JP7225933B2 - Toner, Toner Containing Unit, Developer, Developer Containing Unit, and Image Forming Apparatus - Google Patents

Description

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

2. Description of the Related Art In the electrophotographic industry, technical development of low-temperature fixation of toner is still being carried out day by day due to the need to cope with environmental loads such as miniaturization of image forming apparatuses and reduction of power consumption.
Various techniques have been developed for low-temperature fixation of toner. For example, a method of controlling the thermal properties of the resin itself is known. However, lowering the Tg (glass transition temperature) of the resin causes deterioration in heat resistant storage stability and fixing strength. Further, a decrease in the softening temperature [T(F _1/2 )] due to a decrease in the molecular weight of the resin contained in the toner causes problems such as occurrence of hot offset and excessive gloss (gloss controllability).

Under these circumstances, the main resin composition of current low-temperature fixation toners is polyester resin, which has excellent compatibility between low-temperature fixability and heat-resistant storage, as the main binder, instead of styrene-acrylic resin, which has been widely used in the past. A crystalline polyester resin that exhibits sharp meltability when thermally fixed to a recording medium is used as a sub-binder (see, for example, Patent Documents 1 and 2).

In addition, techniques for optimizing the content of the crystalline polyester resin on the surface of the toner are disclosed in order to suppress side effects such as poor filming resistance and storage stability when the crystalline polyester resin is used (for example, , see Patent Document 3).

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which is excellent in low-temperature fixability and which causes very little image fogging and photoreceptor filming.

The toner of the present invention as a means for solving the above-mentioned problems comprises base particles containing at least a resin,
A toner containing a metal compound and a silicon compound, which is the highest among the peaks observed at 1137 cm ⁻¹ to 1199 cm ⁻¹ of the toner determined by the FTIR-ATR (total reflection absorption infrared spectroscopy) method. The ratio (C/R) between the peak intensity C and the highest peak intensity R among the peaks observed at 784 cm ^-1 to 889 cm ^-1 is 0.15 ≤ C/R ≤ 0.19. , wherein the metal compound contains at least one selected from an aluminum compound and a cerium compound , and the metal compound adhering to the surface of the mother particles with respect to the total amount of the metal compound contained in the toner is 70 % or more and 85 % or less.

According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability and causes very little image fogging and photoreceptor filming.

FIG. 1 is a spectral diagram showing characteristic peaks of a crystalline resin in toner. FIG. 2 is a spectrum diagram showing characteristic peaks of an amorphous resin in toner. FIG. 3 is a diagram showing the relationship between the amount of blow-off charge and the electronegativity of metal ions in contact charging of a metal compound with iron powder. FIG. 4 is a schematic explanatory diagram showing an example of the image forming apparatus of the present invention. FIG. 5 is a schematic explanatory diagram showing another example of the image forming apparatus of the present invention. FIG. 6 is a schematic explanatory diagram showing an example using a tandem-type color image forming apparatus of the image forming apparatus of the present invention. 7 is an enlarged view showing an example of the image forming unit of FIG. 6. FIG.

(toner)
The toner of the present invention is a toner comprising mother particles containing at least a resin, a metal compound, and a silicon compound, and is determined by FTIR-ATR (Total Reflection Absorption Infrared Spectroscopy) ^. The ratio (C/R) of the highest peak intensity C among the peaks observed at ~1199 cm ^-1 and the highest peak intensity R among the peaks observed at 784 cm ^-1 ~889 cm ^-1 is The following formula is satisfied: 0.05≦C/R≦0.20, and the metal compound contains at least one selected from an aluminum compound, a zinc compound, a cerium compound, and a zirconium compound, and is contained in the toner. The ratio of the amount of the metal compound adhering to the surface of the mother particles to the total amount of the metal compound is 60% or more and 90% or less, and further contains other components as necessary.

In the prior art, the inclusion of a crystalline polyester resin in the toner has a dramatic effect on the development of low-temperature fixability, but on the other hand, it hinders the chargeability and heat-resistant storage stability of the toner, Side effects such as deterioration of fluidity due to an increase in the adhesion force between particles are observed, and these effects become more pronounced when a large amount of crystalline polyester resin is present on the toner surface, resulting in image quality problems such as image fogging and photoreceptor filming. problem arises.

Therefore, in the present invention, in a toner in which a large amount of crystalline resin is present near the surface of the toner, a silicon compound and a metal compound are used as an intermediary for allowing the silicon compound to be appropriately present on the surface of the mother particles. The above problem is solved by controlling the adhesion rate of the metal compound adhering to the surface of the mother particles to the range of 60% or more and 90% or less with respect to the total amount of the metal compounds present on the surface of the mother particles. It is possible to obtain a toner which is excellent in low-temperature fixability and which causes very little image fogging and photoreceptor filming.

In the present invention ^, the highest peak intensity ^{C and} It is important that the ratio (C/R) to the intensity R of the highest peak observed at 889 cm ⁻¹ satisfies the following formula: 0.05≦C/R≦0.20.
The intensity C at 1165 cm ⁻¹ of the spectrum obtained by FTIR-ATR (total reflection absorption infrared spectroscopy) is a value that correlates with the content of the crystalline resin on the toner surface. The intensity R at 829 cm ⁻¹ of the spectrum obtained by the method is a value that correlates with the content of the non-crystalline resin on the surface of the mother particle, and the intensity C of the peak (1165 cm ⁻¹ ) derived from the crystalline resin of the toner and the non-crystalline resin The ratio (C/R) of the peak (829 cm ⁻¹ ) derived from the crystalline resin to the intensity R is a value that correlates with the content ratio of the crystalline resin and the amorphous resin on the surface of the mother particle in the toner. is.
When the strength ratio (C/R) satisfies 0.05 or more and 0.20 or less, sufficient low-temperature fixability can be realized without impairing chargeability and heat-resistant storage stability. When the ratio (C/R) is 0.05 or more, the low-temperature fixability is good, a large amount of the crystalline resin having a sharp melting property exists near the surface layer of the adhesive particles, and the amount of heat applied during fixing is reduced by the toner. spread throughout. Further, when the strength ratio (C/R) is 0.20 or less, the chargeability and heat-resistant storage stability are good, and the adhesive force between toner particles is appropriate.

Control of the strength ratio (C/R) is determined by the ratio of the compatible state between the crystalline resin and the non-crystalline resin. However, since it is difficult to measure the degree of crystallinity, in the present invention, the toner is formulated and manufactured so that the intensity ratio (C/R) satisfies 0.05 or more and 0.20 or less by a quality engineering method. We are trying to achieve this by optimizing the conditions.

