JP6729020B2 - Toner, toner containing unit, image forming apparatus, and image forming method - Google Patents

Description

The present invention relates to a toner, a toner containing unit using the toner, an image forming apparatus, and an image forming method.

Due to the recent prosperity of environmentally friendly products, a technique for fixing toner with low energy is desired. Various means are available, but the demand for electrostatic image forming toners capable of fixing at lower temperatures is increasing.
As a means for lowering the fixing temperature of the toner, it is general practice to lower the glass transition point (Tg) of the toner binder. However, if Tg is simply lowered, powder agglomeration (in the present invention, powder agglomeration is referred to as “blocking”) easily occurs, and if the powder agglomerates in the image forming apparatus, it affects the operation of the developing device. It may become inoperable. Even if it becomes impossible to operate, the toner may not be replenished due to the agglomeration of the powder in the toner storage container, the toner concentration may decrease, and an abnormal image may be formed.
Further, when a large number of sheets are continuously printed by a printing machine, the heat applied at the time of fixing is not completely cooled, so that the output sheets are bonded to each other via the fixed image immediately after the discharging (in the present invention, the discharged sheets are stuck to each other). Adhesion of paper is referred to as "paper discharge blocking"). Therefore, it is necessary to improve the discharge blocking resistance of the toner. Further, if Tg is lowered, the storage stability of the toner on the surface of the fixed image also deteriorates. If the fixed image melts and is easily transferred, the output paper may be stored at a high temperature and under a force, and may be attached to another recording medium that is overlaid, and may not be stored for a long time.
This Tg is an important point in the design of the toner binder, but the method of simply lowering the Tg does not cause the blocking or the paper discharge blocking, and obtains a toner having good image storability and capable of low-temperature fixing. It was difficult.

On the other hand, a method of using a crystalline resin as a toner binder has long been known as a means for achieving both blocking resistance, image storability, and low-temperature fixability. However, there is a problem that hot offset occurs due to insufficient elasticity during melting.
A core-shell type toner having a shell by a melt suspension method or an emulsion aggregation method has been proposed as a means for achieving both blocking resistance, image storability and low-temperature fixability (for example, Patent Document 1, 2). However, it is still insufficient to obtain good blocking resistance, image storability, and good discharge blocking resistance while maintaining low-temperature fixability.
Furthermore, in order to solve this problem, a method focusing on a crystalline resin (for example, refer to Patent Document 3) has been proposed, but the external conditions (heat history during manufacturing, storage, and fixing, partial phase mixing, etc.) Since it is easily affected and the crystal structure is not stable, there is a problem that various properties of the toner such as blocking resistance, discharge blocking resistance, and image storability are adversely affected.

On the other hand, there are a conventional example in which a metal salt or complex of a salicylic acid derivative is externally added to a toner as a charge control agent (see, for example, Patent Document 4), and an example in which the surface is attached to the toner in water (see, for example, Patent Document 5). It has been reported.
However, there is a trade-off relationship between the low-temperature fixability of the toner and the securing of blocking resistance, discharge-proof blocking resistance, image storability, etc. In the conventional method, these low-temperature fixability, blocking resistance, and discharge-proof property are used. Toners that are compatible with all of blocking properties and image storability have not been obtained.

An object of the present invention is to provide a toner that has both low-temperature fixability, discharge blocking resistance, and image storability.

The means for solving the above problems are as follows. That is,
The toner of the present invention is a toner containing at least a binder resin,
Particles of a metal complex or salt of an aromatic carboxylic acid derivative having a number average particle size of 0.2 μm or more and 1.0 μm or less are present on the toner surface, and particles of the metal complex or salt of the aromatic carboxylic acid derivative are present. The coverage of the toner surface is 10% or more and 50% or less.

According to the present invention, it is possible to provide a toner having both low-temperature fixability, discharge blocking resistance, and image storability.

FIG. 1 is a schematic diagram for explaining an EDX image of Zr with respect to the toner of the embodiment of the present invention. FIG. 2 is a schematic diagram for explaining an image after binarizing a Zr EDX image with respect to the toner of the embodiment of the present invention. FIG. 3 is a schematic diagram for explaining the peak full width at half maximum (FWHM) of crystalline polyester. FIG. 4 is a schematic configuration diagram showing an example of the image forming apparatus of the present invention. FIG. 5 is a schematic configuration diagram showing an example of a process cartridge.

(toner)
The toner of the present invention contains at least a binder resin.
In the toner, particles of a metal complex or salt of an aromatic carboxylic acid derivative that exhibits a crosslinking ability by heat energy are present on the surface of the toner.
The number average particle diameter of the metal complex or salt particles of the aromatic carboxylic acid derivative is 0.2 μm or more and 1.0 μm or less. The coverage of the toner surface with particles of the metal complex or salt of the aromatic carboxylic acid derivative is 10% or more and 50% or less.
The toner further contains other components such as a release agent and a colorant, if necessary.
As described above, the low temperature fixing property of the toner, the discharge blocking resistance, and the securing of the image storability are in a trade-off relationship, but in order to avoid such a trade-off, the resin structure is not modified, It is conceivable to dispose on the surface of the toner a cross-linking agent that reacts only when placed at a high temperature during fixing. As the cross-linking agent, a salt or complex having a polyvalent metal capable of forming an ionic bond or a coordinate bond with the acid terminal or the hydroxyl terminal of the polyester which is the binder resin is considered, and examples thereof include a metal salt or complex of a salicylic acid derivative. .. However, since it also has a charge controllability, the above-mentioned Patent Document 4 externally added to the toner as a charge control agent and the above Patent Document 5 surface-adhered to the toner in water are known. However, since the purpose in these documents is to improve the charging performance, the location and particle size of the salicylic acid derivative, etc. within the range described here, low temperature fixability, paper discharge blocking resistance, image It was not satisfactory in terms of compatibility with preservability.
The inventors of the present invention configured as described above can prevent the discharge blocking even in a toner that can be fixed at a low temperature by causing a crosslinking reaction on the toner surface at the time of fixing to cause curing of the outermost layer. It was found that good image storability can be ensured.
In the toner of the present invention, the thermal energy at the time of fixing causes a crosslinking reaction between the binder resins with the particles of the metal complex or salt of the aromatic carboxylic acid derivative, which is the resin crosslinking agent, as intermediaries on the surface of the toner. For example, a hydrogen bond, a covalent bond, an ionic bond, or a coordinate bond can be used to induce an interaction between the polymers of the resin. More preferably, the use of an ionic bond or a coordinate bond is effective because changes easily occur at low temperatures. As a result, a high molecular component is generated, and the molecular weight of the toner after heating becomes large.
In the present invention, the aromatic carboxylic acid is used to prevent paper discharge blocking by causing interaction between polymers on the toner surface even when heated at an ultralow temperature of 100° C. by utilizing such bond formation. Utilization of ionic or coordinate bond formation by heating the metal complex or salt of the derivative and the polar group of the binder resin.

<Aromatic carboxylic acid derivative metal complex or salt>
The number average particle diameter of the metal complex or salt particles of the aromatic carboxylic acid derivative is 0.2 μm or more and 1.0 μm or less. More preferably, it is 0.2 μm or more and 0.5 μm or less.
In order for the metal complex or salt of the aromatic carboxylic acid derivative to efficiently react with the binder resin, it is necessary to have a large contact area. When the number average particle diameter is larger than 1.0 μm, the ratio of the area in contact with the toner surface to the amount of the metal complex or salt of the aromatic carboxylic acid derivative added is small, and the crosslinking effect becomes low.
The coverage of the toner surface with particles of the metal complex or salt of the aromatic carboxylic acid derivative is 10% or more and 50% or less. More preferably, it is 10% or more and 40% or less.
When the coverage of the metal complex of the aromatic carboxylic acid derivative or the particles of the salt is less than 10%, the number of reaction points is too small and the surface is not sufficiently cured, resulting in lack of paper ejection blocking performance. If it is more than 50%, the metal complex or salt of the aromatic carboxylic acid derivative which is an inorganic substance acts as a fixing inhibitor and deteriorates the low temperature fixing property.

In order to cause the reaction between the metal complex or salt of the aromatic carboxylic acid derivative and the binder resin by heating at a low temperature, the reaction needs to be carried out effectively. It is important that the metal complex or salt of the aromatic carboxylic acid derivative is dispersed and attached to the toner surface in the form of fine particles. For that purpose, it is effective to provide a step of adhering fine particles of a metal complex or salt of an aromatic carboxylic acid derivative to the surface of the toner, as described in the method for producing a toner below. It is also effective to provide a step of strengthening the adhesive force by heating in a temperature range where the crosslinking reaction does not occur.
The hardness of the toner in the outermost surface layer of the fixed image is important in order to prevent paper discharge blocking and improve image storability. Since the metal complex or salt of the aromatic carboxylic acid derivative serving as the cross-linking agent is present only on the surface of the toner, it is possible to exhibit the same effect of inhibiting discharge blocking with a small addition amount as compared with the case where it is contained inside. Therefore, it is possible to suppress the increase in fixing temperature due to the addition of the metal complex or salt of the aromatic carboxylic acid derivative to a minimum.

The content of the metal complex or salt of the aromatic carboxylic acid derivative is preferably 0.4% by mass to 6% by mass with respect to the toner. When the toner particle size is 5.5 μm to 7 μm, which is generally used for polymerized toner, and the particle size of the metal complex or salt of the aromatic carboxylic acid derivative is 0.4 μm to 0.5 μm, which is easy to prepare, 0.4 If it is less than mass %, the coverage will be less than 10%. Therefore, when the amount of the metal complex or salt of the aromatic carboxylic acid derivative is less than 0.4% by mass, the amount of crosslinking points is small and the molecular weight of the binder resin on the toner surface cannot be effectively increased. If the amount of the metal complex or salt of the aromatic carboxylic acid derivative is larger than 6% by mass, the coverage will be 50% or more. Therefore, when the content is more than 6% by mass, the fixing property of the toner is hindered by the metal complex or salt of the aromatic carboxylic acid derivative on the toner surface.

Examples of the metal complex or salt of the aromatic carboxylic acid derivative include a metal complex or salt of a salicylic acid derivative or a hydroxynaphthoic acid derivative represented by the following general formula.

In the general formula, R _{1 to} R ₆ represent the same or different groups, and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, an alkenyl group having 2 to 12 carbon atoms which may be branched, _{OH, -NH 2, -NH (CH} 3), - N (CH 3) 2, -OCH 3, -OC 2 H 5, shown -COOH, or -CONH _2.
Among them, the metal complex or salt of salicylic acid derivative is more preferable, and the metal complex or salt of salicylic acid derivative is more preferably di-tertiarybutyl salicylic acid metal complex or salt.
The metal species forming the metal complex or salt is preferably any one of Zn ²⁺ , Al ³⁺ , Cr ³⁺ , Fe ³⁺ , and Zr ⁴⁺ , more preferably trivalent or more. Zr ⁴⁺ is particularly preferable.
In order for the crosslinking reaction to proceed rapidly during fixing, it is desirable that the metal complex or salt of the aromatic carboxylic acid derivative be fine and uniformly exist on the toner surface in order to secure the number of reaction points. Further, the smaller the particle size of the metal complex or salt of the aromatic carboxylic acid derivative and the smaller the molecular weight, the higher the coverage can be achieved even with the addition of a small amount, which is advantageous for low temperature fixing.
Particularly, as the zirconium compound, those represented by the following general formula (2) are preferable.
In the general formula (2), m is an integer of 1 to 20, n is an integer of 0 to 20, s is an integer of 0 to 20, and r is an integer of 1 to 20. t-Bu represents a tertiary butyl group.

<<Method of confirming existence state of metal complex of aromatic carboxylic acid derivative or particles of salt>>
In the present invention, as a means for confirming that the metal complex or salt of the aromatic carboxylic acid derivative is present on the surface of the toner, not on the inside of the toner, a method using both the element abundance measurement on the toner surface and the element abundance measurement on the entire toner is used. Conceivable.
X-ray photoelectron spectroscopy (XPS), which can detect a depth of about 5 nm from the surface, can be used as a method for measuring the amount of elements present on the toner surface.
Further, fluorescent X-ray analysis (XRF) can be cited as a method for measuring the amount of elements present in the entire toner.
By normalizing the measurement result of XPS indicating the surface abundance with the measurement result of XRF indicating the total amount, it can be used as an index of the surface abundance with respect to the total amount.

<<<Measurement of surface metal abundance>>>
For XPS measurement, for example, K-Alpha manufactured by Thermo-Fisher Co., Ltd. is used as an apparatus, Al (monochromator) is used as a measurement light source, and toner is sprayed in an analysis range of 400 μm ² .
Pass energy: (wide scan) 200 eV,
(Narrow scan) 50 eV
Energy step: (wide scan) 1.5 eV,
(Narrow scan) 0.2 eV
Relative sensitivity coefficient: Atomic% can be determined by analyzing the relative sensitivity coefficient of Thermo-Fisher under the conditions of use.
It is also possible to analyze the compounding state of the metal of interest by XPS, and it can be seen that the metal element is bonded to an oxygen atom derived from the binder resin or the aromatic carboxylic acid derivative.

<<<Measurement of total content>>>
As the XRF measurement, 3 g of the sample is molded into pellets having a diameter of 40 mm by a tablet molding machine at a pressure of 10 t/cm ² , and the measurement is performed using, for example, Rigaku ZSX-100e as an apparatus.
In order to define the amount of the metal complex or salt of the aromatic carboxylic acid derivative regardless of the metal species and the type of the ligand, the elements contained in the metal complex or salt of the aromatic carboxylic acid derivative are defined. With the compound contained, several pellets with known contents are prepared and a calibration curve is prepared.
The standard pellet can be produced by the following procedure, for example. First, a two-component curing type epoxy resin and a metal compound sample are weighed, and the epoxy resin is sufficiently kneaded with a spatula or the like to be dispersed. A polyring for molding a sample is placed on a plastic bag, and the sample prepared above is poured. After fully cured, remove the sample from the polybag to obtain standard sample pellets.
Here, the amount of the metal complex or the salt of the aromatic carboxylic acid derivative is defined by the mass% in the “metal element conversion” in the pellet.

