperature of the toner of the present invention is preferably 40 ° C to 70 ° C, and more preferably 45 ° C to 65 ° C. If the glass transition temperature is less than 40 ° C. or higher, the heat-resistant storage stability of the toner is good and does not deteriorate, and if it exceeds 70 ° C., the low-temperature fixability may not be sufficient. The glass transition temperature can be measured using a differential scanning calorimeter DSC-60 (manufactured by Shimadzu Corporation).
The density of an image formed using the toner of the present invention is preferably 1.40 or more, more preferably 1.45 or more, and even more preferably 1.50 or more. If the image density is less than 1.40, the image density may be low and high image quality may not be obtained. The image density was determined by using a tandem color image forming apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.), setting the surface temperature of the fixing roller to 160 ± 2 ° C., and developing the copy paper type 6200 (produced by Ricoh Co., Ltd.) A solid image having an adhesion amount of 0.35 ± 0.02 mg / cm ² was formed, and the image density at any five positions in the obtained solid image was measured using a spectrometer 938 spectrodensitometer (manufactured by X-Light Corporation). ), And the average value can be calculated.
The color of the toner of the present invention can be appropriately selected according to the purpose, and can be one or more selected from the group consisting of black toner, cyan toner, magenta toner, and yellow toner. It can be obtained by appropriately selecting a colorant.

<Developer>
The developer of the present invention contains the toner of the present invention and may further contain other components appropriately selected such as a carrier. For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.

  When the developer of the present invention is used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, the blade for thinning the toner, etc. Therefore, good and stable developability and images can be obtained even with long-term stirring in the developing device.

When the developer of the present invention is used as a two-component developer, even if the toner balance is maintained over a long period of time, there is little fluctuation in the particle diameter of the toner. An image is obtained.
Although the said carrier can be suitably selected according to the objective, what has a core material and the resin layer which coat | covers a core material is preferable.

The material of the core material can be appropriately selected from known materials, and examples include manganese-strontium-based materials and manganese-magnesium-based materials of 50 emu / g to 90 emu / g. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g. In addition, it is preferable to use a low-magnetization material such as 30-80 emu / g of copper-zinc system because it can reduce the impact of the developer in a spiked state on the photoconductor and is advantageous for high image quality. . These may be used alone or in combination of two or more.
The volume average particle diameter of the core material is preferably 10 μm to 150 μm, and more preferably 40 μm to 100 μm. When the volume average particle diameter is less than 10 μm, fine powder increases in the carrier, magnetization per particle may decrease and carrier scattering may occur, and when it exceeds 150 μm, the specific surface area decreases, Toner scattering may occur, and in the case of full color with many solid portions, reproduction of the solid portions may be deteriorated.
The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, polyhalogenated olefins, polyester resins Resin, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetra Examples include fluoroterpolymers such as copolymers of fluoroethylene, vinylidene fluoride, and monomers having no fluoro group, silicone resins, and the like. These may be used individually by 1 type and may use 2 or more types together.
Specific examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Specific examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. Specific examples of the polystyrene-based resin include polystyrene and styrene-acrylic copolymer. Specific examples of the polyhalogenated olefin include polyvinyl chloride. Specific examples of the polyester-based resin include polyethylene terephthalate and polybutylene terephthalate.

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

  The resin layer is formed by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then coating and drying the coating solution on the surface of the core using a known coating method, followed by baking. Can do. As a coating method, a dip coating method, a spray method, a brush coating method, or the like can be used. There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, butyl cellosolve etc. are mentioned. The baking may be an external heating method or an internal heating method, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, a method using a microwave, or the like. Is mentioned.

The content of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass. When the content is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. When the content exceeds 5.0% by mass, the resin layer is thick and the carrier Fusion may occur between them, and the uniformity of the carrier may decrease.
The content of the carrier in the two-component developer is preferably 90% by mass to 98% by mass, and more preferably 93% by mass to 97% by mass.

  The developer of the present invention can be 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.

The image forming apparatus includes a toner transfer step for transferring toner from a toner cartridge to a developing unit, a charging step for uniformly charging an image forming area on the surface of the image carrier, an exposure step for writing on the image carrier, The image is fixed on the printing paper after the development process for forming the image with the toner charged with friction, the transfer process for transferring the image on the image carrier directly to the printing paper or indirectly via the intermediate transfer body. The untransferred toner remaining without being transferred onto the image carrier is scraped off from the image carrier by the cleaning process and enters the next image forming process.

  The image forming apparatus of the present invention can be used for either a one-component development method or a two-component development method. When the two-component method is adopted, the toner density and the like in the developing device are detected by detecting the toner density and the like. The mixing ratio is controlled to be constant. Therefore, a toner container such as a toner bottle or a cartridge is provided in or near the unit having the developing device, and the toner is transferred from the toner container to the developing device according to the amount consumed by use. Yes.

  FIG. 1 shows a schematic diagram of a toner transfer device. The toner transfer device replenishes the developing device (1) with toner, and includes a toner storage container (3) storing toner, a means for carrying out the toner stored in the toner storage means, and a developing device. (1) It has a means to move and these means are equipped with the powder pump means (2) as a suction means. This powder pump means (2) serves both as a suction means for carrying out the toner from the toner storage container (3) and a suction means for moving the toner carried out of the container to the developing device.