<Method for measuring intensity ratio (C/R)>
The spectral intensity ratio C/R is calculated from the absorbance spectrum obtained by ATR method (total reflection method) measurement with FT-IR (Fourier transform infrared spectrometer, Avatar 370, manufactured by ThermoElectron).
Since the ATR method requires a smooth surface, the toner is pressure-molded to form a smooth surface. In this pressure molding, a load of 1 t is applied to 2.0 g of toner for 60 seconds to form a pellet having a diameter of 20 mm.
In the ATR method, a Ge crystal was used, and the incident angle was 41.5°, the resolution was 4 cm ⁻¹ , and the number of times of integration was 20.
The peak height of the spectrum characteristic of the crystalline state of the crystalline resin (for example, 1165 cm ^-1 in the case of polyester resin) is C (see FIG. 1, the baseline height is 1137 cm ^-1 to 1199 cm ^-1 ), The peak height of the characteristic spectrum of the amorphous resin (for example, 829 cm ^-1 in the case of polyester resin) is R (see FIG. 2, the baseline height is 784 cm ^-1 to 889 cm ^-1 ), and C/ R was calculated as the peak intensity ratio. The peak intensity ratio in the present invention is obtained by converting the spectrum into absorbance and using the peak height.

In the present invention, a base particle containing at least a resin, a metal compound, and a silicon compound are provided, and the ratio of the electronegativity X (A) of the metal compound to the electronegativity X (Si) of the silicon compound [X(A)/X(Si)] satisfies the following formula: 0.5≦X(A)/X(Si)≦0.8, and It is important that the ratio of the amount of metal compound adhering to the surface of the particles is 60% or more and 90% or less.
The present inventors have found a metal compound in which the electronegativity ratio [X(A)/X(Si)] is 0.5 or more and 0.8 or less, more preferably the ratio [X(A)/X(Si) )] is 0.5 or more and 0.6 or less, the charge is charged even in the state where the crystalline resin necessary for ensuring the low-temperature fixability is present on the surface of the mother particles. It was found that both chargeability and fluidity can be achieved without impairing the properties and fluidity.

The reason for this is not clear, but a metal compound having an electronegativity that is at least a certain distance from the electronegativity of a silicon compound has a weakly negative or weakly positive charge, whereas the silicon compound exhibits a negative chargeability. show gender. When the mother particles are also negatively charged, the other metal compound other than the silicon compound tends to selectively adhere to the surface of the mother particles due to the charge order. In addition, since it is electrically attracted to the silicon compound, it is presumed that the arrangement of the metal compound and the silicon compound can be selectively formed in order from the surface of the base particle. As a result, the functions of the metal compound and the silicon compound are exhibited, and chargeability and fluidity are stably maintained over a long period of time.
When the electronegativity ratio [X(A)/X(Si)] is 0.5 or more, the charging property of the metal compound is appropriate, the charging stability is good, and a high-quality image can be obtained. Further, when the electronegativity ratio [X(A)/X(Si)] is 0.8 or less, the above-described permutation is sufficient, and the chargeability and fluidity are stably maintained over a long period of time. maintained.
Here, electronegativity means the ability of atoms participating in intramolecular bonds to attract electrons, and FIG. It is a diagram showing the relationship, and the electronegativity of various metal compounds is derived from the material and is known (“Powder Technology Journal Vol. 24 No. 12 “Electrification of powder and its application””). Alumina (Al ₂ O ₃ ) is electrically positive and electrically negative silica (SiO ₂ ) can be electrostatically deposited.

The ratio of the amount of the metal compound adhering to the surface of the mother particles to the total amount of the metal compound contained in the toner is 60% or more and 90% or less, preferably 65% or more and 85% or less.
Here, as the metal compounds attached to the surface of the base particles, one is the metal compound (X1) that is directly attached to the base particles, and the other is the metal compound that is indirectly attached to the base particles. and compound (X2) (for example, attached via silicon oxide or other metal compound).
When the ratio of the amount of the metal compound attached is 60% or more, the permutation of the metal compound attached to the base particles can be appropriately performed. Further, when the percentage of the amount of the metal compound attached is 90% or less, the fluidity of the toner is improved.

<Percentage (%) of the amount of the metal compound adhering to the surface of the mother particles with respect to the total amount of the metal compound contained in the toner>
The adhesion amount (X1) of the metallic compound adhering to the surface of the mother particles and the total amount (Y=X1+X2) of the metallic compound contained in the toner can be measured as follows. By (X1/Y)×100, the ratio (%) of the amount of metal compound adhering to the surface of the base particle can be obtained.

-Amount of metal compound adhering to the surface of the mother particle (X1)-
(1) Weigh 5 g of polyoxyalkylene alkyl ether (Noigen ET-165, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in a 500 mL beaker. Add 300 mL of distilled water and sonicate to dissolve. Transfer to a 1,000 mL volumetric flask and fill up (if foaming occurs, leave for a while). A 0.5% by mass dispersion of polyoxyalkylene alkyl ether (Noigen ET-165, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) is prepared by ultrasonication.
(2) 3.75 g of a toner sample is dispersed in 50 mL of a 0.5 mass % polyoxyalkylene alkyl ether (Noigen ET-165, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) dispersion in a 110 mL vial.
(3) Using an ultrasonic homogenizer (trade name: homogenizer, model VCX750, CV33, manufactured by SONICS & MATERIALS), ultrasonic waves are applied at a frequency of 20 kHz, an output of 80 W, and an irradiation energy amount of 20 kJ for a certain period of time. The amount of irradiation energy given at this time is calculated from the product of the output and the irradiation time. At this time, the treatment is carried out while cooling the toner particle dispersion as appropriate so that the temperature of the toner particle dispersion does not exceed 40.degree.
(4) The resulting dispersion was suction-filtered with filter paper (trade name: qualitative filter paper (No. 2, 110 mm), manufactured by Advantec Toyo Co., Ltd.), washed again with ion-exchanged water twice, filtered, and separated. After removing the metal compound, the toner particles are dried.
(5) The intensity (or It is possible to determine the adhesion amount (X1) of the metal compound adhering to the surface of the mother particles by quantifying by calculating mass% from the difference in strength before and after removal).

<Fluorescent X-ray analysis>
3.00 g of the toner is formed into a pellet having a diameter of 3 mm and a thickness of 2 mm, and is used as a measurement sample toner.
Next, the content of the metal element derived from the metal compound in the pellet sample is measured by quantitative analysis using a fluorescent X-ray device.
In the measurement, a metal element standard sample (manufactured by Rigaku Co., Ltd.) is used for correction, and the content is calculated.
・Measuring device: ZSX-100e manufactured by Rigaku Corporation
・X-ray tube: Rh
・X-ray tube voltage: 50 kV
・X-ray tube current: 10mA