<<<Regulation of surface abundance>>>
The presence of the metal complex or salt of the aromatic carboxylic acid derivative on the surface is defined as follows using the above XPS measurement and XRF measurement.
Up to the 5th period in the long-periodic periodic table excluding hydrogen, carbon, oxygen and rare gas elements, which does not exist in components other than the metal complex or salt of the aromatic carboxylic acid derivative and exists only in the complex or salt Element amount M (atomic %) present on the toner surface measured by XPS for one element, and element amount T (mass %) present in the entire toner measured by fluorescent X-ray analysis for the same element And the ratio (M/T) is 0.04 to 0.46.

<<<Measurement of number average particle size and coverage>>>
The toner is fixed on the carbon tape, and the sample coated with carbon for preventing charge-up is observed with a scanning electron microscope (SEM) and an energy dispersive X-ray analyzer (EDX). Observation conditions are SEM of SU8230 manufactured by Hitachi and EDX XFlash FlatQUAD 5060F manufactured by Bruker, acceleration voltage 10 kV, magnification 10000 times, EDX image of metal element used in metal complex or salt of aromatic carboxylic acid derivative. Is obtained for 10 or more particles of toner.
The detected image of the metal element is edited on image editing software (A-image made by Asahi Kasei Engineering).
-Scale setting-
Read the image to be analyzed from the "Image Input/Output" tab, and set the scale for this image based on the scale bar in the image using the "New scale setting" button.
-Image processing-
In the case of a color image, select "Color Image Analysis" from the "Image Analysis" tab, perform appropriate conversion, then select the image with the highest contrast and convert it to a monochrome image.
Then, select the "Laplacian filter" process from the "Image quality improvement" tab to emphasize the edges of the image and reduce blur.
-Calculation of number average particle size and coverage-
[Image processing]
Select "Particle Analysis" from the "Image Analysis" tab.
Select "Manual" as the binarization method/correction method, set the small figure removal area appropriately so that particles of small particle size are not removed, and press the "Execute" button.
While comparing with the original image, an appropriate threshold value is determined and binarized.
In the binarized image, when it is determined that a plurality of particles are originally one particle, it is manually corrected while comparing with the original image, and the “end” button is pressed.
The calculation result is obtained.
[Calculation of each parameter]
Number average particle size: Since the average perimeter is displayed, it is calculated by dividing by the pi.
Coverage: (total area of the metal element particles)/(area of toner portion).
Specifically, from the displayed value, first, the metal particle area is obtained by "the product of the average area and the number of particles" or "the product of the measurement area area and the area ratio".
Next, the areas other than the toner are calculated by approximating each with a triangle. Specifically, "shape measurement" is selected from the "image analysis" tab, the length of the base and height of the triangular portion around the toner is calculated, and the area is calculated. The toner area is obtained by subtracting the sum of the areas of the triangles from the “measurement area area” that is the image area.
Finally, the coverage is calculated by dividing the metal particle area by the toner area.
For reference, a Zr EDX image and a binarized image of the toner of the embodiment of the present invention are shown in FIGS. 1 and 2, respectively.
In this method, due to the problem of resolution of the EDX image, it is not possible to distinguish between the particle distribution of 0.2 μm or less and the case where the metal component uniformly covers the toner surface.

<<<Identification of metal complex or salt of aromatic carboxylic acid derivative on surface>>>
5 g of the toner is wetted with 50 g of methanol, 1 g of 1% HCl is added, and then ultrasonic treatment is performed for 10 minutes to elute the metal cation of the metal complex or salt of the aromatic carboxylic acid derivative on the surface with a proton.
The insoluble toner is filtered with 5B filter paper, the filtrate is collected, and the solvent is distilled off with an evaporator.
The precipitated white solid is transferred to a 5 mg vial and sufficiently suspended in 1.2 g of deuterated chloroform by ultrasonic shaking. This solution is transferred to an NMR tube and ¹ H-NMR is measured to identify an aromatic carboxylic acid derivative.

<Toner characteristics>
The acid value of the toner is preferably 10 mgKOH/g to 50 mgKOH/g, more preferably 20 mgKOH/g to 40 mgKOH/g.
When the acid value is 10 mgKOH/g or more, there are many reaction points with the metal complex or salt of the aromatic carboxylic acid derivative, and the toner surface is sufficiently cured. On the other hand, when the amount is 50 mgKOH/g or less, it is possible to effectively prevent the deterioration of the low temperature fixing property due to the reaction proceeding too much.
When using a plurality of binder resins, a resin having a low molecular weight and a low Tg is mixed as one component in order to attach importance to low temperature fixability. At this time, if the acid value of the resin component having a low molecular weight and low Tg is increased, the crosslinking reaction preferentially occurs with the resin component having a low molecular weight and low Tg, so that the paper discharge blocking effect of the low temperature fixing toner is enhanced. be able to.
The presence of hydroxyl groups is also important for increasing the bondability between polymers. The hydroxyl value of the toner is preferably 5 mgKOH/g to 40 mgKOH/g, more preferably 10 mgKOH/g to 30 mgKOH/g.

<<Measurement of Acid Value of Toner>>
In the present invention, the acid value of the toner is determined by the following method. The basic operation is based on the potentiometric titration method described in JIS K-0070.
(1) About 3 g of the toner sample is put into a 200 mL beaker and weighed to the order of 1 mg. 100 mL of a mixed solution of tetrahydrofuran:acetone:methanol=50:25:50 (volume ratio) is added and dissolved.
(2) After being dissolved by heating in a water bath warmed to 60° C. for 20 minutes, components that have not completely dissolved are ultrasonically shaken for 5 minutes to be uniformly dispersed in a solvent.
(3) After cooling the solution to room temperature, using a 0.1 mol/L ethanol solution of KOH while stirring with a stirrer, titration up to the inflection point using a potentiometric titrator (COM2000 manufactured by HIRANUMA). taking measurement.
(4) The amount of the KOH solution used at this time is S (mL), and the sample weight is W (g). However, f is a factor of an ethanol solution of 0.1 mol/L KOH.
Acid value (mgKOH/g)=[S×f×5.611]/W

<Binder resin>
As the binder resin, a resin having a carboxyl group is preferable. A polyester resin having a carboxyl group at the terminal is particularly preferable.
Further, in order to achieve low temperature fixing, it is effective to use a crystalline polyester resin or a polyester resin having a low glass transition temperature.
As a preferred embodiment of the binder resin, there is an embodiment in which an amorphous polyester resin, a polyester resin, and a crystalline polyester resin are used in combination, as shown in the following examples.
<<Amorphous polyester resin>>
The constituent components of the amorphous polyester resin are as follows.
-Diol-
The diol is not particularly limited as long as it contains 50 mol% or more of an aliphatic diol having 3 to 10 carbon atoms, and can be appropriately selected according to the purpose. For example, ethylene glycol or 1,2-propylene glycol. 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12 An aliphatic diol such as dodecanediol; a diol having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; 1,4-cyclohexanedimethanol, hydrogenated bisphenol A Alicyclic diols such as alicyclic diols; alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide added to alicyclic diols; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols such as ethylene oxide and propylene oxide And alkylene oxide adducts of bisphenols such as those to which alkylene oxides such as butylene oxide are added. Of these, aliphatic diols having 4 to 12 carbon atoms are preferable.
These diols may be used alone or in combination of two or more.

-Dicarboxylic acid-
The dicarboxylic acid is appropriately selected depending on the intended purpose without any limitation, and examples thereof include an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid. Further, these anhydrides may be used, a lower alkyl group having 1 to 3 carbon atoms may be used, or a halide may be used.
The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid and fumaric acid.
The aromatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Aliphatic dicarboxylic acids of 12 or less are preferred.
These dicarboxylic acids may be used alone or in combination of two or more.

-3 aliphatic alcohol or more-
The trihydric or higher aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and dipentaerythritol. To be
Of these, 3 to 4 aliphatic alcohols are preferable. These trihydric or higher aliphatic alcohols may be used alone or in combination of two or more.
The acid value of the amorphous polyester resin is not particularly limited and may be appropriately selected depending on the purpose, but in order to achieve the desired low temperature fixing property from the viewpoint of the affinity between the paper and the resin. 10 mgKOH/g or more is preferable, and 20 mgKOH/g or more is more preferable. On the other hand, in order to improve the high temperature offset resistance, it is preferably 50 mgKOH/g or less.
The hydroxyl value of the amorphous polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. In order to achieve desired low temperature fixing property and good paper discharge blocking property. Is preferably 5 mgKOH/g to 40 mgKOH/g, more preferably 10 mgKOH/g to 30 mgKOH/g.
Further, the viscoelasticity of the toner can be adjusted by the hydrogen bonding force using a polyester resin containing a urethane bond and a urea bond.

<<<<Polyester Resin Containing Urethane Bond and Urea Bond>>>>
The polyester resin containing the urethane bond and the urea bond is obtained by reacting a non-linear reactive precursor with a curing agent. In order to achieve the desired low temperature fixability, it is desirable that the glass transition temperature is -60°C or higher and 0°C or lower.

-Non-linear reactive precursor-
The non-linear reactive precursor is not particularly limited as long as it is a polyester resin having a group capable of reacting with the curing agent (hereinafter, may be referred to as “prepolymer”), depending on the purpose. Can be appropriately selected.
Examples of the group capable of reacting with the curing agent in the prepolymer include a group capable of reacting with an active hydrogen group. Examples of the group capable of reacting with the active hydrogen group include an isocyanate group, an epoxy group, a carboxylic acid, and an acid chloride group. Among these, an isocyanate group is preferable in that a urethane bond or a urea bond can be introduced into the amorphous polyester resin.
The prepolymer is non-linear. The term "non-linear" means having a branched structure provided by at least one of a trivalent or higher valent alcohol and a trivalent or higher carboxylic acid.
The prepolymer is preferably a polyester resin containing an isocyanate group.

---Polyester resin containing isocyanate group---
The polyester resin containing an isocyanate group is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a reaction product of a polyester resin having an active hydrogen group and polyisocyanate. The polyester resin having an active hydrogen group can be obtained, for example, by polycondensing a diol, a dicarboxylic acid, and at least one of a trivalent or higher valent alcohol and a trivalent or higher carboxylic acid. The trihydric or higher alcohol and the trihydric or higher carboxylic acid impart a branched structure to the isocyanate group-containing polyester resin.

---Diol ---
The diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol and 3-methyl. Aliphatic diols such as -1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol; diethylene glycol, triethylene glycol, dipropylene glycol , Diols having an oxyalkylene group such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols containing ethylene oxide, propylene oxide, Addition of alkylene oxides such as butylene oxide; Bisphenols such as bisphenol A, bisphenol F, bisphenol S; Alkylene oxides of bisphenols such as addition of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to bisphenols Examples include adducts. Of these, aliphatic diols having 4 to 12 carbon atoms are preferable.
These diols may be used alone or in combination of two or more.

---Dicarboxylic acid---
The dicarboxylic acid is appropriately selected depending on the intended purpose without any limitation, and examples thereof include an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid. Further, these anhydrides may be used, a lower alkyl group having 1 to 3 carbon atoms may be used, or a halide may be used.
The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid and fumaric acid.
The aromatic dicarboxylic acid is appropriately selected depending on the intended purpose without any limitation, but it is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms. The aromatic dicarboxylic acid having 8 to 20 carbon atoms is appropriately selected depending on the intended purpose without any limitation, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid.
Among these, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferable.
These dicarboxylic acids may be used alone or in combination of two or more.

---Alcohol having 3 or more valences ---
The trihydric or higher alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, trihydric or higher aliphatic alcohol, trihydric or higher polyphenols, trihydric or higher polyphenol alkylene. Examples thereof include oxide adducts.
Examples of the trihydric or higher aliphatic alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolac, and cresol novolac.
Examples of the alkylene oxide adduct of trivalent or higher polyphenols include triphenol or higher polyphenols to which an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide is added.

---Carboxylic acid having a valence of 3 or more---
The trivalent or higher carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trivalent or higher aromatic carboxylic acids. Further, these anhydrides may be used, a lower alkyl group having 1 to 3 carbon atoms may be used, or a halide may be used.
The trivalent or higher aromatic carboxylic acid is preferably a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms. Examples of the trivalent or higher valent aromatic carboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromellitic acid.

-Polyisocyanate-
The polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diisocyanate and trivalent or higher isocyanate.
Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and the like in which these are blocked with a phenol derivative, oxime, caprolactam, or the like.
The aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate and decametine. Examples thereof include diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate and tetramethylhexane diisocyanate.
The alicyclic diisocyanate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.
The aromatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate and 4,4′-diisocyanato. Examples thereof include diphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 4,4′-diisocyanato-3-methyldiphenylmethane, and 4,4′-diisocyanato-diphenyl ether.
The araliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α,α,α′,α′-tetramethylxylylene diisocyanate.
The isocyanurates are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tris(isocyanatoalkyl)isocyanurate and tris(isocyanatocycloalkyl)isocyanurate.
These polyisocyanates may be used alone or in combination of two or more. Further, it is preferably used as a reaction precursor (hereinafter sometimes referred to as “prepolymer”) to be reacted with a curing agent described later.