FIG. 2 is a sectional view of the powder pump means (2). The powder pump means (2) has a suction type uniaxial eccentric powder pump (4) called a conventionally known Mono pump. . The configuration of the powder pump (4) was made in the shape of a screw (screw) eccentric in the shape of a screw with a rigid material such as metal, and in the shape of a double screw made of an elastic body such as rubber. The stator (6) has a holder (7) made of a resin material or the like that wraps these and forms a powder conveyance path. The stator (6) is fixedly installed on the holder (7). The rotor (5) is rotationally driven through a gear (8) and a joint (9) connected to a drive source.
In the powder pump (4) configured in this way, when the rotor (5) is rotated, a strong self-suction force is generated in the pump, and the toner is sucked from the suction portion at the tip of the holder (7), and the sucked toner is removed. It becomes possible to feed out from the discharge part in the vicinity of the shaft joint (9). Further, air is supplied to the powder pump means (2) from an air pump pipe (not shown), fluidization of the toner sent out by the air is promoted, and toner transfer is ensured by the powder pump (4). It becomes. The suction type powder pump (4) is actuated by transmitting the drive to the gear through a dedicated motor or a main motor and a clutch in the image forming apparatus, and the drive is controlled.

  This pump is simple in structure and small in size, and basically transports toner as an air-fuel mixture. Therefore, unlike a pump or a mechanical auger means such as a paddle, the pump itself is not loaded, Although it is said that the toner is not deteriorated by the transfer, even with this suction-type powder pump, the occurrence of loose agglomerates is inevitable.

The toner agglomerates formed here are crushed with a certain degree of history and return to the normal toner powder state, but are completely crushed in the history of each step of image formation. Therefore, the image is transferred to the final fixing medium, and a solid image (single color, toner adhesion amount of 0.45 mg / cm ² ) or the like is formed with a dark color point compared with the solid image ID, and a light color gamut is formed around the periphery. An abnormal image to be formed (hereinafter referred to as “firefly”) occurs.
If the loose agglomerate is an agglomerate having a size of less than 0.2 mm, the fireflies on the image will not be noticeable, but if the size is 0.2 mm or more, it will be noticeable and uncomfortable on the image. give.
Therefore, it is necessary to use a toner that does not generate loose aggregates even if it is transferred by a suction type powder pump. If the amount of aggregates in 20 g of the developer after the transfer step is 10 mg or less, the diameter is 0. It was found that fireflies of 2 mm or more were not generated.

<Image forming apparatus>
3 is a block diagram showing a color printer as an image forming apparatus, FIG. 4 is a cross-sectional view showing the vicinity of the image forming unit, and FIG. 5 is a cross-sectional view showing a toner conveyance path.

As shown in FIG. 3, the toner container housing part (31) located above the image forming apparatus main body (100) has four toner containers (32Y, 32M,...) Corresponding to each color (yellow, magenta, cyan, black). 32C, 32K) are detachably installed.
An intermediate transfer unit (15) is disposed obliquely below the toner container housing (31). Image forming portions (6Y, 6M, 6C, 6K) corresponding to the respective colors (yellow, magenta, cyan, black) are arranged in an oblique direction so as to face the intermediate transfer belt (8) of the intermediate transfer unit (15). It is installed.

As shown in FIG. 4, the image forming section (6Y) corresponding to yellow includes a photosensitive drum (1Y) as an image carrier and a charging section (4Y) disposed around the photosensitive drum (1Y). , A developing unit (5Y), a cleaning unit (2Y), a charge eliminating unit (not shown), and the like.
Then, an image forming process (charging process, exposure process, developing process, transfer process, cleaning process) is performed on the photosensitive drum (1Y), and a yellow image is formed on the photosensitive drum (1Y). become.
Here, the developing section (5Y) of the image forming section (6Y) is connected to a MONO pump (40Y) as a powder pump, and the yellow toner contained in the toner container (32Y) passes through the MONO pump (40Y). The developing unit (5Y) is appropriately replenished.
The other three image forming units (6M, 6C, 6K) have substantially the same configuration as the image forming unit (6Y) corresponding to yellow except that the color of the toner used is different. The color toner is replenished to form an image corresponding to the toner color.

Hereinafter, description of the other three image forming units (6M, 6C, 6K) will be omitted as appropriate, and an image forming unit (6Y) corresponding to yellow will be described as an example.
As shown in FIG. 4, the photosensitive drum (1Y) is rotationally driven in a clockwise direction in FIG. 4 by a drive motor (not shown), and the surface of the photosensitive drum (1Y) is positioned at the charging portion (4Y). The surface of the photosensitive drum (1Y), which is uniformly charged, reaches the irradiation position of the laser beam L emitted from the exposure device (7), and the electrostatic latent image corresponding to yellow by exposure scanning at this position. Is formed.
Thereafter, the surface of the photosensitive drum (1Y) reaches a position facing the developing device (5Y), and the electrostatic latent image is developed at this position to form a yellow toner image.
The surface of the photosensitive drum (1Y) on which the toner image is formed reaches a position opposed to the intermediate transfer belt (8) and the first transfer bias roller (9Y), and at this position on the photosensitive drum (1Y). The toner image is transferred onto the intermediate transfer belt (8) (this is a primary transfer step).
At this time, a small amount of untransferred toner remains on the photosensitive drum (1Y), but the surface of the photosensitive drum (1Y) reaches a position facing the cleaning unit (2Y), and the photosensitive drum (1Y) ) Untransferred toner remaining thereon is collected (this is a cleaning process).
Finally, the surface of the photoconductor drum (1Y) reaches a position facing a neutralization unit (not shown), and the residual potential on the photoconductor drum (1Y) is removed at this position.
Thus, a series of image forming processes performed on the photosensitive drum (1Y) is completed. The image forming process described above is performed in the other image forming units (6M, 6C, 6K) in the same manner as the yellow image forming unit 6Y.