-Total Amount (Y) of Metal Compounds Contained in Toner-
The total amount (Y) of metal compounds contained in the toner can be measured as follows.
Using an ultrasonic homogenizer, the amount of metal compounds in the toner particles irradiated with ultrasonic waves at 1,000 kJ and 1,500 kJ in the same manner as described above was measured by a fluorescent X-ray analyzer (manufactured by Rigaku Denki Co., Ltd., ZSX). -100e), and confirm that there is no decrease in the amount of metal compounds at 1,000 kJ and 1,500 kJ.
If there is no decrease, it can be determined that all the metal compounds are detached from the toner particles. Further, the surfaces of the toner particles after the treatment may be observed with a field emission scanning electron microscope (FE-SEM) to confirm that all the metal compounds are desorbed.
If a change is observed, the amount of irradiation energy is further increased by 500 kJ and the same processing is performed.
From the difference between the amount of the metal compound on the surface of the toner particles from which all the metal compounds have been removed as described above and the amount of the metal compound on the untreated toner particles from which no metal compound has been removed, the amount of the metal compound contained in the toner is determined. A total amount (Y) can be calculated.
After all the metal compounds have been desorbed as described above, when "the amount of metal compounds in the mother particles from which all the metal compounds have been desorbed" is measured by fluorescent X-rays, the amount of metal compounds is either zero or the amount of metal in the mother particles is If a material containing a compound is included, it will be affected and have a certain value. On the other hand, when the amount of metal compound in the untreated toner is measured by fluorescent X-rays, the amount of metal compound is added by the amount of the metal compound and the material containing the metal compound in the mother particles as in the above case. The Rukoto.
Therefore, in order to calculate the total amount (Y) of the metal compound contained in the toner, the total amount of the metal compound in the toner and the amount of the metal compound on the surface of the mother particles from which all the metal compounds have been desorbed are calculated as described above. A method of calculating the total amount (Y) of metal compounds contained in the toner from the difference is employed.

The toner of the present invention has at least mother particles containing a resin, a metal compound, and a silicon compound, and further contains other components as necessary.

The ratio (X(A)/X(Si)) of the electronegativity X(A) of the metal compound to the electronegativity X(Si) of the silicon compound is 0.5 ≦X(A)/X(Si)≦0.8 is satisfied.

<<Metal compound>>
Examples of metal compounds include aluminum oxide, zinc oxide, cerium oxide, and zirconium oxide. These may be used individually by 1 type, and may use 2 or more types together. Among these, aluminum oxide is preferred.

The sphericity represented by the following formula (1) in the metal compound is preferably 0.5 or more, more preferably 0.6 or more and 0.8 or less. When a metal compound having a sphericity of 0.5 or more adheres to the surface of the base particles, it can exert a spacer effect, and a favorable effect of reducing the adhesive force between toner particles can be obtained.
Sphericality=4π×(A/L ² ) Expression (1)
However, in the above formula (1), π represents the circular constant, L represents the peripheral length of the projected image of the metal compound, and A represents the projected area of the metal compound.

The sphericity of the metal compound is obtained by observing the primary particles of the metal compound after dispersing the metal compound in the toner particles with a scanning electron microscope (SEM) device and analyzing the obtained primary particles of the metal compound. can be done. As image analysis software, image analysis software LMeye for OPTELICSC130 manufactured by Lasertec Co., Ltd. can be used, and the following method can be used.
(1) Capture an image observed at 5.0 kV by the SEM (2) Adjust calibration (scale) (3) Perform automatic contrast (4) Perform inversion (5) Perform edge extraction (Sobel) ( 6) Perform edge extraction (Sobel) again. (7) Perform binarization processing (discriminant analysis mode). (8) Calculate shape features (sphericity, absolute maximum length, diagonal width) by measurement. The sphericity of is the 50% sphericity in the cumulative frequency of equivalent circle diameters of 100 primary particles of the metal compound obtained by the above image analysis.

<<Silicon compound>>
Examples of the silicon compound include silicon oxide (silica), silicon carbide, silicon nitride, and silicon tetrachloride. These may be used individually by 1 type, and may use 2 or more types together. Among these, silicon oxide (silica) is preferred.
The number average particle size of the silicon oxide is preferably 50 nm or more and 200 nm or less.
When the number average particle diameter is 50 nm or more, the spacer material is favorable, the durability is improved, and the image quality over time is improved. Further, when the number average particle diameter is 200 nm or less, the fluidity and chargeability are improved.

The other fine particles are not particularly limited and can be appropriately selected depending on the intended purpose, but hydrophobized inorganic fine particles are preferable.
Examples of the shape of the other fine particles include a spherical shape, a needle shape, and an aspherical shape obtained by coalescing several spherical particles.
The other fine particles are not particularly limited and can be appropriately selected depending on the purpose. antimony, etc.), fluoropolymers, and the like.

<Mother particle>
The mother particles contain at least a resin, preferably a crystalline resin and an amorphous resin as the resin, more preferably a colorant, and optionally other components.

In the toner of the present invention, the content of the crystalline resin is preferably 6 parts by mass or more, more preferably 7 parts by mass or more and 13 parts by mass or less with respect to 100 parts by mass of the amorphous resin. When the content of the crystalline resin is 6 parts by mass or more, the low-temperature fixability of the toner is improved.

<<Crystalline Resin>>
The "crystallinity" of a crystalline resin is the ratio of the softening temperature measured by a Koka flow tester to the maximum peak temperature of the heat of fusion measured by a differential scanning calorimeter (DSC) (softening temperature / heat of fusion (maximum peak temperature) is preferably 0.80 to 1.55, and it is a property of sharply softening by heat, and a resin having this property is referred to as a "crystalline resin".
In addition, "amorphous" means that the ratio of the softening temperature to the maximum peak temperature of the heat of fusion (softening temperature/maximum peak temperature of the heat of fusion) is greater than 1.55, and the property is that it softens slowly due to heat. A resin having this property is referred to as an "amorphous resin".

The softening temperature of the resin and toner can be measured using a Koka-type flow tester (eg, CFT-500D, manufactured by Shimadzu Corporation).
While heating 1 g of resin as a sample at a temperature increase rate of 3 ° C./min, a load of 30 kg / cm ² is applied by a plunger, extruded from a nozzle with a diameter of 0.5 mm and a length of 1 mm, and the temperature of the flow tester plunger The amount of descent was plotted, and the temperature at which half of the sample flowed out was taken as the softening temperature.
The maximum peak temperature of the heat of fusion of the resin and toner can be measured using a differential scanning calorimeter (DSC) (eg, TA-60WS and DSC-60, manufactured by Shimadzu Corporation).
The sample subjected to the measurement of the maximum peak temperature of the heat of fusion was pretreated by melting at 130°C, then decreasing the temperature from 130°C to 70°C at a rate of 1.0°C/minute, and then from 70°C to 10°C. The temperature is lowered at a rate of 0.5°C/minute.
Here, once by DSC, the temperature is raised at a temperature increase rate of 20 ° C./min, the change in endothermic heat is measured, and a graph of "endothermic heat amount" and "temperature" is drawn, and the temperature of 20 ° C. or higher observed at this time is measured. The endothermic peak temperature below 100°C is defined as "Ta*".
When there are multiple endothermic peaks, the temperature of the peak with the largest endothermic amount is taken as Ta*. Thereafter, the sample is stored at (Ta*-10)°C for 6 hours, and then further stored at (Ta*-15)°C for 6 hours. Next, the above sample was cooled to 0°C at a temperature drop rate of 10°C/min by DSC, and then heated at a temperature rise rate of 20°C/min to measure changes in endothermic and exothermic changes, and a similar graph was drawn. The temperature corresponding to the maximum peak of the calorific value was taken as the maximum peak temperature of the heat of fusion in the second heating. Further, the amount of heat of fusion at that time can be calculated from the area (peak area) from the temperature at which the endotherm is started to the temperature at which the endotherm is finished.