-Curing agent-
The curing agent is appropriately selected depending on the intended purpose without any limitation, provided that it reacts with the prepolymer, and examples thereof include active hydrogen group-containing compounds.
---Compound containing active hydrogen group---
The active hydrogen group in the active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups. And so on. These may be used alone or in combination of two or more.
The active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose, but amines are preferable because they can form a urea bond.
The amines are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those in which these amino groups are blocked. Can be mentioned. These may be used alone or in combination of two or more.
Among these, diamine and a mixture of diamine and a small amount of trivalent or higher amine are preferable.
The diamine is appropriately selected depending on the intended purpose without any limitation, and examples thereof include aromatic diamine, alicyclic diamine, and aliphatic diamine. The aromatic diamine is appropriately selected depending on the intended purpose without any limitation, and examples thereof include phenylenediamine, diethyltoluenediamine, and 4,4′-diaminodiphenylmethane. The alicyclic diamine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane and isophoronediamine. To be The aliphatic diamine is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ethylenediamine, tetramethylenediamine, and hexamethylenediamine.
The trivalent or higher amine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.
The amino alcohol is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ethanolamine and hydroxyethylaniline.
The amino mercaptan is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminoethyl mercaptan and aminopropyl mercaptan.
The amino acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.
The blocked amino group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the amino group may be obtained by blocking with ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Examples thereof include ketimine compounds and oxazoline compounds.

In order to lower the Tg of the amorphous polyester resin and to easily impart the property of deforming at a low temperature, the amorphous polyester resin contains a diol component as a constituent component, and the diol component has a carbon number of 4 or more. It is preferable to contain 50% by mass or more of 12 or less aliphatic diol. In addition, in order to lower the Tg of the amorphous polyester resin and to easily impart the property of deforming at low temperature, the amorphous polyester resin is an aliphatic diol having 4 to 12 carbon atoms in all alcohol components. Is preferably contained in an amount of 50% by mass or more.
In order to lower the Tg of the amorphous polyester resin and to easily impart the property of deforming at low temperature, the amorphous polyester resin contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component has a carbon number of It is preferable to contain 50% by mass or more of 4 or more and 12 or less aliphatic dicarboxylic acid.
The glass transition temperature of the amorphous polyester resin is −60° C. or higher and 0° C. or lower, and more preferably −40° C. to −20° C. When the glass transition temperature is −60° C. or higher, the flow of the toner at a low temperature cannot be suppressed, the heat-resistant storage stability deteriorates, and the filming resistance deteriorates effectively. You can When the glass transition temperature is 0° C. or lower, the toner cannot be sufficiently deformed by heating and pressurizing at the time of fixing, and the problem that the low temperature fixing property is insufficient can be effectively prevented.
The weight average molecular weight of the amorphous polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is 20,000 or more and 1,000,000 or less in GPC (gel permeation chromatography) measurement. Is preferred. The weight average molecular weight of the amorphous polyester resin is a molecular weight of a reaction product obtained by reacting the non-linear reactive precursor with the curing agent. When the weight average molecular weight is 20,000 or more, the toner may easily flow at a low temperature and may be inferior in heat resistant storage stability, and the viscosity at the time of melting may be low and the high temperature offset property may be deteriorated. This problem can be effectively prevented.

The molecular structure of the amorphous polyester resin can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc., in addition to NMR measurement by a solution or solid. A simple method is to detect, as an amorphous polyester resin, an infrared absorption spectrum having no absorption at 965±10 cm ⁻¹ and 990±10 cm ⁻¹ based on δCH (out-of-plane bending vibration) of an olefin. ..
The content of the amorphous polyester resin used as the prepolymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is 5 to 25 parts by mass with respect to 100 parts by mass of the toner. Is preferred, and 10 parts by mass to 20 parts by mass is more preferred. When the content is less than 5 parts by mass, the low temperature fixability and the high temperature offset resistance may deteriorate, and when the content exceeds 25 parts by mass, the heat resistant storage stability deteriorates and the gloss of the image obtained after fixing is high. The degree may decrease. When the content is within the above more preferable range, it is advantageous in that it is excellent in all of low temperature fixing property, high temperature offset resistance and heat resistant storage stability.

<<Crystalline polyester resin>>
The crystalline polyester resin may be used together with the above-mentioned amorphous polyester resin because it has crystallinity and therefore exhibits a hot-melting property which shows a rapid decrease in viscosity near the fixing start temperature.
By using the crystalline polyester resin having such characteristics together with the amorphous polyester resin, heat resistance and storage stability due to crystallinity are good until just before the melting start temperature, and at the melting start temperature, the crystalline polyester resin is rapidly melted due to melting. Since the viscosity of the toner is lowered, the toner is compatible with the amorphous polyester resin, and the viscosity is rapidly lowered to fix the toner, a toner having good heat-resistant storage stability and low-temperature fixability can be obtained. In addition, the release width (difference between the lower limit fixing temperature and the high temperature resistant offset generation temperature) also shows good results.
The crystalline polyester resin can be obtained by using a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester, or a derivative thereof.
In the present invention, the crystalline polyester resin is a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester, or a derivative thereof, as described above. The resin obtained by modifying the polyester resin, for example, the prepolymer and the resin obtained by subjecting the prepolymer to a crosslinking and/or elongation reaction do not belong to the crystalline polyester resin.

In the crystalline polyester resin of the present invention, the half-value width of the peak in X-ray diffraction of the crystalline polyester resin is preferably less than 1.0°/2θ, more preferably less than 0.6°/2θ. ..
When the peak half width of the crystalline polyester is less than 1.0°/2θ, the crystallinity of the crystalline polyester is low, so that the sharp melt property is inferior and sufficient low-temperature fixability is not effectively prevented. can do.
The half width of the peak in X-ray diffraction when the crystalline polyester is dissolved and recrystallized in an organic solvent is preferably less than 1.0, more preferably less than 0.6. .. If the crystalline polyester has a peak half-value width of less than 1.0 after dissolution and recrystallization, the crystalline polyester present in the toner has low crystallinity, and part of the crystalline polyester is amorphous polyester. Since they are in a compatible state, low-temperature fixability and heat-resistant storage stability are deteriorated, the crystalline polyester is easily filmed in the developing machine, and it is possible to effectively prevent the problems of developing machine contamination and image deterioration. it can.

<<<Measurement of peak half width by X-ray diffraction measurement>>>
The X-ray diffraction measurement of the crystalline polyester can be confirmed by a crystal analysis X-ray diffractometer (X'Pert MRDX'Pert MRD Phillips). The measuring method will be described below. First, the target sample is ground with a mortar to prepare a sample powder, and the obtained sample powder is uniformly applied to the sample holder. Then, the sample holder is set in the diffractometer and measurement is performed to obtain a diffraction spectrum.
The peaks obtained in the range of 20°<2θ<25° from the obtained diffraction peaks are defined as P1, P2,... In descending order of peak intensity.
The peak full width at half maximum (FWHM) is defined as the difference x2-x1 between the points x1 and x2 at which the maximum peak intensity is half, as shown in FIG.
The measurement conditions for X-ray diffraction will be described below.
Tension kV: 45 kV
Current: 40A
MPSS
Upper
Gonio
Scanmode:continuos
Start angle: 3°
End angle: 35°
Angle Step: 0.02°
Lucient beam optics
Diversity slit: Div slit 1/2
Diffraction beam optics
Anti scatter slit: As Fixed 1/2
Receiving slit: Prog rec slit

<<<Dissolution of Crystalline Polyester in Organic Solvent and Recrystallization Method>>>
The method for dissolving and recrystallizing the crystalline polyester in an organic solvent is as follows.
10 g of crystalline polyester and 90 g of organic solvent are stirred at 70° C. for 1 hour.
The solution after stirring is cooled at 20° C. for 12 hours to recrystallize the crystalline polyester.
The organic solvent dispersion of crystalline polyester after recrystallization was applied to Kiriyama funnel (manufactured by Kiriyama Seisakusho), and Kiriyama funnel filter paper No. 4 (manufactured by Kiriyama Seisakusho) is set and suction filtered with an aspirator to separate the organic solvent and the crystalline polyester. The crystalline polyester obtained by separation is dried at 35° C. for 48 hours to obtain a recrystallized product of the crystalline polyester.

The components of the crystalline polyester resin are as shown below.
-Polyhydric alcohol-
The polyhydric alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diols and trihydric or higher alcohols.
Examples of the diol include saturated aliphatic diols. Examples of the saturated aliphatic diol include straight-chain saturated aliphatic diols and branched saturated aliphatic diols. Among these, straight-chain saturated aliphatic diols are preferable, and straight-chain saturated fats having 2 to 12 carbon atoms. Group diols are more preferred. When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin may be lowered and the melting point may be lowered. If the saturated aliphatic diol has more than 12 carbon atoms, it becomes difficult to obtain a practical material. The carbon number is more preferably 12 or less.
Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, 18-octadecanediol, 1,14-eicosandecanediol and the like can be mentioned. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10 in terms of high crystallinity of the crystalline polyester resin and excellent sharp melt property. -Decanediol and 1,12-dodecanediol are preferred. Examples of the trihydric or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. These may be used alone or in combination of two or more.

-Polycarboxylic acid-
The polyvalent carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include divalent carboxylic acids and trivalent or higher carboxylic acids.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, speric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid and 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; and the like, and further include anhydrides thereof and lower (C1 to C3) alkyl esters thereof.
Examples of the trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid and the like, and their anhydrides and these. Lower alkyl (1 to 3 carbon atoms) alkyl ester and the like.
In addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the polycarboxylic acid may include a dicarboxylic acid having a sulfonic acid group. Further, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid having a double bond may be contained. These may be used alone or in combination of two or more.
The crystalline polyester resin is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester resin preferably has a constituent unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a constituent unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. .. By doing so, the crystallinity is high and the sharp melt property is excellent, which is preferable in that excellent low-temperature fixability can be exhibited.
The melting point of the crystalline polyester resin is appropriately selected depending on the intended purpose without any limitation, but it is preferably 60°C or higher and 80°C or lower. If the melting point is lower than 60°C, the crystalline polyester resin may be easily melted at a low temperature and the heat-resistant storage stability of the toner may be deteriorated. If the melting point is higher than 80°C, the crystalline polyester resin may be heated by heat during fixing. Insufficient melting may lower the low temperature fixability.
The molecular weight of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, those having a sharp molecular weight distribution and low molecular weight have excellent low-temperature fixability and many low molecular weight components. From the viewpoint that the heat-resistant storage stability is lowered, the soluble content of orthodichlorobenzene in the crystalline polyester resin has a weight average molecular weight (Mw) of 3,000 to 30,000 and a number average molecular weight (Mn) in GPC measurement. It is preferably 1,000 to 10,000 and Mw/Mn 1.0 to 10. Furthermore, it is preferable that the weight average molecular weight (Mw) is 5,000 to 15,000, the number average molecular weight (Mn) is 2,000 to 10,000, and Mw/Mn is 1.0 to 5.0.

The acid value of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the purpose, but in order to achieve the desired low-temperature fixability from the viewpoint of the affinity between the paper and the resin. 5 mgKOH/g or more is preferable, and 10 mgKOH/g or more is more preferable. On the other hand, in order to improve the high temperature offset resistance, it is preferably 45 mgKOH/g or less.
The hydroxyl value of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. In order to achieve the desired temperature fixing property and good charging characteristics, 0 mgKOH is used. /G to 50 mgKOH/g is preferable, and 5 mgKOH/g to 50 mgKOH/g is more preferable.
The molecular structure of the crystalline polyester resin can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc., in addition to NMR measurement by a solution or solid. A simple method is to detect a crystalline polyester resin having an absorption at 965±10 cm ⁻¹ or 990±10 cm ⁻¹ based on δCH (out-of-plane bending vibration) of an olefin in an infrared absorption spectrum.
The content of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 parts by mass to 20 parts by mass with respect to 100 parts by mass of the toner, and 5 parts by mass. -15 parts by mass is more preferable. If the content is less than 3 parts by mass, the low temperature fixability may be poor due to insufficient sharp melt formation by the crystalline polyester resin, and if it exceeds 20 parts by mass, the heat resistant storage stability may be deteriorated. In addition, fogging of an image may easily occur. When the content is within the more preferable range, it is advantageous in that it is excellent in high image quality and low temperature fixability.

<Other toner constituents>
Examples of other components include a release agent, a colorant, a charge control agent, an external additive, a cleaning property improver, and a magnetic material.

-Release agent-
The release agent is not particularly limited and can be appropriately selected from known release agents. Examples of release agents for waxes and waxes include plant waxes such as carnauba wax, cotton wax, and wax wax rice; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and celsin; paraffin. , Petroleum waxes such as microcrystalline and petrolatum; and other natural waxes.
In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene and polypropylene; synthetic waxes such as esters, ketones and ethers;
Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride, and chlorinated hydrocarbons; low molecular weight crystalline polymer resins such as poly-n-stearyl methacrylate and poly-n. -A homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate); a crystalline polymer having a long side chain alkyl group, or the like may be used. Good.
Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax and polypropylene wax are preferable.
The melting point of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60° C. or higher and 80° C. or lower. When the melting point is 60° C. or higher, the release agent is easily melted at a low temperature and the problem of poor heat resistant storage stability can be prevented. When the melting point is 80° C. or lower, even when the resin melts and is in the fixing temperature range, the release agent is not sufficiently melted to cause fixing offset, which prevents a problem of image loss. it can.
The content of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 parts by mass to 10 parts by mass and preferably 3 parts by mass to 8 parts by mass with respect to 100 parts by mass of the toner. The mass part is more preferable. When the content is 2 parts by mass or more, problems of high-temperature offset resistance during fixing and low-temperature fixability can be effectively prevented, and when it is 10 parts by mass or less, heat resistant storage stability is deteriorated. And the problem that image fogging easily occurs can be effectively prevented. When the content is within the above more preferable range, it is advantageous in improving image quality and fixing stability.

-Colorant-
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow and yellow. Iron oxide, loess, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), balkan fast. Yellow (5G, R), tartrazine lake, quinoline yellow lake, anthrazan yellow BGL, isoindolinone yellow, red iron oxide, red lead, lead vermilion, cadmium red, cadmium mercury red, antimon vermilion, permanent red 4R, para red, phi. Saleyd, Parachlor Ortho Nitroaniline Red, Resor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G , Resor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine. Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkali Blue Lake, Peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine blue, navy blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, Manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green Examples include lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
The content of the colorant is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 part by mass to 15 parts by mass, and preferably 3 parts by mass to 10 parts by mass with respect to 100 parts by mass of the toner. Parts are more preferred.