That is, a laser beam L based on image information is emitted from the exposure unit (7) disposed below the image forming unit onto the photosensitive drum of each image forming unit (6M, 6C, 6K). The
Specifically, the exposure unit (7) emits a laser beam L from a light source, and irradiates the photosensitive drum via a plurality of optical elements while scanning the laser beam L with a polygon mirror that is rotationally driven.
Thereafter, the toner images of the respective colors formed on the respective photosensitive drums through the development process are transferred onto the intermediate transfer belt (8) so as to form a color image on the intermediate transfer belt (8).

Here, the intermediate transfer unit (15) includes an intermediate transfer belt (8), four primary transfer bias rollers (9Y, 9M, 9C, 9K), a secondary transfer backup roller (12), and a cleaning backup roller (13). , A tension roller (14), an intermediate transfer cleaning unit (10), and the like.
The intermediate transfer belt (8) is stretched and supported by three rollers (12 to 14) and is endlessly moved in the direction of the arrow in FIG. 3 by the rotational drive of one roller (12).
Each of the four primary transfer bias rollers (9Y, 9M, 9C, 9K) sandwiches the intermediate transfer belt (8) between the photosensitive drums (1Y, 1M, 1C, 1K) to form a primary transfer nip. Forming.
Then, a transfer bias opposite to the toner polarity is applied to the primary transfer bias rollers (9Y, 9M, 9C, and 9K), and the intermediate transfer belt (8) travels in the direction of the arrow to each primary transfer. It sequentially passes through the primary transfer nip of the bias roller (9Y, 9M, 9C, 9K).
In this way, the toner images of the respective colors on the photosensitive drums (1Y, 1M, 1C, 1K) are primarily transferred on the intermediate transfer belt (8), and the intermediate transfer belt on which the toner images of the respective colors are transferred. (8) reaches the position facing the secondary transfer roller (19). At this position, the secondary transfer backup roller (12) sandwiches the intermediate transfer belt (8) with the secondary transfer roller (19) to form a secondary transfer nip.
The four-color toner images formed on the intermediate transfer belt (8) are transferred onto a transfer material P such as transfer paper conveyed to the position of the secondary transfer nip. At this time, the intermediate transfer belt In (8), untransferred toner that has not been transferred to the transfer material P remains, but the intermediate transfer belt (8) reaches the position of the intermediate transfer cleaning section (10), and at this position, the intermediate transfer belt is reached. (8) The upper untransferred toner is collected.
Thus, a series of transfer processes performed on the intermediate transfer belt (8) is completed.

Here, the transfer material P transported to the position of the secondary transfer nip is fed from a paper feed unit (26) disposed below the apparatus main body (100) to a paper feed roller (27) or a pair of registration rollers ( 28) etc.
Specifically, a plurality of transfer materials P such as transfer paper are stored in the paper supply unit (26) in a stacked manner.
When the paper feed roller (27) is rotationally driven in the counterclockwise direction in FIG. 3, the uppermost transfer material P is fed between the rollers of the registration roller pair (28).
The transfer material P conveyed to the registration roller pair (28) is temporarily stopped at the position of the roller nip of the registration roller pair (28) whose rotation driving is stopped, and the timing is adjusted to the color image on the intermediate transfer belt (8). Thus, the registration roller pair (28) is driven to rotate, and the transfer material P is conveyed toward the secondary transfer nip.
In this way, the desired color image is transferred onto the transfer material P, and the transfer material P on which the color image is transferred at the position of the secondary transfer nip is conveyed to the position of the fixing unit (20), and the fixing roller and The color image transferred to the surface is fixed on the transfer material P by the heat and pressure of the pressure roller, and the transfer material P is discharged outside the apparatus through the rollers of the discharge roller pair (29). Is done.
The transferred P discharged from the apparatus by the discharge roller pair (29) is sequentially stacked on the stack unit (30) as an output image.
Thus, a series of image forming processes in the image forming apparatus is completed.

Next, the configuration and operation of the developing unit in the image forming unit will be described in more detail with reference to FIG.
The developing section (5Y) is arranged in a developing roller (51Y) facing the photosensitive drum (1Y), a doctor blade (52Y) facing the developing roller (51Y), and a developer accommodating section (53Y, 54Y). The two conveying screws (55Y) provided, a toner concentration sensor (56Y) for detecting the toner concentration in the developer, and the like.
The developing roller (51Y) includes a magnet fixed inside, a sleeve rotating around the magnet, and the like.
In the developer accommodating portions (53Y, 54Y), a two-component developer G composed of a carrier and toner is accommodated.
The developer accommodating portion (54Y) of the developing portion (5Y) communicates with the mono pump (40Y) through the opening.
The developing unit (5Y) configured as described above operates as follows.
The sleeve of the developing roller (51Y) rotates in the direction of the arrow in FIG.
The developer G carried on the developing roller (51Y) by the magnetic field formed by the magnet moves on the developing roller (51Y) as the sleeve rotates.
Here, the developer G in the developing portion (5Y) is adjusted so that the ratio of toner in the developer (toner concentration) falls within a predetermined range.
Specifically, according to the consumption of toner in the developing unit (5Y), the toner contained in the toner container (32Y) is transferred to the developer containing unit via the tube (49Y) or the mono pump (40Y) serving as a toner conveyance path. The toner replenished in (54Y) and replenished in the developer accommodating portion (54Y) is mixed and stirred together with the developer G by the two conveying screws (55Y), and the two developer accommodating portions (53Y). , 54Y) (the movement in the direction perpendicular to the paper surface of FIG. 4).
The toner in the developer G is attracted to the carrier by frictional charging with the carrier, and is carried on the developing roller (51Y) together with the carrier by the magnetic force formed on the developing roller (51Y). The developer is conveyed in the direction of the arrow and the developer amount is adjusted to an appropriate amount at the position of the doctor blade (52Y), and then conveyed to the position facing the photosensitive drum (1Y) (development area).
The toner is attracted to the latent image formed on the photosensitive drum (1Y) by the electric field formed in the developing region, and the developer G remaining on the developing roller (51Y) is developed as the sleeve rotates. It reaches above the storage portion (53Y) and is detached from the developing roller (51Y) at this position.