-Crystalline polyester resin-
The crystalline polyester resin (hereinafter, sometimes referred to as "crystalline polyester resin C") has high crystallinity, and therefore exhibits a thermal melting property showing a sharp viscosity near the fixing start temperature. By using the crystalline polyester resin C having such properties together with the non-crystalline polyester resin, the heat-resistant storage stability due to the crystallinity is good until just before the melting start temperature, and the crystalline polyester resin C melts at the melting start temperature. causes a sharp drop in viscosity (sharp melt property), and along with that, it is compatible with the amorphous polyester resin B described later, and both are fixed by a sharp drop in viscosity, so good heat-resistant storage stability and low-temperature fixability It is possible to obtain a toner having both Good results are also obtained with respect to the release width (difference between minimum fixing temperature and high-temperature offset generating temperature).

The crystalline polyester resin C is obtained by using a polyhydric alcohol, a polycarboxylic acid such as a polycarboxylic acid, a polycarboxylic acid anhydride, a polycarboxylic acid ester, or a derivative thereof.
In the present invention, the crystalline polyester resin C is, as described above, a polyhydric alcohol, a polycarboxylic acid such as a polycarboxylic acid, a polycarboxylic anhydride, a polycarboxylic acid ester, or a derivative thereof. and a modified polyester resin, for example, a prepolymer described later and a resin obtained by cross-linking and / or elongation reaction of the prepolymer, the crystalline polyester resin C do not belong

-- Polyhydric alcohol --
The polyhydric alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include diols and trihydric or higher alcohols.
Examples of the diols include saturated aliphatic diols. The saturated aliphatic diols include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated aliphatic diols having 2 to 12 carbon atoms are more preferable. If the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin C may be lowered and the melting point may be lowered. Moreover, when the number of carbon atoms of the saturated aliphatic diol exceeds 12, it becomes difficult to obtain the material for practical use. It is more preferable that the number of carbon atoms is 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. These may be used individually by 1 type, and may use 2 or more types together. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,8-octanediol, 1,8-octanediol, 1,8-octanediol, 1,8-octanediol, 10-decanediol and 1,12-dodecanediol are preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These polyhydric alcohols may be used singly or in combination of two or more.

-- Polycarboxylic acid --
The polyvalent carboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include divalent carboxylic acid and trivalent or higher carboxylic acid.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sperinic 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 also their anhydrides and lower alkyl esters (having 1 to 3 carbon atoms).
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, anhydrides thereof, and and lower (1 to 3 carbon atoms) alkyl esters of.
In addition to the saturated aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, the polyvalent carboxylic acid may also contain a dicarboxylic acid having a sulfonic acid group. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid having a double bond may be contained.
These polyvalent carboxylic acids may be used singly or in combination of two or more.

The crystalline polyester resin C 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 C may have a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. preferable. 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 C is not particularly limited and can 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 less than 60°C, the crystalline polyester resin C tends to melt at a low temperature, and the heat-resistant storage stability of the toner may deteriorate. The melting of C is insufficient, and the low-temperature fixability may deteriorate.

The molecular weight of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the intended purpose. From the viewpoint that the heat-resistant storage stability decreases if the amount is large, the ortho-dichlorobenzene soluble portion of the crystalline polyester resin C has a weight average molecular weight (Mw) of 3,000 or more and 30,000 or less and a number average molecular weight of 3,000 or more and 30,000 or less in GPC measurement. (Mn) is preferably 1,000 or more and 10,000 or less, and Mw/Mn is preferably 1.0 or more and 10 or less.
More preferably, the weight average molecular weight (Mw) is 5,000 or more and 15,000 or less, the number average molecular weight (Mn) is 2,000 or more and 10,000 or less, and the Mw/Mn is 1.0 or more and 5.0 or less.

The acid value of the crystalline polyester resin C is not particularly limited and can be appropriately selected according to the purpose. is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more. On the other hand, 45 mgKOH/g or less is preferable in order to improve high temperature offset resistance.
The hydroxyl value of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the intended purpose. 0 mgKOH/g or more and 50 mgKOH/g or less are preferable, and 5 mgKOH/g or more and 50 mgKOH/g or less are more preferable.
The molecular structure of the crystalline polyester resin C can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc., in addition to NMR measurement using a solution or solid. A simple method is to detect a crystalline polyester resin C having absorption based on δCH (out-of-plane bending vibration) of an olefin at 965 cm ⁻¹ ±10 cm ⁻¹ or 990 cm ⁻¹ ±10 cm ⁻¹ in an infrared absorption spectrum. is mentioned.

The content of the crystalline polyester resin C is not particularly limited and can be appropriately selected according to the purpose. It is more preferably from 15 parts by mass to 15 parts by mass. When the content is 3 parts by mass or more, sharp melting by the crystalline polyester resin C is achieved, and low-temperature fixability is improved. Further, when the content is 20 parts by mass or less, the heat-resistant storage stability is improved, and a high-quality image can be obtained.

-Amorphous polyester resin-
The amorphous polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose. preferable.

--Amorphous polyester resin A--
The amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the purpose, but preferably has a glass transition temperature (Tg) of -40°C or higher and 20°C or lower.
The amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably obtained by reaction between a non-linear reactive precursor and a curing agent.
Further, the non-crystalline polyester resin A preferably has at least one of urethane bonds and urea bonds from the viewpoint of better adhesion to recording media such as paper. Since the amorphous polyester resin A has either a urethane bond or a urea bond, the urethane bond or the urea bond behaves like a pseudo-crosslinking point, and the rubber-like properties of the amorphous polyester resin A become stronger. , the heat-resistant storage stability and high-temperature offset resistance of the toner are more excellent.

--- Nonlinear 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 sometimes referred to as "prepolymer"). can be selected as appropriate.
Examples of the groups in the prepolymer that can react with the curing agent include groups that can react with active hydrogen groups. Examples of the group capable of reacting with the active hydrogen group include isocyanate group, epoxy group, carboxylic acid group and 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.
Said prepolymer is non-linear. The term "non-linear" means having a branched structure provided by at least one of a trihydric or higher alcohol and a trihydric or higher carboxylic acid.
Moreover, as the prepolymer, a polyester resin containing an isocyanate group is preferable.

The isocyanate group-containing polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include reaction products of a polyester resin having an active hydrogen group and a 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 trihydric or higher alcohol and a trihydric or higher carboxylic acid. The alcohol having a valence of 3 or more and the carboxylic acid having a valence of 3 or more give a branched structure to the isocyanate group-containing polyester resin.

The diol is not particularly limited and can be appropriately selected depending on the intended purpose. -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 , polyethylene glycol, polypropylene glycol, diol having an oxyalkylene group such as polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols, ethylene oxide, propylene oxide, Products obtained by adding alkylene oxides such as butylene oxide; bisphenols such as bisphenol A, bisphenol F and bisphenol S; alkylene oxides of bisphenols such as products obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to bisphenols Additions and the like can be mentioned. Among these, aliphatic diols having 4 to 12 carbon atoms are preferred.
These diols may be used singly or in combination of two or more.

The dicarboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Anhydrides of these may be used, lower alkyl esters (having 1 to 3 carbon atoms), or halides thereof 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 can be appropriately selected depending on the purpose, but an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable. The aromatic dicarboxylic acid having 8 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.
Among these, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferred.
These dicarboxylic acids may be used individually by 1 type, and may use 2 or more types together.

The trihydric or higher alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. and oxide adducts.
Examples of trihydric or higher aliphatic alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
Examples of the trivalent or higher polyphenols include trisphenol PA, phenol novolak, and cresol novolak.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.
The non-crystalline polyester resin A preferably contains a trihydric or higher aliphatic alcohol as a constituent component.
Since the amorphous polyester resin A contains a trihydric or higher aliphatic alcohol as a constituent component, it has a branched structure in the molecular skeleton, and the molecular chain has a three-dimensional network structure, so that it deforms at low temperatures. However, it has a rubber-like property that it does not flow. Therefore, it is possible to maintain the heat-resistant storage stability and high-temperature offset resistance of the toner.
The non-crystalline polyester resin A can use a carboxylic acid having a valence of 3 or more, epoxy, or the like as a cross-linking component. Due to the high density, a fixed image formed by heat-fixing the toner may not exhibit sufficient gloss. When a cross-linking agent such as epoxy is used, the cross-linking reaction must be carried out after the polyester is polymerized. It reacts with the oligomer at the time of formation and tends to form a portion with a high cross-linking density.

The carboxylic acid having a valence of 3 or more is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aromatic carboxylic acids having a valence of 3 or more. Anhydrides of these may be used, lower alkyl esters (having 1 to 3 carbon atoms), or halides thereof may be used.
As the trivalent or higher aromatic carboxylic acid, a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms is preferable. Examples of the trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromellitic acid.

The polyisocyanate is not particularly limited and can 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 those obtained by blocking these with phenol derivatives, oximes, caprolactam, and the like.
The aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate and the like.
The alicyclic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.
The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. diphenyl, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 4,4'-diisocyanato-3-methyldiphenylmethane, 4,4'-diisocyanato-diphenyl ether and the like.
The araliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include α,α,α',α'-tetramethylxylylene diisocyanate.
The isocyanurates are not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include tris(isocyanatoalkyl)isocyanurate and tris(isocyanatocycloalkyl)isocyanurate.
These polyisocyanates may be used singly or in combination of two or more.

-Curing agent-
The curing agent is not particularly limited as long as it can react with the non-linear reactive precursor to form the amorphous polyester resin A, and can be appropriately selected according to the purpose. , for example, an active hydrogen group-containing compound.

--Active hydrogen group-containing compound--
The active hydrogen group in the active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the intended purpose. etc. These may be used individually by 1 type, and may use 2 or more types together.
The active hydrogen group-containing compound is not particularly limited and can 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 can be appropriately selected depending on the intended purpose. mentioned. These may be used individually by 1 type, and may use 2 or more types together.
Among these, diamines and mixtures of diamines and a small amount of trivalent or higher amines are preferred.
The diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aromatic diamines, alicyclic diamines, and aliphatic diamines. The aromatic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane and the like. The alicyclic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. be done. The aliphatic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include ethylenediamine, tetramethylenediamine and hexamethylenediamine.
The trivalent or higher amine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.
The aminoalcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.
The aminomercaptan is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aminoethylmercaptan and aminopropylmercaptan.
The amino acid is not particularly limited and can 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 can be appropriately selected depending on the intended purpose. ketimine compounds, oxazoline compounds, and the like.

In order to lower the Tg of the amorphous polyester resin A and easily impart the property of being deformed at low temperatures, the amorphous polyester resin A contains a diol component as a constituent component, and the diol component has a carbon number of It is preferable to contain 4 to 12 aliphatic diols in an amount of 50% by mass or more.
In addition, in order to lower the Tg of the amorphous polyester resin A and easily impart the property of being deformed at low temperatures, the amorphous polyester resin A contains fats having 4 to 12 carbon atoms in the total alcohol component. It is preferable to contain group diols in an amount of 50% by mass or more.
In order to lower the Tg of the amorphous polyester resin A and easily impart the property of being deformed at a low temperature, the amorphous polyester resin A contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component is It is preferable to contain 50% by mass or more of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms.
The weight-average molecular weight of the amorphous polyester resin A is not particularly limited and may be appropriately selected depending on the intended purpose. The following is preferable, 50,000 to 300,000 is more preferable, and 100,000 to 200,000 is particularly preferable. If the weight-average molecular weight is less than 20,000, the toner tends to flow at low temperatures, which may result in poor heat-resistant storage stability. Moreover, the viscosity at the time of melting becomes low, and the high-temperature offset property may deteriorate.
The molecular structure of the amorphous polyester resin A can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc., in addition to NMR measurement using a solution or solid. A simple method is to detect an amorphous polyester resin that does not have absorption based on δCH (out-of-plane bending vibration) of an olefin at 965±10 cm ⁻¹ and 990±10 cm ⁻¹ in the infrared absorption spectrum. .

The content of the amorphous polyester resin A is not particularly limited and can be appropriately selected according to the intended purpose. 10 parts by mass or more and 20 parts by mass or less is more preferable. If the content is less than 5 parts by mass, low-temperature fixability and high-temperature offset resistance may deteriorate. may decrease in intensity. When the content is within the range more preferable than the above, it is advantageous in terms of excellent low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability.

--Amorphous polyester resin B--
The amorphous polyester resin B preferably has a glass transition temperature (Tg) of 40° C. or higher and 80° C. or lower.
As the amorphous polyester resin B, a linear polyester resin is preferable.
As the amorphous polyester resin B, an unmodified polyester resin is preferable. The unmodified polyester resin is a polyester resin obtained by using a polyhydric alcohol, a polycarboxylic acid such as a polycarboxylic acid, a polycarboxylic anhydride, a polycarboxylic acid ester, or a derivative thereof. , is a polyester resin that has not been modified with an isocyanate compound or the like.
The amorphous polyester resin B preferably does not have urethane bonds and urea bonds.
The amorphous polyester resin B preferably contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component preferably contains 50 mol % or more of terephthalic acid. By doing so, it is advantageous in terms of heat resistant storage stability.

Examples of the polyhydric alcohols include diols.
Examples of the diol include polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane. Ethylene glycol, propylene glycol; hydrogenated bisphenol A, alkylene of hydrogenated bisphenol A (2 to 3 carbon atoms), etc. Oxide (average addition mole number 1 to 10) adducts and the like are included.
These may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyvalent carboxylic acid include dicarboxylic acids.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid; dodecenylsuccinic acid, octylsuccinic acid, and other alkyl groups having 1 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms. and succinic acid substituted with a group. These may be used individually by 1 type, and may use 2 or more types together.