The colorant can also be used as a masterbatch compounded with a resin. Examples of the resin to be manufactured or kneaded with the masterbatch include, in addition to the above-mentioned amorphous polyester resin, polymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and the like or substituted polymers thereof; styrene-p. -Chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene- Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethacrylic acid Methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer Styrene-based copolymers such as polymer and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide , Polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used alone or in combination of two or more.
The masterbatch can be obtained by mixing a resin for a masterbatch and a colorant by applying a high shearing force and kneading the mixture to obtain a masterbatch. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Further, a method of so-called flushing method in which an aqueous paste containing water of a colorant is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and water and an organic solvent component are also removed. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three roll mill is preferably used.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdic acid chelate pigments, rhodamine dyes, and alkoxys. -Based amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), alkylamide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, and salicylic acid derivative metal salt, etc. Can be mentioned. Specifically, the Nigrosine dye Bontron 03, the quaternary ammonium salt Bontron P-51, the metal-containing azo dye Bontron S-34, the oxynaphthoic acid metal complex E-82, and the salicylic acid metal complex E-. 84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Industry Co., Ltd.), TP-302, TP-415 (above, manufactured by Hodogaya Chemical Industry Co., Ltd.) of a quaternary ammonium salt molybdenum complex, LRA- 901, a boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. Is mentioned.
The content of the charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 part by mass to 10 parts by mass with respect to 100 parts by mass of the toner, and 0.2 More preferably, it is from 5 parts by mass to 5 parts by mass. When the content is 10 parts by mass or less, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, and the fluidity of the developer is lowered. Also, it is possible to prevent the problem that the image density is lowered. These charge control agents can be melt-kneaded together with the masterbatch and the resin and then dissolved and dispersed, or, of course, may be added when directly dissolved or dispersed in an organic solvent, or fixed after the toner particles are prepared on the toner surface. May be.

-External additive-
The external additive is not particularly limited and may be appropriately selected depending on the purpose, but particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. The hydrophobized fine particles can be obtained by treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane.
Examples of the hydrophobized silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.).
Examples of the hydrophobized titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (Fuji Titanium Industry Co., Ltd.). (Manufactured by corporation), MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation), and the like.
The content of the external additive is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass of the toner, and 0.3 It is more preferably 3 parts by mass to 3 parts by mass.

<Characteristics of toner>
The toner preferably has a glass transition temperature (Tg1st) in the first temperature rise of differential scanning calorimetry (DSC) of 20° C. or higher and 50° C. or lower.
The toner of the present invention has a lower Tg than conventional toners. However, since the amorphous polyester resin, which is a low Tg component, in the toner is non-linear, the toner of the present invention can maintain heat resistant storage stability. In particular, when the amorphous polyester resin has a urethane bond or a urea bond having a high cohesive force, the effect of retaining the heat resistant storage stability becomes more remarkable.
The toner has a glass transition temperature (Tg1st) of 20° C. or more and 50° C. or less in the first temperature rise of differential scanning calorimetry (DSC), and a glass transition temperature (Tg2nd) of the second temperature rise is 0° C. or more and 30° C. The following is good. The difference (Tg1st-Tg2nd) between the glass transition temperature (Tg1st) at the first temperature increase and the glass transition temperature (Tg2nd) at the second temperature increase in the differential scanning calorimetry (DSC) of the toner is not particularly limited. The temperature can be appropriately selected according to the purpose, but it is preferably 10°C or higher. The upper limit of the difference is appropriately selected depending on the intended purpose without any limitation, but it is preferably 50°C or lower.
When the crystalline polyester resin is used in the toner of the present invention, the crystalline polyester resin which was present in an incompatible state before heating (before the first temperature increase) and the amorphous polyester resin are heated after heating. (After the first temperature rise) means to be in a compatible state.
When Tg1st is 20° C. or higher, problems such as deterioration in heat resistant storage stability, blocking in the developing machine, and filming on the photoconductor can be prevented, and when Tg1st is 50° C. or lower, low temperature fixing of the toner is performed. It is possible to prevent deterioration of sex. If the Tg2nd is 0° C. or higher, it is possible to prevent the problem of the paper discharge blocking resistance of the fixed image (printed matter) being reduced, and if it is 30° C. or lower, sufficient low temperature fixability and glossiness cannot be obtained. Can prevent problems.
The volume average particle diameter of the toner is appropriately selected depending on the intended purpose without any limitation, but it is preferably 3 μm or more and 7 μm or less. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Further, it is preferable to contain a component having a volume average particle diameter of 2 μm or less in an amount of 1 to 10% by number.

<<Calculation method and analysis method of various characteristics of toner and toner constituents>>
Although the Tg, acid value, hydroxyl value, molecular weight, and melting point of the amorphous polyester resin, the crystalline polyester resin, and the release agent may be measured by themselves, they may be gel permeated from the actual toner. The SP value, Tg, molecular weight, melting point, and mass ratio of the constituents may be calculated by performing separation by chromatography (GPC) or the like and adopting the analytical method described below for each separated component.
The weight average molecular weight Mw of the toner and the resin is obtained by measuring the THF-soluble content of the resin with a GPC measuring device GPC-150C (manufactured by Waters). KF801 to 807 (manufactured by Showdex) is used for the column, and RI (refractive index) detector is used for the detector.
Separation of each component by GPC can be performed, for example, by the following method.
In GPC measurement using THF (tetrahydrofuran) as a mobile phase, the eluate is fractionated by a fraction collector or the like, and the fractions corresponding to the desired molecular weight portion in the total integration of the elution curve are summarized.

The concentrated eluate is concentrated and dried by an evaporator and the like, and then the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF and ¹ H-NMR measurement is performed. The constituent monomer ratio of is calculated.
As another method, after concentrating the eluate, hydrolysis is performed with sodium hydroxide or the like, and the decomposition product is qualitatively and quantitatively analyzed by high performance liquid chromatography (HPLC) or the like to calculate the constituent monomer ratio.
In the case where the toner production method forms toner base particles while producing an amorphous polyester resin by an elongation reaction and/or a crosslinking reaction between the non-linear reactive precursor and the curing agent, May be separated from the actual toner by GPC or the like to determine the Tg or the like of the amorphous polyester resin. Alternatively, the elongation reaction between the non-linear reactive precursor and the curing agent and/or Alternatively, an amorphous polyester resin may be synthesized by a crosslinking reaction, and Tg or the like may be measured from the synthesized amorphous polyester resin.

<<<Toner Component Separating Means>>>>
An example of means for separating each component when analyzing the toner will be described in detail.
First, 1 g of the toner is put into 100 mL of THF, and a soluble liquid in which soluble components are dissolved is obtained while stirring at 25° C. for 30 minutes.
This is filtered through a membrane filter having an opening of 0.2 μm to obtain a THF-soluble component in the toner.
Then, this is dissolved in THF to prepare a sample for GPC measurement, and the sample is injected into GPC used for measuring the molecular weight of each resin described above.
On the other hand, a fraction collector is placed at the eluate outlet of the GPC, and the eluate is collected at each predetermined count, and the eluate is collected every 5% in area ratio from the elution start of the elution curve (rise of the curve). To get
Then, for each eluate, 30 mg of sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance.
The solution was filled in a glass tube for NMR measurement having a diameter of 5 mm, and a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.) was used to carry out integration 128 times at a temperature of 23° C. to 25° C. to obtain a spectrum. ..
The monomer composition such as the amorphous polyester resin and the crystalline polyester resin contained in the toner, and the composition ratio can be determined from the peak integration ratio of the obtained spectrum.
For example, peaks are assigned as follows, and the component ratio of the constituent monomers is determined from the respective integral ratios.
Peak attribution is, for example,
Approximately 8.25 ppm: Derived from the benzene ring of trimellitic acid (for one hydrogen)
Around 8.07 ppm to 8.10 ppm: Derived from benzene ring of terephthalic acid (for 4 hydrogens)
Around 7.1 ppm to 7.25 ppm: derived from the benzene ring of bisphenol A (4 hydrogens)
Around 6.8 ppm: Bisphenol A derived from benzene ring (4 hydrogens) and fumaric acid derived from double bond (2 hydrogens)
Around 5.2 ppm to 5.4 ppm: bisphenol A propylene oxide adduct derived from methine (one hydrogen)
3.7 ppm to 4.7 ppm or so: bisphenol A propylene oxide adduct derived from methylene (2 hydrogens) and bisphenol A ethylene oxide adduct derived from methylene (4 hydrogens)
Around 1.6 ppm: Derived from the methyl group of bisphenol A (6 hydrogens)
Can be
From these results, for example, the extract recovered in the fraction in which the amorphous polyester resin accounts for 90% or more can be treated as the amorphous polyester resin.
Similarly, the extract recovered in the fraction in which the crystalline polyester resin accounts for 90% or more can be treated as the crystalline polyester resin.

<<Measuring method of melting point and glass transition temperature (Tg)>>
The melting point and glass transition temperature (Tg) in the present invention can be measured using, for example, a DSC system (differential scanning calorimeter) (“Q-200”, manufactured by TA Instruments).
Specifically, the melting point and glass transition temperature of the target sample can be measured by the following procedure.
First, about 5.0 mg of the target sample is placed in a sample container made of aluminum, the sample container is placed on a holder unit, and set in an electric furnace. Next, in a nitrogen atmosphere, heating is performed from −80° C. to 150° C. at a heating rate of 10° C./min (first heating). Then, the temperature is decreased from 150° C. to −80° C. at a temperature decrease rate of 10° C./min, and further heated to 150° C. at a temperature increase rate of 10° C./min (second temperature increase). In each of the first temperature increase and the second temperature increase, a DSC curve is measured using a differential scanning calorimeter (“Q-200”, manufactured by TA Instruments).
From the obtained DSC curve, the analysis program in the Q-200 system can be used to select the DSC curve during the first temperature increase, and the glass transition temperature of the target sample during the first temperature increase can be determined. Similarly, the DSC curve at the time of the second temperature increase can be selected to determine the glass transition temperature of the target sample at the second temperature increase.
Further, from the obtained DSC curve, the DSC curve at the time of the first heating is selected by using the analysis program in the Q-200 system, and the endothermic peak top temperature at the first heating of the target sample is determined as the melting point. You can Similarly, the DSC curve at the time of the second temperature increase is selected, and the endothermic peak top temperature at the second temperature increase of the target sample is determined as the melting point. The glass transition temperature at the time of temperature increase is Tg1st, and the glass transition temperature at the time of the second temperature increase is Tg2nd.
In addition, in the present specification, the glass transition temperature and melting point of the other components such as the amorphous polyester resin, the crystalline polyester resin, and the mold release agent are the second temperature increase unless otherwise specified. The endothermic peak top temperature and Tg at the time are defined as the melting point and Tg of each target sample.

<About toner manufacturing method>
It is considered that the metal complex or salt of the aromatic carboxylic acid derivative takes a cross-linking structure with the polyester resin in the toner when the temperature rises, and increases the molecular weight of the binder resin present on the toner surface to cure the toner surface. Let
In order to attach the metal complex or salt of the aromatic carboxylic acid derivative to the toner surface, the temperature is set to 70° C. or lower. When the temperature is 70° C. or higher, the crosslinking reaction with the toner proceeds in this adhesion step, the storage elastic modulus of the toner at the time of temperature increase increases, and the low temperature fixability is impaired.
In order to effectively cure the toner surface without impairing the low-temperature fixability, it is preferable that the metal complex or salt of the aromatic carboxylic acid derivative is attached only to the toner surface.
As a method of attaching the metal compound to the toner surface, there is a method of attaching it from the aqueous phase. Since the polymerized toner has a step of being dispersed in the aqueous phase during the production of the toner, when the metal complex or salt of the aromatic carboxylic acid derivative is applied to the surface of the polymerized toner, it is attached from the aqueous phase. The method is suitable. As a method of adhering from the aqueous phase, a finely dispersed solution of a metal complex of an aromatic carboxylic acid derivative or a salt is put in an aqueous phase in which the toner is present, agglomerated with an acid or salt, and adhered to the toner surface. You can
That is, when the toner is manufactured, a dispersion liquid in which particles of the metal complex or salt of the aromatic carboxylic acid derivative are dispersed to a volume average particle size of 1.0 μm or less is used as a metal complex or salt of the aromatic carboxylic acid derivative. It is preferable to have a step of adding to a dispersion liquid in which particles not containing are dispersed.
In addition, after the particles of the metal complex or salt of the aromatic carboxylic acid derivative are adhered to the toner surface, the temperature of the aqueous phase is increased (for example, 40 to 70 to increase the adhesion of the particles to the toner surface). It is better to keep the state). This enables stable immobilization.
In particular, by attaching the metal complex or salt of the aromatic carboxylic acid derivative to the toner surface instead of dispersing it inside the toner, the cross-linking reaction by the metal complex or salt of the aromatic carboxylic acid derivative on the fixed image surface is often caused. Occurs, and the effect of preventing paper discharge blocking and improving the image storability is enhanced.

The method for producing the toner is not particularly limited and may be appropriately selected depending on the purpose such as a polymerization method and a pulverization method. The toner contains the amorphous polyester resin and the crystalline polyester resin. Further, if necessary, it is preferable to granulate by dispersing an oil phase containing the release agent, the colorant and the like in an aqueous medium.
Further, the toner contains a polyester resin which is a prepolymer having a urethane bond and a urea bond as the amorphous polyester resin, a polyester resin having no urethane bond and a urea bond, and the crystalline polyester resin, and further, if necessary. Accordingly, it is more preferable to granulate by dispersing an oil phase containing the curing agent, the release agent, the colorant and the like in an aqueous medium.
As an example of the method for producing the toner, a known dissolution suspension method can be mentioned. As an example of the method for producing the toner, a method for forming toner base particles while extending an amorphous polyester resin by an extension reaction and/or a crosslinking reaction between the prepolymer and the curing agent will be shown below. In such a method, preparation of an aqueous medium, preparation of an oil phase containing a toner material, emulsification or dispersion of the toner material, and removal of an organic solvent are carried out.
However, in the method for producing a toner of the present invention, further, as described below, preparation of a fine dispersion of a metal complex or salt of an aromatic carboxylic acid derivative or surface attachment of a metal complex or salt of an aromatic carboxylic acid derivative. It is characterized by having the process of.
Each step will be described below.