Next, a toner replenishing unit (a toner container (32Y), a tube (49Y), and a Mono pump (40Y)) that supplies toner to the developing unit (5Y) will be described.
As described above with reference to FIG. 3, four toner containers (32Y, 32M, 32C, 32K) are detachably installed in the toner container housing portion (31).
The toner containers (32Y, 32M, 32C, 32K) are respectively replaced with new ones when they reach the end of their lives (when almost all the toner to be stored is consumed and emptied). The toner of each color stored in the toner container (32Y, 32M, 32C, 32K) is appropriately supplied to the developing unit of each image forming unit (6Y, 6M, 6C, 6K) via a tube and a mono pump. To be replenished.
As shown in FIG. 5, the toner container (32Y) is provided with a bag-like container main body and a base having an opening as a toner discharge portion, and the toner accommodated therein is discharged from the opening.
Specifically, when the opening of the new toner container (32Y) engages with the nozzle (34Y) attached to the tip of the tube (49Y), the toner container (32Y) and the nozzle (34Y) communicate with each other, and the MONO pump The toner can be sucked by (40Y).
Here, an intake port (33Y) covered with a toner filter is provided above the toner container (32Y) (above in the installed state), and through this intake port (33Y), Air is periodically sent from the outside toward the inside of the toner container (32Y) by an unillustrated intake means (such as a fan).
As a result, aggregation of the toner in the toner container (32Y) is suppressed, and a decrease in the internal pressure of the toner container (32Y) is suppressed, so that stable toner supply from the toner container (32Y) to the developing unit (5Y) is achieved. Is possible.
As shown in FIG. 5, one end of a tube (49Y) made of a flexible rubber material such as silicon rubber is connected to the nozzle (34Y) to which the toner container (32Y) is connected, as shown in FIGS. As described above, one end of the MONO pump (40Y) is connected to the other end of the tube (49Y).
Further, as shown in FIG. 4, the developer accommodating portion (54Y) of the developing portion (5Y) is connected to the other end of the MONO pump (40Y).
The mono pump (40Y) includes a rotor (42Y), a stator (43Y), a suction port (41Y), a rotor drive shaft (44Y), a drive gear (45Y), a motor (46Y), and the like. The rotor (42Y) is formed such that a shaft made of a metal material is twisted spirally.
One end of the rotor (42Y) is rotatably connected to a motor (46Y) via a rotor drive shaft (44Y) and a drive gear (45Y).
The stator (43Y) is made of a rubber material, and its hole is formed such that an oval cross section is spirally twisted, and the rotor (42Y) is inserted into the hole of the stator (43Y). .

The MONO pump (40Y) configured in this manner causes the motor (46Y) to rotationally drive the rotor (42Y) in the stator (43Y) in a predetermined direction, so that the toner in the toner container (32Y) is transferred to the tube (49Y). To the suction port (41Y).
The toner sucked up to the suction port (41Y) is fed into the gap between the stator (43Y) and the rotor (42Y), and is sent to the other end along the rotation of the rotor (42Y).
The delivered toner is discharged from the delivery port of the mono pump (40Y) and replenished into the developer accommodating portion (54Y) of the developing portion (5Y).
The toner replenished to the developer accommodating portion (54Y) is mixed and stirred with the two-component developer G in the developing portion (5Y).
Here, as described above with reference to FIG. 3, the four image forming units (6Y, 6M, 6C, and 6K) are arranged in parallel in an oblique direction.
That is, the four developing units (5Y, 5M, 5C, and 5K) are disposed at positions having different heights in the vertical direction (the vertical direction in FIG. 3).
In the developing units (5Y, 5M, 5C, 5K) arranged in this way, the positional relationship between the toner container and the Mono pump is equalized.
Specifically, as shown in FIG. 5, the vertical length H (height) from the toner discharge portion (opening) of the toner container (32Y) to the mono pump (40Y) is configured to be equivalent to each color. ing.
Further, the horizontal length L from the toner discharge portion of the toner container (32Y) to the mono pump (40Y) is configured to be equivalent to each color.

(Process cartridge)
The process cartridge of the present invention can be mounted on an image forming apparatus. An electrostatic latent image carrier that carries an electrostatic latent image, and an electrostatic latent image carried on the electrostatic latent image carrier, A developing unit that develops a visible image by developing using a developer, and further, a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit, which are appropriately selected as necessary. It has other means such as.
The developing means includes a developer container that contains the toner or developer of the present invention, and an electrostatic latent image carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.

  The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, facsimiles, and printers, and is preferably provided detachably in the image forming apparatus.

Here, for example, as shown in FIG. 6, the process cartridge includes a photosensitive member (101), and further includes a charging unit (102), a developing unit (104), and a cleaning unit (107). Depending on the case, it has other members. The process cartridge example of FIG. 6 has a transfer means (108) for transferring the toner image on the developed photoreceptor (101) to the image receiving paper (105).
As the photoreceptor (101), a known one can be used.
A light source capable of writing with high resolution is used for the exposure means (103).
An arbitrary charging member is used for the charging means (102).