For the purpose of adjusting the acid value and hydroxyl value, the amorphous polyester resin B may contain at least one of a trivalent or higher carboxylic acid and a trivalent or higher alcohol at the end of the resin chain. .
Examples of the tricarboxylic or higher carboxylic acid include trimellitic acid, pyromellitic acid, and acid anhydrides thereof.
Examples of the trihydric or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.
The molecular weight of the amorphous polyester resin B is not particularly limited and can be appropriately selected according to the purpose. Durability may be inferior, and if the molecular weight is too high, the viscoelasticity of the toner when it is melted may increase, resulting in poor low-temperature fixability. ) is preferably 3,000 to 10,000. Also, the number average molecular weight (Mn) is preferably 1,000 to 4,000. Also, Mw/Mn is preferably 1.0 to 4.0.
The weight average molecular weight (Mw) is more preferably 4,000 to 7,000. The number average molecular weight (Mn) is more preferably 1,500 to 3,000. The Mw/Mn is more preferably 1.0 to 3.5.

The acid value of the amorphous polyester resin B is not particularly limited, and can be appropriately selected according to the purpose. more preferred. When the acid value is 1 mgKOH/g or more, the toner tends to be negatively charged, and furthermore, the affinity between the toner and the paper is improved when the toner is fixed on the paper, and the low-temperature fixability can be improved. . Further, when the acid value is 50 mgKOH/g or less, the charging stability, particularly the charging stability against environmental changes, is improved.
The hydroxyl value of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 5 mgKOH/g or more.

The glass transition temperature (Tg) of the amorphous polyester resin B is preferably 40° C. or higher and 80° C. or lower, more preferably 50° C. or higher and 70° C. or lower. When the glass transition temperature is 40° C. or higher, the toner has sufficient heat-resistant storage stability and durability against stress such as agitation in a developing machine, and also has good filming resistance. When the glass transition temperature is 80° C. or lower, the toner is sufficiently deformed by heat and pressure during fixing, and good low-temperature fixability is obtained.

The molecular structure of the amorphous polyester resin B can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc., in addition to NMR measurement using a solution or solid. A simple method is to detect an amorphous polyester resin that does not have absorption based on δCH (out-of-plane bending vibration) of an olefin at 965±10 cm ⁻¹ and 990±10 cm ⁻¹ in the infrared absorption spectrum. .

The content of the amorphous polyester resin B is not particularly limited and can be appropriately selected according to the intended purpose. 60 parts by mass or more and 80 parts by mass or less is more preferable. When the content is less than 50 parts by mass, the dispersibility of the pigment and release agent in the toner deteriorates, and fogging and disturbance of images may easily occur. Since the contents of the polyester resin C and the amorphous polyester resin A are reduced, the low-temperature fixability may be poor. When the content is within the range more preferable than the above, it is advantageous in that both high image quality and low-temperature fixability are excellent.

In order to further improve the low-temperature fixability, it is preferable to use the amorphous polyester resin A and the crystalline polyester resin C together. In order to achieve both low-temperature fixability and high-temperature and high-humidity storage stability, the amorphous polyester resin A preferably has a very low glass transition temperature. Since it has a very low glass transition temperature, it has the property of being deformed at low temperature, deformed by heat and pressure during fixing, and has the property of being easily adhered to a recording medium such as paper at a lower temperature. In one aspect of the amorphous polyester resin A, since the reactive precursor is nonlinear, it has a branched structure in the molecular skeleton and the molecular chain has a three-dimensional network structure. It deforms at low temperatures, but has rubber-like properties that do not flow. Therefore, it is possible to maintain the heat-resistant storage stability and high-temperature offset resistance of the toner.
When the amorphous polyester resin A has urethane bonds or urea bonds with high cohesive energy, the adhesiveness to recording media such as paper is more excellent. In addition, since the urethane bond or urea bond behaves like a pseudo-crosslinking point, the rubber-like properties become stronger, and as a result, the heat-resistant storage stability and high-temperature offset resistance of the toner become more excellent.
That is, in the toner of the present invention, when the amorphous polyester resin A, the crystalline polyester resin C, and, if necessary, other amorphous polyester resin B are used in combination, the toner exhibits excellent low-temperature fixability. becomes. Furthermore, by using the amorphous polyester resin A having a glass transition temperature in the ultra-low temperature region, it is possible to maintain heat-resistant storage stability and high-temperature offset resistance even if the glass transition temperature of the toner is set low, and the toner is improved. By lowering the glass transition temperature, the low-temperature fixability is excellent.

<<coloring agent>>
The coloring agent is not particularly limited and can be appropriately selected depending on the intended purpose. Yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast yellow (5G, R), tartrazine lake, quinoline yellow lake, anthrazane yellow BGL, isoindolinone yellow, red iron oxide, red lead, red lead, cadmium red, cadmium mercury red, antimony vermillion, permanent red 4R, para red, Phise Red, Parachlororthonitroaniline Red, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fastlubin B, Brilliant Scarlet G , Risol 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 vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue lake, Peacock blue lake, Victoria blue lake, Metal-free phthalocyanine blue, Phthalocyanine blue, Fast sky blue, Indanthrene blue (RS, BC), Indigo, Ultramarine blue, Prussian 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 lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon, and the like. These may be used individually by 1 type, and may use 2 or more types together.

The content of the coloring agent is not particularly limited and can be appropriately selected according to the intended purpose. 10 parts by mass or less is more preferable.

The colorant can also be used as a masterbatch combined with a resin. Examples of resins to be used in the production of the masterbatch or kneaded together with the masterbatch include, in addition to the above amorphous polyester resins, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, or polymers of substituted styrenes 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 Styrenic copolymers such as coalescence, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide , polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type, and may use 2 or more types together.

The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant by applying a high shearing force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, in which an aqueous paste containing colorant water is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and the water and organic solvent components are removed. Since the cake can be used as it is, there is no need to dry it, and it is preferably used. For mixing and kneading, a high-shear dispersing device such as a three-roll mill is preferably used.

<<Other Ingredients>>
Examples of the other components include release agents, charge control agents, fluidity improvers, cleanability improvers, and magnetic materials.

-Release agent-
The release agent is not particularly limited and can be appropriately selected according to the intended purpose. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, and tree wax rice wax; Animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cersin; petroleum waxes such as paraffin, microcrystalline and petrolatum; and 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; poly-n-stearyl methacrylate and poly-n, which are low-molecular-weight crystalline polymer resins; - homopolymers or copolymers of polyacrylates such as lauryl methacrylate (for example, copolymers of n-stearyl acrylate-ethyl methacrylate); crystalline polymers having long alkyl groups in side chains;
Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax and polypropylene wax are preferred.

The melting point of the release agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60° C. or higher and 80° C. or lower. When the melting point is 60°C or higher, the heat-resistant storage stability is good. Further, when the melting point is 80° C. or less, a high-quality image can be obtained.

The content of the release agent is not particularly limited and can be appropriately selected according to the purpose. 8 parts by mass or less is more preferable.