-Preparation of aqueous medium (aqueous phase)-
The aqueous medium can be prepared, for example, by dispersing resin particles in the aqueous medium. The amount of the resin particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the aqueous medium. ..
The aqueous medium is appropriately selected depending on the intended purpose without any limitation, and examples thereof include water, a solvent miscible with water, and a mixture thereof. These may be used alone or in combination of two or more. Of these, water is preferable.
The solvent miscible with water is appropriately selected depending on the intended purpose without any limitation, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. The alcohol is appropriately selected depending on the intended purpose without any limitation, and examples thereof include methanol, isopropanol, and ethylene glycol. The lower ketones are appropriately selected depending on the intended purpose without any limitation, and examples thereof include acetone and methyl ethyl ketone.

-Preparation of oil phase-
The oil phase containing the toner material is prepared by the amorphous polyester resin which is a prepolymer having a urethane bond and a urea bond, the polyester resin having no urethane bond and a urea bond, and the crystalline polyester resin. It is possible to carry out by dissolving or dispersing a toner material containing at least and, if necessary, the curing agent, the release agent, the colorant and the like in an organic solvent.
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably an organic solvent having a boiling point of less than 150° C. from the viewpoint of easy removal.
The organic solvent having a boiling point of less than 150° C. is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, and 1 , 1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like. These may be used alone or in combination of two or more.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is more preferable.

-Preparation of metal complex of aromatic carboxylic acid derivative or fine dispersion of salt-
A method may be considered in which a metal complex or salt of an aromatic carboxylic acid derivative (for example, salicylic acid derivative salt is described below as an example) is prepared as fine particles, and the particles are attached to the surface in the form of particles by aggregating salt or pH adjustment.
The salicylic acid derivative salt as fine particles is obtained as a precipitate by first mixing a salicylic acid derivative and a salt of a metal that forms a coordinate bond with the salicylic acid derivative in water. At this time, it is preferable to carry out the reaction under basic condition because of deprotonation of the carboxyl group of the salicylic acid derivative.
The salicylic acid derivative salt obtained as a precipitate is filtered and dispersed again in water. A surfactant is added to this to prevent reaggregation, and the mixture is pulverized by a bead mill or the like to obtain fine particles.
Here, the particles of the metal complex or salt of the aromatic carboxylic acid derivative may be dispersed to a volume average particle size of 1.0 μm or less.

-Emulsification or dispersion-
The emulsification or dispersion of the toner material can be carried out by dispersing an oil phase containing the toner material in the aqueous medium. Then, when the toner material is emulsified or dispersed, the curing agent and the prepolymer can undergo an elongation reaction and/or a crosslinking reaction.
The reaction conditions (reaction time, reaction temperature) for producing the prepolymer are not particularly limited and may be appropriately selected depending on the combination of the curing agent and the prepolymer.
The reaction time is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours.
The reaction temperature is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0°C to 150°C, more preferably 30°C to 50°C.
The method for stably forming the dispersion in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the toner material is dissolved or dispersed in a solvent in the aqueous medium phase. Examples of the method include adding the oil phase prepared by the above method, and dispersing with an shearing force.
The disperser for the dispersion is not particularly limited and may be appropriately selected according to the purpose. For example, a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser. , An ultrasonic disperser and the like.
Among these, the high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.
When the high-speed shearing disperser is used, conditions such as the number of revolutions, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose.
The rotation speed is appropriately selected depending on the intended purpose without any limitation, but it is preferably 1,000 rpm to 30,000 rpm, more preferably 5,000 rpm to 20,000 rpm.
The dispersion time is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.1 minutes to 5 minutes in the case of a batch method.
The dispersion temperature is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0°C to 50°C and more preferably 30°C to 45°C under pressure. Generally, the higher the dispersion temperature, the easier the dispersion.
The amount of the aqueous medium used when emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose, but is 50 parts by mass to 2 parts by mass with respect to 100 parts by mass of the toner material. 1,000 parts by mass is preferable, and 100 parts by mass to 1,000 parts by mass is more preferable.
When the amount of the aqueous medium used is 50 parts by mass or more, it is possible to prevent the problem that the toner material is not well dispersed and the toner base particles having a predetermined particle diameter cannot be obtained. When the amount is 000 parts by mass or less, the problem of increased production cost can be prevented.
When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets, forming a desired shape and sharpening the particle size distribution. ..
The dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include surfactants, sparingly water-soluble inorganic compound dispersants, and polymeric protective colloids. These may be used alone or in combination of two or more. Among these, the surfactant is preferable.
The surfactant is appropriately selected depending on the intended purpose without any limitation, and examples thereof include anionic surfactant, cationic surfactant, nonionic surfactant, and amphoteric surfactant. be able to.
The anionic surfactant is appropriately selected depending on the intended purpose without any limitation, and examples thereof include alkylbenzene sulfonate, α-olefin sulfonate, and phosphoric acid ester. Among these, those having a fluoroalkyl group are preferable.

-Removal of organic solvent and surface attachment of metal complex or salt of aromatic carboxylic acid derivative-
The method for removing the organic solvent from the dispersion liquid such as the emulsified slurry is not particularly limited and may be appropriately selected depending on the intended purpose. For example, by gradually raising the temperature of the entire reaction system, oil droplets Examples thereof include a method of evaporating the organic solvent and a method of spraying the dispersion liquid in a dry atmosphere to remove the organic solvent in the oil droplets.
The organic solvent is removed to obtain a dispersion slurry. The dispersed slurry is washed, dried, etc., and then the obtained filter cake is dispersed to obtain a toner slurry liquid.
Subsequent to the washing and drying steps, a step of adhering a metal complex or salt of an aromatic carboxylic acid derivative serving as a cross-linking agent on the toner surface is performed. Particles containing a metal complex or salt of an aromatic carboxylic acid derivative dispersed to a volume average particle size of 1.0 μm or less, and containing the metal complex or salt of the aromatic carboxylic acid derivative in the dispersion. Is added to the slurry liquid of the dispersed toner.
As a metal complex or salt of an aromatic carboxylic acid derivative, for example, when a salicylic acid derivative salt is attached, the method of attaching the salicylic acid derivative salt may be particulate attachment. The prepared dispersion liquid of salicylic acid derivative salt particles and an acid or a salt as an aggregating agent are added to the toner slurry liquid to adhere the salicylic acid derivative salt particles to the surface of the toner. In order to strengthen the adhesive force, it is preferable to subsequently carry out the heat treatment in a temperature range where the crosslinking reaction with the binder resin does not occur.
The same applies to hydroxynaphthoate.
Next, toner base particles are obtained by filtering, drying and classifying the toner slurry liquid in which the particles of the metal complex or salt of the aromatic carboxylic acid derivative adhere to the surface of the toner.
The obtained toner base particles may be mixed with particles such as the external additive and the charge control agent. At this time, by applying a mechanical impact force, it is possible to suppress detachment of particles such as the external additive from the surface of the toner base particles.
The method of applying the mechanical impact force is not particularly limited and may be appropriately selected depending on the purpose. For example, a method of applying the impact force to the mixture using a blade rotating at high speed, in a high-speed air stream A method of charging the mixture into and accelerating the particles to collide with each other or with an appropriate collision plate can be mentioned.
The apparatus used in the method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples of the device include a lowering device, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.
Thus, toner particles having a volume average particle diameter of 5.5 μm to 7 μm are obtained.

(Developer)
The developer of the present invention contains at least the toner and optionally other components such as a carrier, if necessary.
Therefore, it is possible to stably form a high-quality image with excellent transferability and chargeability. The developer may be a one-component developer or a two-component developer, but when it is used in a high-speed printer or the like that is compatible with the recent improvement in information processing speed, it has a long life. A two-component developer is preferred because of its improved properties.
When the developer is used as a one-component developer, the toner particle size does not fluctuate even if the balance of the toner is achieved, and the filming of the toner to the developing roller and a member such as a blade for thinning the toner Fusing of the toner to the toner is small, and good and stable developability and image can be obtained even after a long-term stirring in the developing device.
When the developer is used as a two-component developer, the toner particle size does not fluctuate even if the toner balance is maintained for a long period of time, and good and stable developability and an image are obtained even when the developer is agitated for a long period of time. can get.

<Career>
The carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably one having a core material and a resin layer coating the core material.
-Core material-
The material for the core material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 50 emu/g to 90 emu/g manganese-strontium-based material, 50 emu/g to 90 emu/g manganese Examples include magnesium-based materials. Further, in order to secure 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 emu/g to 120 emu/g. In addition, since the impact of the developer in the spiked state on the photoconductor can be relaxed, which is advantageous for high image quality, a low-magnetization material such as 30 emu/g to 80 emu/g of a copper-zinc system is used. Is preferred.
These may be used alone or in combination of two or more.
The volume average particle diameter of the core material is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 μm to 150 μm, more preferably 40 μm to 100 μm. When the volume average particle diameter is 10 μm or more, it is possible to prevent the problem that the amount of fine powder in the carrier is increased and the magnetization per particle is reduced to cause carrier scattering, and when it is 150 μm or less, It is possible to prevent the problem that the surface area is reduced and the toner may scatter, and in full color where there are many solid portions, reproduction of the solid portions may be particularly poor.
When the toner is used as a two-component developer, it may be mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the purpose, but is 90 parts by mass to 98 parts by mass with respect to 100 parts by mass of the two-component developer. Parts are preferred, and 93 parts by mass to 97 parts by mass are more preferred.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component developing method, a non-magnetic one-component developing method and a two-component developing method.

(Toner storage unit)
The toner containing unit in the present invention refers to a unit containing toner in a unit having a function of containing toner. Here, examples of the toner storage unit include a toner storage container, a developing device, a process cartridge, and the like.
The toner storage container refers to a container that stores toner.
The developing device refers to one having a means for accommodating and developing toner.
The process cartridge is a cartridge in which at least an image bearing member and a developing unit are integrated with each other, the toner is contained, and the cartridge is detachable from the image forming apparatus. The process cartridge may further include at least one selected from a charging unit, an exposing unit, and a cleaning unit.
By mounting the toner storage unit of the present invention on an image forming apparatus to form an image, image formation is carried out by utilizing the characteristics of the toner having both low temperature fixing property, discharge blocking resistance, and image storability. be able to.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention has at least an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further has other means as required.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be suitably performed by the image forming apparatus, the electrostatic latent image forming step can be suitably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. And other steps can be suitably performed by the other means.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and can be appropriately selected from known materials. Examples of the material include inorganic photoconductors such as amorphous silicon and selenium. , Organic photoconductors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.

<Electrostatic latent image forming means>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples include means having at least a charging member that charges the surface of the electrostatic latent image carrier and an exposure member that exposes the surface of the electrostatic latent image carrier imagewise.

-Charging member and charging-
The charging member is not particularly limited and may be appropriately selected according to the purpose. For example, a contact charger known per se provided with a conductive or semiconductive roller, brush, film, rubber blade, or the like. , Non-contact chargers using corona discharge such as Corotron and Scorotron.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.

The shape of the charging member may be any shape such as a magnetic brush or a fur brush other than the roller, and can be selected according to the specifications and the shape of the image forming apparatus.
The charging member is not limited to the contact type charging member, but it is preferable to use the contact type charging member because an image forming apparatus in which ozone generated from the charging member is reduced can be obtained.

-Exposure member and exposure-
The exposure member is appropriately selected depending on the intended purpose without any limitation, as long as it can expose the surface of the electrostatic latent image carrier charged by the charging member to an image to be formed. Examples thereof include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
The light source used for the exposure member is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), and a semiconductor laser. (LD), electroluminescence (EL), and other luminescent materials in general.
Further, various filters such as a sharp cut filter, a bandpass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
The exposure can be performed, for example, by imagewise exposing the surface of the electrostatic latent image carrier using the exposure member.
In addition, in the present invention, a back light system may be adopted in which the back surface of the electrostatic latent image carrier is imagewise exposed.

<Developing means>
The developing means is not particularly limited as long as it is a developing means provided with toner, which develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image, and may be used depending on the purpose. Can be appropriately selected.

As the developing means, a stirrer for frictionally stirring the toner to charge it, and a magnetic field generating means fixed inside are provided, and the surface of the developing means carries a developer containing the toner and is rotatable. A developing device having a body is preferred.

<Other means>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a charge eliminating means, a recycling means, and a control means.

-Transfer means-
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. An embodiment having a primary transfer means for forming a transfer image and a secondary transfer means for transferring the composite transfer image onto a recording medium is preferable.
Here, when the image to be secondarily transferred onto the recording medium is a color image composed of toners of a plurality of colors, the transfer means sequentially superimposes the toners of the respective colors on the intermediate transfer member, and the intermediate transfer is performed. An image can be formed on the body, and the image on the intermediate transfer body can be secondarily transferred onto the recording medium all at once by the intermediate transfer unit.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt is suitable.

It is preferable that the transfer unit (the primary transfer unit or the secondary transfer unit) includes at least a transfer unit that peels and charges the visible image formed on the photoconductor to the recording medium side. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer the unfixed image after development, and can be appropriately selected according to the purpose. A PET base or the like can also be used.

-Fixing means-
The fixing unit is not particularly limited as long as it is a unit that fixes the transfer image transferred to the recording medium, and can be appropriately selected according to the purpose, but a known heating and pressing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, for each color toner, the recording medium is used. May be carried out each time it is transferred to, or may be carried out at the same time in the state where the toners of respective colors are laminated.
The fixing step can be performed by the fixing unit.
The heating by the heating and pressing member is usually preferably 80°C to 200°C.
In the present invention, a known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

The surface pressure in the fixing step is not particularly limited and may be appropriately selected depending on the intended ^purpose, it is preferably ^{10N / cm 2 ~80N / cm 2} .