Examples of the present invention will be described below, but the present invention is not limited to the following examples. In Examples, “part” and “%” in each example are based on mass, and “mol” means molar ratio.
First, methods for measuring various physical properties and the like of the materials used in Examples and Comparative Examples and the obtained toner will be described.

<Measurement of amount of residual amine in toner>
The tertiary amine compound in the toner is measured by adding 1 g of toner to 100 g of dimethyl sulfoxide, dissolving or dispersing with an ultrasonic disperser for 30 minutes, and then removing solids with a 0.45 μm PTFE membrane filter. The tertiary amine compound in the solution was extracted at a temperature of 190.degree. C. for 10 minutes with a cryotrap; -190.degree. C. (N2 Liq), and extracted with a GC / MS spectrometer (M-80B manufactured by Hitachi, Ltd.). analyzed. The column used was Ultra ALLOY-5 L = 30 m ID = 0.25 mm Film = 0.25 μm (manufactured by Frontier Labs), column heating condition: 50 ° C. (holding 1 min) to 5 ° C./min to 80 ° C. to 40 ° C. / It was performed at min to 280 ° C. (holding 5 minutes).

<Measurement of weight loss of wax at 165 ° C.>
The measurement of the weight loss at 165 ° C. in the present invention is specifically determined by the following procedure. Shimadzu TA-60WS and DTG-60 were used as measurement devices, and the measurement was performed under the following measurement conditions.

Measurement conditions Sample container: Aluminum sample pan Sample amount: 5 mg
Reference: Aluminum sample pan (sample pan only)
Atmosphere: Nitrogen (flow rate 50ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 165 ° C
Retention time: 60 minutes

The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation.
The weight loss analysis method at 165 ° C. is calculated by the following equation, where A is the weight at 165 ° C. for 0 minutes, and B is the weight after holding for 60 minutes.
Weight loss at 165 ° C. = (A−B) / A × 100

<Measurement of average circularity of toner>
The average circularity is represented by the circumference of a circle having the same area as the projected area of the particle / the circumference of the projected image of the particle, and the suspension containing the toner is passed through the imaging unit detection zone on the flat plate, and the CCD camera. The particle image can be measured by an optical detection band method for optically detecting and analyzing the particle image using a flow type particle image analyzer FPIA-3000 (manufactured by Sysmex Corporation).

<Measurement of mass average molecular weight of resin>
Gel permeation chromatography (GPC) measuring device: GPC-8220 GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-H 15cm triple (manufactured by Tosoh Corporation)
Temperature: 40 ° C
Solvent: THF
Flow rate: 0.35 ml / min
Sample: 0.4 ml of 0.15% sample was injected Sample pretreatment: Toner was dissolved in tetrahydrofuran THF (containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15%, and then filtered through a 0.2 μm filter. The filtrate is used as a sample. 100 μl of the THF sample solution is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.
As a standard polystyrene sample for preparing a calibration curve, Showd STANDARD Std. No. S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, and toluene were used.
An RI (refractive index) detector was used as the detector.

<THF insoluble matter measurement>
The THF-insoluble matter can be specified by the measurement method shown below.
About 1.0 g (A) of toner is weighed.
To this, about 50 g of THF (tetrahydrofuran) is added and allowed to stand at 20 ° C. for 24 hours.
This is first separated by centrifugation and filtered using a quantitative filter paper.
The solvent content of this filtrate is vacuum-dried, and the residual amount (B) is measured only for the resin content.
This residual amount is the amount dissolved in THF.
The THF insoluble content (%) is obtained from the following formula.
THF insoluble matter (%) = [(A−B) / A] × 100

<Average particle diameter of toner>
The volume average particle diameter (Dv), number average particle diameter (Dn), and Dv / Dn of the toner are measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm, and analyzed software The analysis was performed with (Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10% surfactant (alkylbenzene sulfonate Neogen SC-A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml beaker made of glass, and 0.5 g of each toner is added. Stir and then add 80 ml of ion exchanged water. The obtained dispersion was subjected to dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II; manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

<Measurement of glass transition temperature and melting point>
The glass transition point (Tg) and melting point in the present invention are specifically determined by the following procedure. Using Shimadzu TA-60WS and DSC-60 as measuring devices, the measurement was performed under the following measurement conditions.
(Measurement condition)
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation.
The glass transition temperature is analyzed using the peak analysis function of the analysis software by specifying a range of ± 5 ° C around the point showing the maximum peak on the lowest temperature side of the DrDSC curve which is the DSC differential curve of the second temperature increase. To obtain the peak temperature. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the Tg of the toner.
The melting point is analyzed using the peak analysis function of the analysis software, specifying a range of ± 5 ° C around the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the second temperature increase. Find the temperature. The temperature shown here corresponds to the melting point.
The method of distinguishing the glass transition point and the melting point is the glass transition point when the DSC curve does not return to the exothermic direction in the DSC curve, and the melting point when the DSC curve after the endotherm returns to the DSC curve (baseline) before the endotherm. it can.