- Charge control agent -
The charge control agent is not particularly limited and can be appropriately selected depending on the intended purpose. Alkoxy-based amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus elements or compounds, tungsten elements or compounds, fluorine-based activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. is 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-based metal complex E-82, and the salicylic acid-based metal complex E. -84, phenolic condensate E-89 (manufactured by Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), LRA -901, LR-147 (manufactured by Nippon Carlit Co., Ltd.) which is a boron complex, copper phthalocyanine, perylene, quinacridone, azo pigments, other sulfonic acid groups, carboxyl groups, polymer systems having functional groups such as quaternary ammonium salts compound.
The content of the charge control agent is not particularly limited and can be appropriately selected according to the purpose. .2 parts by mass or more and 5 parts by mass or less is more preferable.

- Fluidity improver -
The fluidity improver is not particularly limited as long as it can be subjected to surface treatment to increase hydrophobicity and prevent deterioration of fluidity and chargeability even under high humidity, and can be appropriately selected according to the purpose. Examples include silane coupling agents, silylating agents, silane coupling agents having alkyl fluoride groups, organic titanate-based coupling agents, aluminum-based coupling agents, silicone oils, and modified silicone oils. be done. It is particularly preferred that the silica and titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

- Cleanability improver -
The cleaning improver is not particularly limited as long as it is added to the toner in order to remove the developer remaining on the photoreceptor or the primary transfer medium after transfer, and may be appropriately selected according to the purpose. Examples thereof include zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, polymethyl methacrylate fine particles, polystyrene fine particles and the like produced by soap-free emulsion polymerization. The fine polymer particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle size of 0.01 μm to 1 μm.

－Magnetic materials－
The magnetic material is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include iron powder, magnetite, and ferrite. Among these, white ones are preferable in terms of color tone.

(Toner manufacturing method)
The method for producing the toner of the present invention is a method for producing the toner of the present invention, and includes a step of mixing the mother particles and the metal compound, and then further mixing the mother particles and the silicon compound (hereinafter referred to as a “mixing step”). ), and further includes other steps as necessary.

The base particles contain the non-crystalline polyester resin A, the non-crystalline polyester resin B, and the crystalline polyester resin C, and if necessary, the oil phase containing the releasing agent, the coloring agent, and the like. is preferably granulated by dispersing in an aqueous medium.
Further, the base particles contain the non-linear reactive precursor, the non-crystalline polyester resin B, and the crystalline polyester resin C, and if necessary, the curing agent, the release agent, Granulation is preferably carried out by dispersing the oil phase containing the colorant and the like in an aqueous medium.
An example of the method for producing such base particles is a known dissolution suspension method. As an example of the method for producing the base particles, a method for forming toner base particles while stretching the non-crystalline polyester resin A through an elongation reaction and/or a cross-linking reaction between the prepolymer and the curing agent will be described below. In such a method, an aqueous medium is prepared, an oil phase containing a toner material is prepared, the toner material is emulsified or dispersed, and an organic solvent is removed. After that, the toner is obtained by mixing the obtained mother particles with a metal compound and a silicon compound.

<Preparation of aqueous medium (aqueous phase)>
The aqueous medium can be prepared, for example, by dispersing the resin particles in the aqueous medium. The amount of the resin particles added to the aqueous medium is not particularly limited and can be appropriately selected according to the purpose. preferable.
The aqueous medium is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include water, water-miscible solvents, and mixtures thereof. These may be used individually by 1 type, and may use 2 or more types together. Among these, water is preferred.
The water-miscible solvent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include alcohols, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones and the like. The alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include methanol, isopropanol, ethylene glycol and the like. The lower ketones are not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include acetone and methyl ethyl ketone.

<Preparation of oil phase>
The preparation of the oil phase containing the toner material includes at least the non-linear reactive precursor, the non-crystalline polyester resin B, and the crystalline polyester resin C, and optionally the cured It can be carried out by dissolving or dispersing the toner material containing the agent, the releasing agent, the coloring agent, etc. in an organic solvent.
The organic solvent is not particularly limited and can be appropriately selected depending on the intended purpose, but an organic solvent having a boiling point of less than 150° C. is preferable because it is easy to remove.
The organic solvent having a boiling point of less than 150° C. is not particularly limited and can be appropriately selected depending on the intended purpose. , 1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferred, and ethyl acetate is more preferred.

<Emulsification or dispersion>
The emulsification or dispersion of the toner material can be performed by dispersing the oil phase containing the toner material in the aqueous medium. Then, when emulsifying or dispersing the toner material, the non-crystalline polyester resin A is produced by subjecting the curing agent and the non-linear reactive precursor to elongation reaction and/or cross-linking reaction.
The amorphous polyester resin A can be produced, for example, by the following methods (1) to (3).
(1) An oil phase containing the non-linear reactive precursor and the curing agent is emulsified or dispersed in an aqueous medium, and the curing agent and the non-linear reactive precursor are mixed in the aqueous medium. A method of producing the amorphous polyester resin A by elongation reaction and/or cross-linking reaction.
(2) The oil phase containing the non-linear reactive precursor is emulsified or dispersed in an aqueous medium to which the curing agent is added in advance, and the curing agent and the non-linear reactive precursor are emulsified or dispersed in the aqueous medium. A method of producing the amorphous polyester resin A by subjecting the body to elongation reaction and/or cross-linking reaction.
(3) After emulsifying or dispersing the oil phase containing the non-linear reactive precursor in an aqueous medium, the curing agent is added to the aqueous medium, and the curing agent is dispersed from the particle interface in the aqueous medium. and the non-linear reactive precursor are subjected to an elongation reaction and/or cross-linking reaction to form the amorphous polyester resin A.

When the curing agent and the non-linear reactive precursor are subjected to an elongation reaction and/or a cross-linking reaction from the particle interface, the non-crystalline polyester resin A is preferentially formed on the surface of the generated toner, A concentration gradient of the amorphous polyester resin A may be provided in the toner.
The reaction conditions (reaction time, reaction temperature) for producing the amorphous polyester resin A are not particularly limited, and depending on the combination of the curing agent and the non-linear reactive precursor, It can be selected as appropriate.
The reaction time is not particularly limited and can be appropriately selected according to the purpose, but is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours.
The reaction temperature is not particularly limited and can be appropriately selected depending on the intended purpose.
The method for stably forming the dispersion containing the non-linear reactive precursor in the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. Another method is to add an oil phase prepared by dissolving or dispersing a toner material in a solvent and to disperse it by shearing force.
The disperser for the dispersion is not particularly limited and can be appropriately selected according to the purpose. , an ultrasonic disperser, and the like.
Among these, a high-speed shear type disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 μm or more and 20 μm or less.
When the high-speed shear type disperser is used, the conditions such as rotation speed, dispersion time, and dispersion temperature can be appropriately selected according to the purpose.
The rotation speed is not particularly limited and can be appropriately selected according to the purpose, but is preferably 1,000 rpm or more and 30,000 rpm or less, more preferably 5,000 rpm or more and 20,000 rpm or less.
The dispersion time is not particularly limited and can be appropriately selected according to the purpose.
The dispersion temperature is not particularly limited and can be appropriately selected according to the intended purpose. In general, the higher the dispersion temperature, the easier the dispersion.
The amount of the aqueous medium used in emulsifying or dispersing the toner material is not particularly limited and can be appropriately selected according to the intended purpose. ,000 parts by mass or less, and more preferably 100 parts by mass or more and 1,000 parts by mass or less.
When the amount of the aqueous medium used is 50 parts by mass or more, the toner material is well dispersed, and mother particles having a predetermined particle size can be obtained. Further, when the amount of the aqueous medium used is 2,000 parts by mass or less, the production cost can be suppressed.