-Cleaning means-
The cleaning unit is not particularly limited as long as it is a unit that can remove the toner remaining on the photoconductor, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, Examples include magnetic roller cleaners, blade cleaners, brush cleaners, and web cleaners.

− Static elimination means −
The charge removing unit is not particularly limited as long as it is a unit that applies a charge removing bias to the photoconductor to remove the charge, and can be appropriately selected according to the purpose, and examples thereof include a charge removing lamp.

-Recycling means-
The recycle unit is not particularly limited as long as it is a unit that recycles the toner removed in the cleaning step to the developing device, and can be appropriately selected according to the purpose. Can be mentioned.

Next, one mode for carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG.
The image forming apparatus 1 is a printer, but the image forming apparatus is not particularly limited as long as it can form an image using toner of a copying machine, a facsimile, a multi-function peripheral, or the like.
The image forming apparatus 1 includes a paper feeding unit 210, a conveying unit 220, an image forming unit 230, a transfer unit 240, and a fixing device 250.
The paper feeding unit 210 includes a paper feeding cassette 211 in which papers P to be fed are stacked, and a paper feeding roller 212 that feeds the papers P stacked in the paper feeding cassette 211 one by one.
The transport unit 220 sandwiches the roller 221 that transports the paper P fed by the paper feed roller 212 toward the transfer unit 240 and the leading end of the paper P transported by the roller 221, and waits for the paper P to reach a predetermined position. A pair of timing rollers 222 for sending to the transfer section 240 at a timing and a paper discharge roller 223 for discharging the paper P on which the color toner image is fixed to the paper discharge tray 224 are provided.
The image forming unit 230 has an image forming unit Y that forms an image using a developer having a yellow toner and a cyan toner at a predetermined interval in order from the left to the right in the drawing. The image forming unit C using the developer, the image forming unit M using the developer having magenta toner, the image forming unit K using the developer having black toner, and the exposure unit 233 are provided.
In addition, when an arbitrary image forming unit is shown among the image forming units (Y, C, M, K), it is referred to as an image forming unit.
The developer has toner and carrier.
The four image forming units (Y, C, M, K) are different from each other only in the developer used, and have substantially the same mechanical structure.
The transfer unit 240 includes a driving roller 241 and a driven roller 242, an intermediate transfer belt 243 that can rotate counterclockwise in the drawing with the driving of the driving roller 241, and an intermediate transfer belt 243 sandwiched therebetween. A primary transfer roller (244Y, 244C, 244M, 244K) provided so as to face the body drum 231 and a secondary opposite roller provided so as to face the intermediate transfer belt 243 at the transfer position of the toner image onto the paper. 245 and a secondary transfer roller 246.
The fixing device 250 is provided with a heater therein, and is provided with a pressure roller 252 that forms a nip by rotatably pressing the fixing belt 251 that heats the paper P to the fixing belt 251. .. As a result, heat and pressure are applied to the color toner image on the paper P, and the color toner image is fixed. The paper P on which the color toner image is fixed is discharged to the paper discharge tray 224 by the paper discharge roller 223, and a series of image forming processes is completed.

<Process cartridge>
The process cartridge relating to the present invention is detachably formed in various image forming apparatuses, and develops the photoconductor carrying the electrostatic latent image and the electrostatic latent image carried on the photoconductor with the developer of the present invention. And at least a developing means for forming a toner image. The process cartridge of the present invention may further include other means, if necessary.
The developing means has at least a developer accommodating portion for accommodating the developer of the present invention and a developer carrier for carrying and transporting the developer accommodated in the developer accommodating portion. The developing means may further include a regulating member for regulating the thickness of the carried developer.
FIG. 5 shows an example of the process cartridge according to the present invention. The process cartridge 110 includes the photosensitive drum 10, the corona charger 58, the developing device 40, the transfer roller 80, and the cleaning device 90.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples. Unless otherwise specified, "%" means "mass %", and "part" means "part by mass".
Each measured value in the following examples was measured by the method described above.

<Synthesis of Amorphous Polyester Resin A1>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, bisphenol A ethylene oxide 2 mol adduct (BisA-EO), bisphenol A propylene oxide 3 mol adduct (BisA-PO), Trimethylolpropane (TMP), terephthalic acid, and adipic acid are added in a molar ratio of bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, and trimethylol propane (bisphenol A ethylene oxide 2 mol Adduct/bisphenol A propylene oxide 3 mol adduct/trimethylol propane) 38.6/57.9/3.5, and terephthalic acid and adipic acid have a molar ratio (terephthalic acid/adipic acid) of 85. /15, so that OH/COOH, which is the molar ratio of hydroxyl groups to carboxyl groups, is 1.2, and titanium tetraisopropoxide (500 ppm with respect to the resin component) and atmospheric pressure at 230° C. for 8 hours After reacting and further reacting under reduced pressure of 10 mmHg to 15 mmHg for 4 hours, trimellitic anhydride was added to the reaction vessel so as to be 1 mol% with respect to all resin components, and reacted at 180° C. and normal pressure for 3 hours. Quality polyester resin A1] was obtained.

<Synthesis of Amorphous Polyester Resin A2>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, bisphenol A ethylene oxide 2 mol adduct (BisA-EO), bisphenol A propylene oxide 3 mol adduct (BisA-PO), Trimethylolpropane (TMP), terephthalic acid, and adipic acid are added in a molar ratio of bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, and trimethylol propane (bisphenol A ethylene oxide 2 mol). Adduct/bisphenol A propylene oxide 3 mol adduct/trimethylol propane) 38.6/57.9/3.5, and terephthalic acid and adipic acid have a molar ratio (terephthalic acid/adipic acid) of 85. /15, and OH/COOH, which is the molar ratio of hydroxyl groups to carboxyl groups, was 1.2, and was mixed with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 230° C. for 8 hours at atmospheric pressure. After reacting and further reacting under reduced pressure of 10 mmHg to 15 mmHg for 4 hours, trimellitic anhydride was added to the reaction vessel so as to be 3 mol% with respect to all resin components, and reacted at 180° C. under normal pressure for 3 hours. Quality polyester resin A2] was obtained.

<Synthesis of Amorphous Polyester Resin A3>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, bisphenol A ethylene oxide 2 mol adduct (BisA-EO), bisphenol A propylene oxide 3 mol adduct (BisA-PO), Trimethylolpropane (TMP), terephthalic acid, and adipic acid are added in a molar ratio of bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, and trimethylol propane (bisphenol A ethylene oxide 2 mol Adduct/bisphenol A propylene oxide 3 mol adduct/trimethylolpropane) 38.6/57.9/3.5, and terephthalic acid and adipic acid have a molar ratio (terephthalic acid/adipic acid) of 85. /15, so that OH/COOH, which is the molar ratio of hydroxyl groups to carboxyl groups, is 1.2, and titanium tetraisopropoxide (500 ppm with respect to the resin component) and atmospheric pressure at 230° C. for 8 hours After reacting and further reacting under reduced pressure of 10 mmHg to 15 mmHg for 4 hours, trimellitic anhydride was added to the reaction vessel so as to be 0.25 mol% with respect to all resin components, and reacted at 180° C. under normal pressure for 3 hours, Amorphous polyester resin A3] was obtained.

<Synthesis of Prepolymer B>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 97 mol% of 3-methyl-1,5-pentanediol as an alcohol component, 3 mol% of trimethylolpropane (TMP), and adipine as an acid component. The acid was 100 mol% and terephthalic acid was 50 mol %, and the mixture was charged together with titanium tetraisopropoxide (300 ppm relative to the resin component) so that OH/COOH = 1.1. Then, the temperature was raised to 200° C. in about 4 hours, and then raised to 230° C. over 2 hours, and the reaction was performed until the outflow water disappeared. Then, the mixture was further reacted under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate polyester B-1].
Next, in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, [intermediate polyester B-1] and isophorone diisocyanate (IPDI) were used in a molar ratio (isocyanate group of IPDI/hydroxyl group of intermediate polyester). 2.1, and diluted with ethyl acetate to be a 48% ethyl acetate solution, and then reacted at 100° C. for 5 hours to obtain a non-linear polyester resin B [prepolymer B] having a reactive group. It was

<Synthesis of crystalline polyester resin C>
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was charged with sebacic acid and 1,6-hexanediol, and OH/COOH, which was the molar ratio of the hydroxyl group and the carboxyl group. It was charged so as to be 0.9, reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180° C. for 10 hours, then heated to 200° C. and reacted for 3 hours, and further 8.3 kPa A crystalline polyester resin C was obtained by reacting at a pressure of 2 hours for 2 hours.
The physical properties of each resin are shown in Table 1 below.

(Slurry liquid of toner 1)
<Masterbatch (MB) adjustment>
600 parts of water, 500 parts of carbon black (manufactured by Nipex 60 Dexa) and 500 parts of amorphous polyester resin A1 were added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and the mixture was heated at 150° C. using a two-roll mill. After kneading for 30 minutes, the mixture was rolled, cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

<Synthesis of organic fine particle emulsion (fine particle dispersion liquid)>
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of methacrylic acid ethylene oxide adduct sulfuric acid ester (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 138 parts of styrene, 138 parts of methacrylic acid. , And 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white emulsion. After heating, the temperature in the system was raised to 75° C., and the reaction was carried out for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75° C. for 5 hours, and an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-ethylene methacrylic acid ethylene oxide adduct sulfate sodium salt) [fine particles Dispersion] was obtained.
The volume average particle diameter of the [fine particle dispersion] measured by LA-920 (manufactured by HORIBA) was 0.14 μm.

<Preparation of aqueous phase>
2240 parts of water, 80 parts of [fine particle dispersion], 80 parts of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Kasei Co., Ltd.), and 200 parts of ethyl acetate were mixed and stirred to give a milky white color. A liquid was obtained. This was designated as [water phase].

<Preparation of WAX dispersion>
100 parts of ester wax (WEP-3, NOF Corporation, melting point 70° C., acid value 0.1 mgKOH/g) and 400 parts of ethyl acetate were charged as a mold release agent into a container in which a stirring bar and a thermometer were set, and stirred. The temperature was raised to 80° C. and kept at 80° C. for 5 hours, then cooled to 20° C. for 1 hour, and a bead mill (Ultra Visco Mill, manufactured by AIMEX Co., Ltd.) was used to deliver liquid at a rate of 1 kg/hr and a disc. [WAX dispersion liquid] was obtained by dispersing 0.5 mm zirconia beads in an amount of 80% by volume at a peripheral speed of 6 m/sec under the condition of 3 passes.

<Preparation of crystalline polyester resin C dispersion>
100 parts of crystalline polyester resin C and 400 parts of ethyl acetate were placed in a container equipped with a stir bar and a thermometer, heated to 80° C. under stirring, kept at 80° C. for 5 hours, and then heated to 20° C. in 1 hour. After cooling, a bead mill (Ultra Visco Mill, manufactured by AIMEX Co., Ltd.) was used to disperse liquid at a liquid feed rate of 1 kg/hr, a disk peripheral velocity of 6 m/sec, 80% by volume of 0.5 mm zirconia beads and 3 passes. Then, [Crystalline polyester resin C dispersion liquid] was obtained.

<Preparation of oil phase>
[Ethyl acetate] 302 parts, [WAX dispersion 1] 250 parts, [Crystalline polyester resin C dispersion] 500 parts, [Amorphous polyester resin A1] 650 parts, [Masterbatch 1] 100 parts were put in a container. , TK homomixer (manufactured by Tokushu Kiki) for 60 minutes at 5,000 rpm. Then, 300 parts of [prepolymer B in ethyl acetate] and 2 parts of isophoronediamine as a curing agent were added, and mixed for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika) to obtain [oil phase].

<Emulsification/solvent removal>
[Oil phase] was added to a container containing 2,600 parts of [aqueous phase] and mixed with a TK homomixer at a rotation speed of 13,000 rpm for 3 minutes to obtain [emulsified slurry]. At this time, the volume average particle diameter after the dissolution was adjusted to 5.5 μm.
[Emulsified slurry] was put into a container equipped with a stirrer and a thermometer, the solvent was removed at 30° C. for 8 hours, and the mixture was aged at 45° C. for 4 hours to obtain [dispersed slurry].

<Washing/drying>
[Dispersion slurry] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed 12,000 rpm for 10 minutes), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (rotation speed 12,000 rpm for 30 minutes), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed 12,000 rpm for 10 minutes), and then filtered.
(4): Operation of the above (1) to (4), wherein 300 parts of ion-exchanged water is added to the filter cake of (3), mixed with a TK homomixer (rotation speed 12,000 rpm for 10 minutes) and then filtered. Was performed twice to obtain a filter cake. Further, ion-exchanged water was added to the filter cake so that the solid content was 50%, and the mixture was mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes) to obtain a "slurry liquid of toner 1".

(Synthesis of zirconium compound)
<Zirconium complex or salt of salicylic acid derivative>
322.3 g of zirconium oxychloride (octahydrate) is dissolved in 9,677.7 g of ion-exchanged water to prepare an aqueous solution of 0.1 mmol/g. 500.7 g of 3,5-di-t-butylsalicylic acid is dissolved in 7,999.4 g of 1% caustic soda water and 1,535.9 g of ion-exchanged water to prepare a basic 0.1 mmol/g aqueous solution. .. While stirring the zirconium oxychloride aqueous solution, a caustic soda aqueous solution of 3,5-di-t-butylsalicylic acid was gradually mixed to synthesize a zirconium compound A. The zirconium compound A was filtered and washed by repeating redispersion in ion-exchanged water to obtain a filter cake. The filter cake was dried at 45° C. for 48 hours with a circulating air drier to obtain a zirconium compound A.
100 parts of zirconium compound A, 899 parts of ion-exchanged water, and 1 part of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Kasei Co., Ltd.) were mixed, and a bead mill (Ultraviscomill, manufactured by Aimex Co., Ltd.) was mixed. ), a liquid feed rate of 1 kg/hr, a disk peripheral velocity of 6 m/sec, and 80% by volume of 0.5 mm zirconia beads were filled, and dispersion was performed under the condition of 10 passes [Zirconium compound A dispersion liquid (1)]. Got
The volume average particle diameter of the obtained dispersion liquid measured by LA-920 (manufactured by HORIBA) was 0.25 μm.
Dispersion was also performed under the conditions of 7 passes, 6 passes, 3 passes, and 2 passes, respectively, and [dispersion liquid of zirconium compound A (2)], [dispersion liquid of zirconium compound A (3)], and [zirconium A dispersion liquid (4) of compound A and a dispersion liquid (5) of zirconium compound A were obtained.
The volume average particle diameters of the obtained dispersion liquid measured by LA-920 (manufactured by HORIBA) were 0.39 μm, 0.51 μm, 0.99 μm and 1.24 μm, respectively.