<Fixing characteristics>
The fixing property of the toner was evaluated as follows. Was evaluated by Ricoh Co. imagio Neo 450 in modified machine equipped with a belt heat fixing device shown in FIG. The base of the belt is 100 μm polyimide, the intermediate elastic layer is 100 μm silicon rubber, the surface offset prevention layer is 15 μm PFA, the fixing roller is silicon foam, the pressure roller metal cylinder is SUS, and the thickness is 1 mm. The pressure roller offset prevention layer was made of PFA tube + silicon rubber with a thickness of 2 mm, the heating roller with a thickness of 2 mm, and a surface pressure of 1 × 10 ⁵ Pa.
The criteria for each characteristic evaluation are as follows.
(Low temperature fixability-5-level evaluation)
A: Less than 110 ° C. O: 110-120 ° C. □; 120-130 ° C. (Triangle | delta); 130-140 degreeC. ×: 140 ° C or higher

<Heat resistant storage stability>
Weigh 10 g of toner, put it in a 20 ml glass container, tap the glass bottle 150 times, leave it in a thermostatic chamber set at a temperature of 55 ° C. and a humidity of 80% for 24 hours, and then check the penetration with a penetration meter. It was measured. The toner stored in a low-temperature and low-humidity (10 ° C., 15%) environment was similarly evaluated for penetration, and the value with the lower penetration was employed in a high-temperature and high-humidity and low-temperature and low-humidity environment. From the good one, ◎: 20 mm or more, ◯: 15 mm or more and less than 20 mm, Δ: 10 mm or more to less than 15 mm, x: less than 10 mm.

<Cleaning evaluation>
After printing 10,000 sheets of solid images using RICOH imagio MP C 455, printing was stopped during printing one sheet of solid images, and the transfer residual toner on the photoconductor passed through the cleaning process was scotch tape (Sumitomo 3M) Made with a Macbeth reflection densitometer RD514, and the difference between the blank (the density of the scotch tape pasted on the white paper) and 0 to 0.01 is ◎ (good), 0. The evaluation was evaluated as O for 02 to 0.05, Δ for 0.06 to 0.1, and X (defect) for exceeding.

<Backside of printing paper>
A solid black image was created using IMAGIO Neo 450 manufactured by Ricoh, a white solid image was output after outputting 1 million images, and the back stain of the printing paper was evaluated.
5: No back dirt, 4 ... Between 3 and 5, 3 ... Some dirt is seen, 2 ... Between 1 and 3, 1 ... It is recognized that there is clearly back dirt.

<Measurement of amount of toner aggregate after toner transfer step>
All the toner and equipment used in the aggregate amount measurement and evaluation (Ricoh's imagio MP C 455) are left in the environment room at 25 ° C. and 50% for 1 day, and then the toner moves from the toner replenishing device of the image forming apparatus main body to the developing device ( A jig capable of collecting the toner is mounted between the pump outlet and the developing device inlet, and only the toner replenishing device is operated to collect 20 g of toner. The collected toner was sieved with a 106 μm mesh, and the amount of aggregate remaining on the sieve was measured.
A: 0 mg, ◯: 10 mg, Δ: -20 mg, x: 20 mg or more.

<Firefly image evaluation>
All the toner and device used for image evaluation (Ricoh's imagio MP C 455) are left in an environmental chamber at 25 ° C. and 50% for 1 day, and then the developing device is attached to the main body of the image forming apparatus. Allow only the developing device to idle for 5 minutes. Both the developing sleeve and the photosensitive member were rotated by trailing at a target linear velocity, and the charging potential and the developing bias were adjusted so that the toner on the photosensitive member was 0.4 ± 0.05 mg / cm ² . Under the above development conditions, after adjusting the transfer current so that the transfer rate is 96 ± 2%, 50 continuous solid images are output continuously, the number of fireflies in the full solid image is counted, and per A4 copy paper The average value of was calculated.
A: No occurrence of fireflies, O: Average; less than 1.0, Δ: 1.0 or more and less than 2.0, ×: 2.0 or more.

<Toner material liquid preparation process>
--- Synthesis of unmodified polyester (low molecular weight polyester)-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 46 parts by mass of adipic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. A modified polyester was synthesized.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 47 ° C., and an acid value of 18 mgKOH / g.

-Preparation of master batch (MB)-
600 parts by weight of water, 400 parts by weight of carbon black (“Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5) as the colorant, and 600 parts by weight of the unmodified polyester were added to Henschel. Mixing was performed using a mixer (Mitsui Mining Co., Ltd.). The mixture was kneaded with a two-roller at 150 ° C. for 30 minutes, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a pigment master batch.

-Preparation of organically modified layered inorganic mineral master batch-
300 parts by weight of water, 550 parts by weight of Clayton APA (manufactured by Southern Clay Products), and 1,450 parts by weight of the unmodified polyester are added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Got a mixture. The mixture was kneaded at 145 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to obtain an organically modified layered inorganic mineral masterbatch.

--Synthesis of wax dispersant--
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 600 parts of xylene and 300 parts of low molecular weight polyethylene (Sanwa Kasei Kogyo Co., Ltd. Sun Wax LEL-400: softening point 128 ° C.) are sufficiently dissolved, and after nitrogen replacement , 2310 parts of styrene, 270 parts of acrylonitrile, 150 parts of butyl acrylate, 78 parts of di-t-butylperoxyhexahydroterephthalate and 455 parts of xylene were added dropwise at 175 ° C. over 3 hours to polymerize, Hold at temperature for 30 minutes. Next, the solvent was removed to obtain a wax dispersant.

(Production Example 1)
-Preparation of wax dispersion-
In a reaction vessel equipped with a stirrer and a thermometer, 378 parts by mass of the unmodified polyester, 110 parts by mass of wax (Bsquare 180 White melting point 86.4 ° C., manufactured by Toyo Adre), 50 parts by mass of a wax dispersant, and acetic acid 947 parts by mass of ethyl was charged, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour to obtain a wax dispersion (1).

-Preparation of organic solvent phase-
The wax dispersion (1) is added to 2493 parts by mass, 500 parts by mass of the pigment masterbatch, 73.6 parts of the organic modified layered inorganic mineral masterbatch and 1012 parts by mass of ethyl acetate are mixed for 1 hour to obtain a raw material solution. Obtained.
1324 parts by mass of the obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm zirconia. The carbon black and the wax were dispersed by three passes under the condition of 80% by volume of beads. Next, 1324 parts by mass of a 65% by mass ethyl acetate solution of the unmodified polyester was added to the dispersion. One pass was performed in a bead mill under the same conditions as described above, and the mixture was dispersed to prepare an organic solvent phase.
The solid content concentration (measurement condition: 130 ° C., by heating for 30 minutes) of the obtained organic solvent phase was 50% by mass.