<Zirconium complex or salt of hydroxynaphthoic acid derivative>
322.3 g of zirconium oxychloride (octahydrate) is dissolved in 9,677.7 g of ion-exchanged water to prepare an aqueous solution of 0.1 mmol/g. 376.4 g of 3-hydroxy-2-naphthoic acid is dissolved in 7,999.4 g of 1% caustic soda water and 1,535.9 g of ion-exchanged water to prepare a basic 0.1 mmol/g aqueous solution. While stirring the zirconium oxychloride aqueous solution, a caustic soda aqueous solution of 3-hydroxy-2-naphthoic acid was gradually mixed to synthesize a zirconium compound B. The zirconium compound B was filtered and washed by repeating redispersion in ion-exchanged water to obtain a filter cake. The filter cake was dried at 45° C. for 48 hours with a circulating air dryer to obtain a zirconium compound B.
100 parts of zirconium compound B, 899 parts of ion-exchanged water, and 1 part of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Kasei Co., Ltd.) were mixed, and a bead mill (Ultraviscomill, manufactured by Aimex Co., Ltd.) was mixed. ) Was used to carry out dispersion at a liquid feed rate of 1 kg/hr, a disk peripheral speed of 6 m/sec, and 80% by volume of 0.5 mm zirconia beads, and dispersion was carried out under the conditions of 7 passes to obtain [dispersion liquid of zirconium compound B]. ..
The volume average particle diameter of the obtained dispersion liquid measured by LA-920 (manufactured by HORIBA) was 0.40 μm.

(Synthesis of iron(III) compound)
<Iron complex or salt of salicylic acid derivative>
270.3 g of iron(III) chloride (hexahydrate) is dissolved in 9,729.7 g of ion-exchanged water to prepare an aqueous solution of 0.1 mmol/g. 500.7 g of 3,5-di-t-butylsalicylic acid is dissolved in 7,999.4 g of 1% caustic soda water and 1,535.9 g of ion-exchanged water to prepare a basic 0.1 mmol/g aqueous solution. .. While stirring the iron(III) chloride aqueous solution, an aqueous solution of 3,5-di-t-butylsalicylic acid in sodium hydroxide was gradually mixed to synthesize an iron(III) compound C. The iron (III) compound C was filtered and washed by repeating redispersion in ion-exchanged water to obtain a filter cake. The filter cake was dried at 45° C. for 48 hours with a circulating air drier to obtain an iron(III) compound C.
100 parts of iron (III) compound C, 899 parts of ion-exchanged water, and 1 part of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Kasei Co., Ltd.) were mixed, and a bead mill (Ultraviscomyl, (Made by IMEX Co., Ltd.), a liquid transfer rate of 1 kg/hr, a disk peripheral velocity of 6 m/sec, a volume of 0.5 mm zirconia beads was filled at 80% by volume, and dispersion was performed under the conditions of 7 passes [iron (III) compound C Dispersion] was obtained.
The volume average particle diameter of the obtained dispersion liquid measured by LA-920 (manufactured by HORIBA) was 0.38 μm.

(Synthesis of chromium compounds)
<Chromium complex or salt of salicylic acid derivative>
266.5 g of chromium chloride (hexahydrate) is dissolved in 9,733.5 g of ion-exchanged water to prepare an aqueous solution of 0.1 mmol/g. 500.7 g of 3,5-di-t-butylsalicylic acid is dissolved in 7,999.4 g of 1% caustic soda water and 1,535.9 g of ion-exchanged water to prepare a basic 0.1 mmol/g aqueous solution. .. While stirring the chromium chloride aqueous solution, a caustic soda aqueous solution of 3,5-di-t-butylsalicylic acid was gradually mixed to synthesize a chromium compound D. The chromium compound D was filtered and washed by repeating redispersion in ion-exchanged water to obtain a filter cake. The filter cake was dried at 45° C. for 48 hours with a circulating air dryer to obtain a chromium compound D.
100 parts of chromium compound D, 899 parts of ion-exchanged water, and 1 part of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Kasei Co., Ltd.) were mixed, and a bead mill (Ultraviscomill, manufactured by AIMEX Co., Ltd.) was mixed. ) Was used to disperse liquid at a liquid feed rate of 1 kg/hr, a disk peripheral velocity of 6 m/sec, 80% by volume of 0.5 mm zirconia beads, and 7 passes to obtain a dispersion of a chromium compound D. ..
The volume average particle diameter of the obtained dispersion liquid measured by LA-920 (manufactured by HORIBA) was 0.40 μm.

(Synthesis of aluminum compound)
<Aluminum complex or salt of salicylic acid derivative>
241.4 g of aluminum chloride (hexahydrate) is dissolved in 9,758.6 g of ion-exchanged water to prepare an aqueous solution of 0.1 mmol/g. 500.7 g of 3,5-di-t-butylsalicylic acid is dissolved in 7,999.4 g of 1% caustic soda water and 1,535.9 g of ion-exchanged water to prepare a basic 0.1 mmol/g aqueous solution. .. While stirring the aluminum chloride aqueous solution, an aqueous solution of 3,5-di-t-butylsalicylic acid in sodium hydroxide was gradually mixed to synthesize an aluminum compound E. The aluminum compound E was filtered and washed by repeating redispersion in ion-exchanged water to obtain a filter cake. The filter cake was dried at 45° C. for 48 hours with a circulating air dryer to obtain an aluminum compound E.
100 parts of aluminum compound E, 899 parts of ion-exchanged water, and 1 part of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Kasei Co., Ltd.) were mixed, and a bead mill (Ultraviscomill, manufactured by AIMEX Co., Ltd.) was mixed. ) Was used to carry out dispersion under the conditions of 7 kg/80 kg/hr of 0.5 mm zirconia beads at a liquid feed rate of 1 kg/hr, a disk peripheral velocity of 6 m/sec, and [aluminum compound E dispersion liquid] was obtained. ..
The volume average particle diameter of the obtained dispersion liquid measured by LA-920 (manufactured by HORIBA) was 0.39 μm.

(Synthesis of zinc compound)
<Zinc complex or salt of salicylic acid derivative>
136.3 g of zinc chloride is dissolved in 9,863.7 g of ion-exchanged water to prepare an aqueous solution of 0.1 mmol/g. 500.7 g of 3,5-di-t-butylsalicylic acid is dissolved in 7,999.4 g of 1% caustic soda water and 1,535.9 g of ion-exchanged water to prepare a basic 0.1 mmol/g aqueous solution. .. A zinc compound F was synthesized by gradually mixing an aqueous solution of 3,5-di-t-butylsalicylic acid in sodium hydroxide while stirring the aqueous zinc chloride solution. The zinc compound F was filtered and washed by repeating redispersion in ion-exchanged water to obtain a filter cake. The filter cake was dried at 45° C. for 48 hours with a circulating air dryer to obtain a zinc compound F.
100 parts of zinc compound F, 899 parts of ion-exchanged water, and 1 part of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Kasei Co., Ltd.) were mixed, and a bead mill (Ultraviscomill, manufactured by AIMEX Co., Ltd.) was mixed. ) Was used to disperse liquid at a liquid feed rate of 1 kg/hr, a disk peripheral velocity of 6 m/sec, 0.5 mm zirconia beads at 80% by volume, and dispersion was performed for 7 passes to obtain [dispersion liquid of zinc compound F]. ..
The volume average particle diameter of the obtained dispersion liquid measured by LA-920 (manufactured by HORIBA) was 0.37 μm.

(Example 1)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25 mass% and 6.3 parts of [dispersion liquid (1) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours with a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 1]. For toner base 1 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.). Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a mesh of 25 μm to obtain [Toner of Example 1].

(Example 2)
200 parts of "slurry liquid of toner 1" having a solid content of 25 mass% and 25.0 parts of [dispersion liquid (4) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air drier, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 2]. For toner base 2 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.). Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 2].

(Example 3)
200 parts of "slurry liquid of toner 1" having a solid content of 25 mass% and 5.0 parts of [dispersion liquid (2) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 3]. With respect to Toner Base 3 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 3].

(Example 4)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25 mass% and 10.0 parts of [dispersion liquid (2) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in an air-circulation dryer, and sieved with a 75 μm mesh to obtain [Toner Base 4]. For toner base 4 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.). Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 4].

(Slurry liquid of toner 5)
The slurry liquid of Toner 5 differs from the slurry liquid of Toner 1 in the emulsification/desolvation step, and the target volume average particle diameter after desolubilization is different, and is prepared to be 7.0 μm. The other steps were the same as those for the toner 1 slurry liquid.

(Example 5)
200 parts of "slurry liquid of toner 5" having a solid content adjusted to 25 mass% and 7.9 parts of [dispersion liquid (2) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 5. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 5]. Toner base 5 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a mesh of 25 μm to obtain [Toner of Example 5].

(Example 6)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25% by mass and 10.0 parts of [dispersion liquid of zirconium compound B] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound B on the toner 1. This liquid is held at 50° C. for 1 hour to fix the zirconium compound B on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours with a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 6]. Toner base 6 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 6].

(Example 7)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25 mass% and 8.7 parts of [dispersion liquid of aluminum compound E] are mixed. As the aggregating agent, 1% by mass hydrochloric acid is slowly added until pH=2, so that the aluminum compound E is aggregated on the toner 1. This liquid is held at 50° C. for 1 hour to fix the aluminum compound E on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours with a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 7]. Toner base 7 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 7].

(Example 8)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25% by mass and 9.1 parts of [chromium compound D dispersion liquid] are mixed. As a coagulant, 1 mass% hydrochloric acid is slowly added until pH=2 to coagulate the chromium compound D on the toner 1. This liquid is held at 50° C. for 1 hour to fix the chromium compound D on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 8]. With respect to the toner base 8 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.). Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved through a 25 μm mesh to obtain [Toner of Example 8].

(Example 9)
200 parts of "slurry liquid of toner 1" whose solid content is adjusted to 25% by mass and 9.1 parts of [dispersion liquid of iron (III) compound C] are mixed. As the aggregating agent, 1 mass% hydrochloric acid is slowly added until pH=2, and the iron (III) compound C is aggregated on the toner 1. This solution is held at 50° C. for 1 hour to fix the iron(III) compound C on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours with a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 9]. Toner base 9 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.). Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 9].

(Example 10)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25% by mass and 9.3 parts of [dispersion liquid of zinc compound F] are mixed. As the aggregating agent, 1% by mass hydrochloric acid is slowly added until pH=2, whereby the zinc compound F is aggregated on the toner 1. This liquid is held at 50° C. for 1 hour to fix the zinc compound F on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours with a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 10]. With respect to the toner base 10 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 10].

(Example 11)
200 parts of "slurry liquid of toner 1" having a solid content of 25 mass% and 20.0 parts of [dispersion liquid (2) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 11]. Toner base 11 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 11].

(Slurry liquid of toners 12, 13, 14, and 15)
In the slurry liquids of Toners 12, 13, 14, and 15, the mixing ratio of amorphous polyesters A1 to A3 was made different from that of Toner 1 in the <Preparation of oil phase> step as shown in Table 2 below. The other steps are the same as those for the toner 1 slurry liquid.

(Example 12)
200 parts of "slurry liquid of toner 12" having a solid content adjusted to 25 mass% and 10.0 parts of [dispersion liquid (2) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 12. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours with a circulating air drier, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 12]. Toner base 12 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 12].

(Example 13)
200 parts of "slurry liquid of toner 13" having a solid content adjusted to 25 mass% and 10.0 parts of [dispersion liquid (2) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 13. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 13]. With respect to the toner base 13 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 13].

(Example 14)
200 parts of "slurry liquid of toner 14" having a solid content adjusted to 25 mass% and 10.0 parts of [dispersion liquid (2) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 14. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 14]. With respect to the toner base 14 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 14].

(Example 15)
200 parts of "Toner 15 slurry liquid" having a solid content adjusted to 25 mass% and 10.0 parts of [dispersion liquid (2) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 15. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 15]. Toner base 15 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 15].

(Example 16)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25 mass% and 12.5 parts of [dispersion liquid (3) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 16]. With respect to the toner base 16 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 16].

(Example 17)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25% by mass and 22.5 parts of [dispersion liquid (2) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in an air-circulation dryer, and sieved with a 75 μm mesh to obtain [toner base 17]. For toner base 17 (100 parts), Nippon Aerosil NX-90S (1.0 part), Teika JMT-150IB (1.0 part), Fuso Chemical Co., Ltd. HSP-160A (1.0). Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 17].

(Example 18)
200 parts of "slurry liquid of toner 1" having a solid content of 25 mass% and 28.1 parts of [dispersion liquid (3) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 18]. For toner base 18 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 18].