--Synthesis of prepolymer--
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2 mol adduct, 81 parts of bisphenol A propylene oxide 2 mol adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 7 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, a peak molecular weight of 3000, a Tg of 54 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 52 mgKOH / g.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate mass% of 1.53 mass% and a solid content of 49.1 wt%.

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

-Preparation of toner material liquid-
In a reaction vessel, 749 parts by mass of the organic solvent phase, 15 parts by mass of [Prepolymer 1], and 2.9 parts by mass of the ketimine compound were charged, and a tertiary amine compound represented by the general formula (1) ( U-CAT660M Sanyo Kasei Kogyo Co., Ltd.) is added at 0.4 wt% with respect to the toner solids, and the toner is mixed for 1 minute at 7.5 m / s using a TK homomixer (made by Tokushu Kika Kogyo). A material solution was prepared.

-Preparation of organic resin fine particle dispersion-
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 20 parts by mass of a sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30" manufactured by Sanyo Chemical Industries), 78 parts by mass of styrene , 78 parts by mass of methacrylic acid, 120 parts by mass of butyl acrylate, and 1 part by mass of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours. Vinyl resin particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) (Copolymer) aqueous dispersion (organic resin fine particle dispersion) was prepared.
The volume average particle diameter (Dv) of the organic resin fine particles contained in the obtained organic resin fine particle dispersion was measured with a particle size distribution measuring device (“nanotrac UPA-150EX”; manufactured by Nikkiso Co., Ltd.), and found to be 55 nm. . Further, a part of the organic resin fine particle dispersion was dried to isolate the resin component, and the glass transition temperature (Tg) of the resin component was measured. It was 450,000.

-Preparation of aqueous medium phase-
990 parts by weight of water, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), 15 parts by weight of the organic resin fine particle dispersion, and 90 parts by weight of ethyl acetate Were mixed and stirred to obtain a milky white liquid (aqueous medium phase).

<Toner granulation process>
-Emulsification or dispersion-
1200 parts by mass of the aqueous medium phase is added to the toner material liquid, and mixed for 20 minutes at a peripheral speed of 15 m / s with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). An emulsified slurry) was prepared.
-Removal of organic solvent-
The emulsified slurry after particle size control was placed in a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain a dispersed slurry.
-Cleaning and drying-
After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at a rotation speed of 10.0 m / s), and then filtered. 100 parts by mass of ion-exchanged water was added to the obtained filter cake, and mixed with a TK homomixer (10 minutes at a rotation speed of 10.0 m / s). The pH at this time was 6.3. Thereafter, filtration under reduced pressure was performed. To the obtained filter cake, 100 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed with a TK homomixer (10 minutes at a rotation speed of 10.0 m / s), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at a rotation speed of 10.0 m / s for 10 minutes), and then filtered twice. The aqueous dispersion at that time was pH 6.2 for the first time and 6.4 for the second time. After adding 300 parts by mass of ion-exchanged water to the obtained filter cake, mixing with a TK homomixer (10 minutes at a rotation speed of 10.0 m / s), adjusting to pH 4 with a 10% by mass hydrochloric acid solution 1 Stir for hours and filter. 300 parts by mass of ion-exchanged water was added to the obtained filter cake, mixed with a TK homomixer (10 minutes at a rotation speed of 10.0 m / s), and then filtered twice to obtain a final filter cake. .
The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours and sieved with a mesh having an opening of 75 μm to obtain toner base particles of Example 1.

-External additive treatment-
Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) was added to 1.5 parts by mass of hydrophobic silica as an external additive and 0.5 parts by mass of hydrophobized titanium oxide with respect to 100 parts by mass of the obtained toner base particles of Example 1. The toner of Example 1 was produced by mixing the mixture and sieving with a mesh having an opening of 35 μm.

A toner was prepared in the same manner as in Example 1 except that the amount of the tertiary amine compound added was changed to 0.1 wt% in the preparation of the toner material liquid.

A toner was prepared in the same manner as in Example 1 except that the pH was 6 with a 10% by mass hydrochloric acid solution in washing and drying.

A toner was prepared in the same manner as in Example 1 except that the addition amount of the tertiary amine compound was changed to 0.8 wt% in the preparation of the toner material liquid.

A toner was prepared in the same manner as in Example 1 except that the amount of the tertiary amine compound added in the preparation of the toner material liquid was changed to 1.2 wt%, and the washing and drying were changed to pH 6 with a 10 mass% hydrochloric acid solution.

(Comparative Example 1)
A toner was prepared in the same manner as in Example 1 except that the pH was not adjusted with a 10% by mass hydrochloric acid solution in washing and drying.

(Comparative Example 2)
A toner was prepared in the same manner as in Example 1 except that the tertiary amine compound was not added in the preparation of the toner material liquid.

(Comparative Example 3)
A toner was prepared in the same manner as in Example 1 except that Besquare 180 White was changed to paraffin wax having a melting point of 96.8 ° C. in the preparation of the wax dispersion.
Table 1 shows the evaluation results of the toners of Examples and Comparative Examples.

(Comparative Example 4)
A toner was prepared in the same manner as in Example 1 except that Besquare 180 White was changed to HNP-10 (melting point: 75.0 ° C., manufactured by Nippon Seiwa Co., Ltd.) in the preparation of the wax dispersion.

The evaluation results of the toners of Examples 1 to 5 and Comparative Examples 1 to 4 are shown in Table 1, and the volume average particle diameter (Dv), number average particle diameter (Dn), and particle size distribution (volume average particle diameter (Dv ) / Number average particle diameter (Dn)) was measured by the above method. The results are shown in Table 2.

(About Figures 1 and 2)
DESCRIPTION OF SYMBOLS 1 Developing apparatus 2 Powder pump means 3 Toner storage container 4 Suction type powder pump 5 Rotor 6 Stator 7 Holder 8 Gear 9 Joint (About FIG. 3, 4, 5)
5Y, 5M, 5C, 5K Development section
6Y, 6M, 6C, 6K Image forming unit 32Y, 32M, 32C, 32K Toner container 33Y Intake port
34Y nozzle
40Y, 40M, 40C, 40K MONO pump (powder pump)
41Y suction port
42Y rotor
43Y stator
44Y Rotor drive shaft
45Y drive gear
46Y motor
49Y, 49M, 49C, 49K Tube (toner transport path)
51Y Development roller
52Y Doctor Blade
55Y conveying screw
100 Image forming apparatus body (apparatus body)
(About Figure 6)
DESCRIPTION OF SYMBOLS 101 Photoconductor 102 Charging means 103 Exposure means 104 Developing means 105 Image receiving paper 107 Cleaning means 108 Transfer means

US Pat. No. 2,297,691 JP-A-10-020552 JP 11-007156 A JP 2004-226669 A Japanese Patent No. 2666316 Japanese Patent No. 3225899 Japanese Patent Application Laid-Open No. 2002-6541 JP 2004-246345 A JP 2005-49858 A JP-T-2003-515795 Special table 2006-500605 gazette JP-T-2006-503313 JP 2003-202708 A JP 2009-588949 A

Claims (21)

A toner obtained through a step of emulsifying or dispersing a toner material liquid containing a liquid containing a material constituting the toner in an aqueous medium, wherein the toner material liquid contains at least the binder resin (A) and / or It contains a precursor of the binder resin (B), a wax, a layered inorganic mineral, and a tertiary amine, and the wax has a melting point of 60 to 95 ° C. with a weight loss at 165 ° C. of 10% by mass or less. The layered inorganic mineral is obtained by modifying at least part of ions between layers with organic ions, the toner has an average circularity of 0.955 to 0.975, and a toner. A toner characterized in that the tertiary amine compound remaining therein is 0.1 wt% or less.   The toner according to claim 1, wherein the toner material liquid contains a tertiary amine compound in an amount of 0.05 wt% to 1.5 wt% with respect to the toner solid content. The toner according to claim 1, wherein the wax is at least a microcrystalline wax. The binder resin (B) precursor contains an active hydrogen group-containing compound and a polymer having reactivity with the active hydrogen group, and the binder resin (B) is emulsified in the aqueous medium. Or a reaction product obtained by reacting the active hydrogen group-containing compound with a polymer having reactivity with the active hydrogen group in the dispersing step. The toner described. The toner according to claim 4, wherein the polymer having reactivity with the active hydrogen group contains a modified polyester resin.   The toner according to claim 5, wherein the modified polyester resin has a weight average molecular weight of 3,000 to 45,000.   The toner according to claim 1, wherein the binder resin (A) is an unmodified polyester.   The toner according to claim 7, wherein the acid value of the unmodified polyester is 12 to 30 (mg KOH / g).   The toner according to claim 1, wherein the glass transition point of the unmodified polyester is 30 to 70 ° C.   The weight-average molecular weight of the THF-soluble component of the binder resin containing the binder resin (A) and the binder resin (B) is 3,000 to 30,000. The toner according to any one of the above.   The toner according to claim 10, wherein a glass transition point of the binder resin is 35 ° C. to 65 ° C. The toner according to claim 1, wherein a tetrahydrofuran (THF) insoluble matter contained in the toner is 5 to 25% by mass. The toner according to claim 1, wherein the toner contains 10 to 300 mass% of a wax dispersant with respect to the wax. 14. The toner according to claim 1, wherein the volume average particle diameter of the dispersed particles of the wax in the toner material liquid is 0.1 to 2 μm. The toner according to claim 1, wherein the toner particles have a volume average particle diameter / number average particle diameter of 1.00 to 1.25. The toner according to claim 1, wherein the toner particles have a volume average particle diameter of 1 to 7 μm.   A developer comprising the toner according to claim 1 and a carrier. A toner-containing container comprising the toner according to claim 1. In the process cartridge that integrally supports the electrostatic latent image carrier, the developing unit, the charging unit and / or the cleaning unit and is detachable from the image forming apparatus main body, the developing unit holds toner, and The process cartridge according to claim 1, wherein the toner is the toner according to claim 1. An image is formed by an image forming apparatus having a toner transfer process for supplying toner to the development process according to the amount of toner consumed from the toner cartridge, a development process for developing the developer containing the toner, a transfer process, and a fixing process. 17. The image forming method according to claim 1, wherein the toner is the toner according to any one of claims 1 to 16, and the amount of toner aggregates having a diameter of 0.2 mm or more in the developer after the toner transfer step is two. An image forming method, wherein An image forming apparatus comprising: a toner transfer step for supplying toner to a development step according to an amount consumed by toner use from a toner cartridge; a development step for developing a developer containing the toner; a transfer step; and a fixing step. The toner is the toner according to any one of claims 1 to 16, wherein the amount of toner aggregates having a diameter of 0.2 mm or more in the developer after the toner transfer step is less than two. Image forming apparatus.

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