<Preparation of Salicylic Acid Derivative Metal Salt Dispersion in Ethyl Acetate>
3,5-di-t-butyl zirconium salicylate (SZr) 50 parts Amorphous polyester resin A1 50 parts Ethyl acetate 400 parts are put into a container in which a stirring bar and a thermometer are set.
These were heated to 30° C. with stirring and kept at 30° C. for 1 hour to dissolve the resin to obtain a salicylic acid derivative metal salt dispersion. After cooling to 20° C. for 1 hour, using a bead mill (Ultra Visco Mill, manufactured by AIMEX Co., Ltd.), a liquid feed rate of 1 kg/hr, a disk peripheral velocity of 6 m/sec, 0.5 mm zirconia beads were filled at 80% by volume, 7 passes Dispersion was performed under the conditions described above, and ethyl acetate was added to obtain a [3,5-di-t-butylsalicylate zirconium (SZr) dispersion] adjusted to a solid content of 20% by mass. The volume average particle diameter of the obtained dispersion liquid measured by LA-920 (manufactured by HORIBA) was 0.40 μm.

(Slurry liquid of toner 19)
The method for preparing the oil phase of the slurry liquid of the toner 19 differs from that of the toner liquid of the toner 1 as follows. The other steps are the same as those of the toner base 1.
<Preparation of oil phase>
[Ethyl acetate] 302 parts, [WAX dispersion 1] 250 parts, [Crystalline polyester resin dispersion] 500 parts, [Amorphous polyester resin A1] 650 parts, [Masterbatch 1] 100 parts, [(SZr) Dispersion] 279 parts were placed in a container and mixed with TK homomixer (manufactured by Tokushu Kiki) at 5,000 rpm for 60 minutes. After that, 300 parts of [ethyl acetate solution of amorphous polyester resin A3] and 2 parts of isophoronediamine as a curing agent were added, and the mixture was mixed for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika) to obtain [oil phase]. Obtained.

(Example 19)
200 parts of "slurry liquid of toner 19" having a solid content adjusted to 25 mass% and 10.0 parts of [dispersion liquid (2) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 19. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 19]. Toner base 19 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.). Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Example 19].

(Comparative Example 1)
The "slurry liquid of Toner 1" was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 20]. With respect to the toner base 20 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Comparative Example 1].

(Slurry liquid of toner 21)
The slurry liquid of the toner 21 is different from the slurry liquid of the toner 1 in the method of preparing the oil phase as follows. The other steps are the same as those of the toner base 1.
<Preparation of oil phase>
[Ethyl acetate] 302 parts, [WAX dispersion 1] 250 parts, [Crystalline polyester resin dispersion] 500 parts, [Amorphous polyester resin A1] 650 parts, [Masterbatch 1] 100 parts, [(SZr) Dispersion] 477.7 parts was placed in a container and mixed with TK homomixer (made by Tokushu Kiki) at 5,000 rpm for 60 minutes. After that, 300 parts of [ethyl acetate solution of amorphous polyester resin A3] and 2 parts of isophoronediamine as a curing agent were added, and the mixture was mixed for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika) to obtain [oil phase]. Obtained.

(Comparative example 2)
The "slurry liquid of toner 21" was filtered, dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 21]. With respect to the toner base 21 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a HENSCHEL MIXER manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Comparative Example 2].

(Comparative example 3)
To the toner base 20 (100 parts), 0.44 parts of BONTRON X-11 (Fe-salicylic acid derivative complex) manufactured by Orient Chemical Industry Co., Ltd. was mixed strongly with a Q mixer manufactured by Mitsui Mining Co., Ltd. It was fixed to obtain [Mother toner 22]. With respect to the toner base 22 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a mesh of 25 μm to obtain [Toner of Comparative Example 3].

(Comparative example 4)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25 mass% and 30.0 parts of [dispersion liquid (5) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in an air-circulation dryer, and sieved with a 75 μm mesh to obtain [toner base 23]. With respect to the toner base 23 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.). Part) was mixed with a HENSCHEL MIXER manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Comparative Example 4].

(Comparative example 5)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25 mass% and 1.0 part of [dispersion liquid (1) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in an air-circulation dryer, and sieved with a 75 μm mesh to obtain [toner base 24]. With respect to the toner base 24 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a mesh of 25 μm to obtain [Toner of Comparative Example 5].

(Comparative example 6)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25 mass% and 32.5 parts of [dispersion liquid (2) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in an air-circulation dryer, and sieved with a 75 μm mesh to obtain [toner base 25]. For toner base 25 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Comparative Example 6].

(Comparative Example 7)
200 parts of "slurry liquid of toner 1" having a solid content adjusted to 25% by mass and 5.0 parts of [dispersion liquid (3) of zirconium compound A] are mixed. As a coagulant, 1% by mass hydrochloric acid is slowly added until pH=2 to coagulate the zirconium compound A on the toner 1. This solution is held at 50° C. for 1 hour to fix the zirconium compound A on the toner surface. This liquid was filtered and dried at 45° C. for 48 hours in a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 26]. With respect to the toner base 26 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Comparative Example 7].

(Comparative Example 8)
To the toner base 20 (100 parts), 0.25 parts of BONTRON E-84 (Zn-salicylic acid derivative complex) manufactured by Orient Chemical Industry Co., Ltd. was mixed strongly with a Q mixer manufactured by Mitsui Mining Co., Ltd. It was fixed to obtain [toner base 27]. Toner base 27 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Comparative Example 8].

(Comparative Example 9)
Toner 250 (100 parts) is added to 250 parts by weight of ion-exchanged water having a concentration of 0.1% by weight of sodium lauryl sulfate with stirring, and the mixture is stirred for 10 minutes as it is.
After 10 minutes, it is visually confirmed that the toner base 20 is completely wet with the aqueous solution without any floating powder, and further that the particles are separated and dispersed by an optical microscope.
The obtained dispersion is separated by centrifugation, the supernatant is removed, and redispersed with the same amount of ion-exchanged water as the removed supernatant. This operation was repeated 3 times to obtain a purified dispersion liquid of the toner base 20.
To this, 3.75 parts of [dispersion liquid of zinc compound F] was added with stirring, and this liquid was held at 50° C. for 10 minutes to immobilize the zinc compound F on the toner surface.
This liquid was filtered and dried at 45° C. for 48 hours with a circulating air dryer, and sieved with a mesh having a mesh of 75 μm to obtain [toner base 28]. With respect to the toner base 28 (100 parts), NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A (1.0 part manufactured by Fuso Chemical Industry Co., Ltd.) Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a 25 μm mesh to obtain [Toner of Comparative 9].

Table 3 shows the addition amount of the metal complex or salt of the aromatic carboxylic acid derivative, the toner particle size, and the amorphous polyester ratio in Examples 1 to 19 and Comparative Examples 1 to 9. In addition, as a result of image analysis of each toner in Examples 1 to 19 and Comparative Examples 1 to 9, the number average particle size of the metal complex of the aromatic carboxylic acid derivative or the salt, and the metal complex of the aromatic carboxylic acid derivative. Table 4 shows the measurement results of the coverage of the toner particles with the salt particles. In Tables 3 and 4, a metal complex or salt of an aromatic carboxylic acid derivative is simply referred to as a metal compound.

(Evaluation result in image forming apparatus)
The toners of Examples 1 to 19 and Comparative Examples 1 to 9 were put in an image forming apparatus, and the following items were evaluated. The evaluation results are shown in Table 5 below. As the image forming apparatus, a digital full-color multifunction machine MP C6003 manufactured by Ricoh Co., Ltd. was used.

<Evaluation of cold offset property>
A rectangular solid image of 3 cm×15 cm was formed on a PPC paper type 6000 <70 W>A4 T-th eye (manufactured by Ricoh Co., Ltd.) so that the toner adhesion amount was 0.85 mg/cm ^2, and was output. An image was output by adjusting the fixing temperature and decreasing the temperature from 160° C. in steps of 1° C.
The temperature at which cold offset begins to occur was measured.

<Evaluation of paper discharge blocking resistance>
PPC paper type 6000 <70 W> A4 T-th size (manufactured by Ricoh Co., Ltd.), a rectangular solid image of 3 cm × 15 cm is formed so that the toner adhesion amount is 0.85 mg/cm ^2, and one side is continuously output 200 sheets. did. The fixing temperature was controlled so that the cold offset temperature +20° C. was the center. The 200 output images were left standing for 1 hour while being stacked, and then the sticking of the images to each other was evaluated.
[Ejection-resistant blocking evaluation criteria]
A: There is no sticking between the sheets.
B: There is a little sticking of the paper sheets, but the paper sheets are easily peeled off and there is no problem in the image when separated.
C: There is a little sticking of the sheets, and a slight noise is generated when the sheets are separated, but there is no problem in image quality.
D: There is a little sticking of the paper sheets, and the glossiness of the image changes when the paper sheets are separated.
E: There is sticking between the sheets, and the images and the sheets are damaged when the sheets are separated.

<Evaluation of image storability>
A rectangular solid image of 3 cm×15 cm was formed on a PPC paper type 6000<70 W>A4 T-th sheet (manufactured by Ricoh Co., Ltd.) so that the amount of adhered toner was 0.85 mg/cm ^2, and one-sided output was performed. The fixing temperature was controlled so that the cold offset temperature +20° C. was the center. The obtained image surfaces were overlapped with each other, brought into contact with each other, and a weight equivalent to 8 kPa was placed on the image surfaces and left at 60° C. and 50% RH for 1 week. After standing, the two stacked sheets were peeled off, and the state at the time of peeling was observed by weft.
[Evaluation criteria for image storability]
A: There is no sticking between the sheets and there is no image loss or transfer.
B: There is a little sticking at the time of peeling (a slight peeling noise is generated), but the sheets are easily peeled off, and when separated, there is no image loss or transfer in the image.
C: Papers are stuck to each other, and image loss and transfer are observed.
D: There is sticking between the sheets, and when the sheets are separated from each other, image loss is severe and the sheets are damaged.

From the above results, it can be confirmed that the image forming apparatus using the toner of the present invention can perform low-temperature fixing, can reduce power consumption, and can output an image having excellent discharge blocking resistance and image storability. It was

Aspects of the present invention are as follows, for example.
<1> A toner containing at least a binder resin,
Particles of a metal complex or salt of an aromatic carboxylic acid derivative having a number average particle size of 0.2 μm or more and 1.0 μm or less exist on the toner surface, and particles of the metal complex or salt of the aromatic carboxylic acid derivative are present. The toner has a coverage of 10% or more and 50% or less on the surface of the toner.
<2> The toner according to <1>, wherein the metal complex or salt of the aromatic carboxylic acid derivative is a salicylic acid derivative metal complex or salt represented by the following general formula (1).
In the general formula (1), R _{1 to} R ₄ represent the same or different groups, and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, an alkenyl having 2 to 12 carbon atoms which may be branched. _{groups, -OH, -NH 2, -NH (} CH 3), - N (CH 3) 2, -OCH 3, -OC 2 H 5, shown -COOH, or -CONH _2.
<3> The toner according to any one of <1> to <2>, wherein the salicylic acid derivative metal complex or salt is a di-tert-butyl salicylic acid metal complex or salt.
<4> The toner according to any one of <1> to <3>, wherein the metal species forming the metal complex or the salt is any one of Zn ²⁺ , Al ³⁺ , Cr ³⁺ , Fe ³⁺ , and Zr ^4+. Is.
<5> The toner according to any one of <1> to <4>, wherein the number average particle diameter of the metal complex or salt particles is 0.2 μm or more and 0.5 μm or less.
<6> The toner according to any one of <1> to <5>, wherein the metal species forming the metal complex or the salt is any one of Al ³⁺ , Cr ³⁺ , Fe ³⁺ , and Zr ⁴⁺ .
<7> The toner according to any one of <1> to <6>, wherein the acid value of the toner is in the range of 10 to 50 mgKOH/g.
<8> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image formed on the electrostatic latent image carrier with toner. And a developing step of forming a visible image,
The image forming method is characterized in that the toner is the toner according to any one of <1> to <7>.
<9> A toner containing unit containing the toner according to any one of <1> to <7>.
<10> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image formed on the electrostatic latent image carrier. A developing unit including a toner for developing the image to form a visible image,
The image forming apparatus is characterized in that the toner is the toner according to any one of <1> to <7>.

The toner according to any one of <1> to <7>, the image forming method according to <8>, the toner containing unit according to <9>, and the image forming apparatus according to <10>. For example, it is possible to solve the above-mentioned problems in the related art and achieve the object of the present invention.

The toner of the present invention can be preferably applied to an electrophotographic image forming apparatus such as a copying machine, a printer, and a FAX.

JP, 2009-053695, A JP, 2011-150229, A JP, 2011-123483, A Japanese Patent No. 3631468 Japanese Patent No. 3945797

Claims (7)

A toner containing at least a binder resin,
The surface of the toner, the number average particle diameter is externally added particles of zirconium complex or salt of 1.0μm or less of an aromatic carboxylic acid derivative or 0.2 [mu] m, and a zirconium complex or salt of the aromatic carboxylic acid derivative the toner surface coverage Ri der 50% 10% or more by the particle
A toner having an acid value of 10 to 50 mgKOH/g . The toner according to claim 1, wherein the zirconium complex or salt of the aromatic carboxylic acid derivative is a salicylic acid derivative zirconium complex or salt represented by the following general formula (1).
In the general formula (1), R _{1 to} R ₄ represent the same or different groups, and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, an alkenyl having 2 to 12 carbon atoms which may be branched. _{groups, -OH, -NH 2, -NH (} CH 3), - N (CH 3) 2, -OCH 3, -OC 2 H 5, shown -COOH, or -CONH _2. The toner according to claim 1, wherein the salicylic acid derivative zirconium complex or salt is a di-tert-butyl zirconium salicylate complex or salt. The toner according to claim 1, wherein the number average particle diameter of the zirconium complex or salt particles is 0.2 μm or more and 0.5 μm or less. The electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image formed on the electrostatic latent image carrier are developed with toner to make visible. And a developing step for forming an image,
An image forming method, wherein the toner is the toner according to any one of claims 1 to 4. A toner containing unit containing the toner according to claim 1. An electrostatic latent image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image formed on the electrostatic latent image carrier. To form a visible image, and a developing unit including toner,
An image forming apparatus, wherein the toner is the toner according to any one of claims 1 to 4.