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 can be appropriately selected depending on the intended purpose. Examples thereof include surfactants, poorly water-soluble inorganic compound dispersants, polymeric protective colloids, and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, surfactants are preferred.
The surfactant is not particularly limited and can be appropriately selected depending on the purpose. For example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc. be able to.
The anionic surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters. Among these, those having a fluoroalkyl group are preferred.
A catalyst can be used for the elongation reaction and/or the cross-linking reaction when the amorphous polyester resin A is produced.
The catalyst is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include dibutyltin laurate and dioctyltin laurate.

<Removal of organic solvent>
The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and can be appropriately selected according to the purpose. A method of evaporating the organic solvent, a method of spraying the dispersion into a dry atmosphere to remove the organic solvent in the oil droplets, and the like can be mentioned.
When the organic solvent is removed, mother particles are formed. The mother particles can be washed, dried, and further classified. The classification may be carried out by removing fine particles in a liquid using a cyclone, decanter, centrifugation, or the like, or may be carried out after drying.

<Mixing process>
The obtained mother particles are mixed with a metal compound and a silicon compound. After the metal compound is adhered to the surface of the mother particles, the silicon compound is further adhered to the surface of the mother particles. Thereby, the silicon compound can be firmly immobilized on the surface of the base particle.
The amount of the metal compound added is preferably 0.2 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the mother particles.
The amount of the silicon compound added is preferably 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the mother particles.
A general powder mixer is used for mixing the metal compound and the silicon compound, and it is preferable to equip the mixer with a jacket or the like so that the internal temperature can be adjusted. In addition, in order to change the history of the load applied to the metal compound and the silicon compound, the metal compound and the silicon compound may be added midway or gradually. In this case, the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed.
Alternatively, a strong load may be applied first, followed by a relatively weak load, or vice versa. Mixing equipment that can be used includes, for example, a V-type mixer, a rocking mixer, a Loedige mixer, a Nauta mixer, a Henschel mixer, and the like. Then, it is passed through a sieve of 250 mesh or more to remove coarse particles and agglomerated particles to obtain a toner.

(developer)
The developer of the present invention has the toner of the present invention and a carrier.
The carrier is not particularly limited and can be appropriately selected depending on the intended purpose, but one having a core material and a resin layer covering the core material is preferable.

The material of the core material is not particularly limited and can be appropriately selected according to the purpose. Mn--Mg) materials are preferable, and from the viewpoint of securing image density, highly magnetized materials such as iron powder (100 emu/g or more) and magnetite (75 emu/g or more and 120 emu/g or less) are preferable. In addition, since the contact of the toner on the photoreceptor in a bristling state can be weakened and it is advantageous for high image quality, a copper-zinc (Cu—Zn) system (30 emu/g or more and 80 emu/g or less) or the like is used. Weakly magnetized materials are preferred. These may be used individually by 1 type, and may use 2 or more types together.

The volume average particle size of the core material is preferably 25 μm or more and 200 μm or less.

The material of the resin layer is not particularly limited and can be appropriately selected depending on the intended purpose. , polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride Polymers, fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, and the like. These may be used individually by 1 type, and may use 2 or more types together.

As for the mixing ratio of the toner and the carrier in the two-component developer, the mass ratio of the toner to the carrier is preferably 2.0% by mass or more and 12.0% by mass or less, more preferably 2.5% by mass or more and 10.0% by mass or less. .

(toner storage unit)
The toner containing unit of the present invention means a unit having a function of containing toner and containing toner. Here, examples of the toner storage unit include a toner storage container, a developing device, and a process cartridge.
A toner container is a container containing toner.
A developing device means a device having a means for containing toner and developing the toner.
A process cartridge is a cartridge that integrates at least an electrostatic latent image carrier (also referred to as an image carrier) and developing means, contains at least toner, and is detachable from an image forming apparatus. The process cartridge may further comprise at least one selected from charging means, exposure means and cleaning means.

(developer storage unit)
The developer containing unit of the present invention is a unit containing the developer of the present invention in a container.
Here, examples of the developer accommodating unit include a container containing developer, a developing device, a process cartridge, and the like.
A developer-containing container is a container containing a developer.
A developing device means a device having a means for accommodating developer and developing.
A process cartridge is a cartridge that integrates at least an image carrier and developing means and is detachable from an image forming apparatus. At least one of the charging means, the exposing means, and the cleaning means may be integrated with the image carrier and the developing means.

<Process cartridge>
A process cartridge according to the present invention includes an electrostatic latent image carrier that carries an electrostatic latent image, and a visible image formed by developing the electrostatic latent image carried on the electrostatic latent image carrier with toner. and developing means, and further means appropriately selected as necessary such as charging means, exposure means, developing means, transfer means, cleaning means, and static elimination means.
The developing means includes a developer container for containing the toner or developer of the present invention, and a developer carrier for carrying and transporting the toner or developer contained in the developer container. , and may further have a layer thickness regulating member or the like for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably installed in various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably installed in the image forming apparatus of the present invention, which will be described later.

(Image forming method and image forming apparatus)
The image forming apparatus of the present invention has an electrostatic latent image bearing member, electrostatic latent image forming means, and developing means, and further includes static eliminating means, cleaning means, recycling means, control means, and the like, if necessary. have other means.
The image forming method relating to the present invention includes an electrostatic latent image forming step and a developing step, and further includes other steps such as a static elimination step, a cleaning step, a recycling step and a control step, if necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming means, and the developing step can be performed by the developing means. and the other steps can be preferably performed by the other means.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on an electrostatic latent image carrier.
The material, shape, structure, size, etc. of the electrostatic latent image carrier (hereinafter sometimes referred to as "electrophotographic photoreceptor" or "photoreceptor") are not particularly limited, and may be selected from known ones. Although it can be selected as appropriate, the shape thereof is preferably a drum shape, and the material thereof includes, for example, inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors (OPC) such as polysilane and phthalopolymethine. are mentioned. Among these, an organic photoreceptor (OPC) is preferable in that a higher definition image can be obtained.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then imagewise exposing it to light. can be done.
The electrostatic latent image forming means includes, for example, charging means (charger) for uniformly charging the surface of the electrostatic latent image carrier, and exposure for imagewise exposing the surface of the electrostatic latent image carrier. means (exposure device).

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and can be appropriately selected depending on the intended purpose. , corotron, scorotron, and other non-contact chargers using corona discharge.
Preferably, the charger is placed in contact with or not in contact with the electrostatic latent image carrier, and charges the surface of the electrostatic latent image carrier by superimposing DC and AC voltages.
Further, the charger is a charging roller which is arranged in non-contact proximity to the electrostatic latent image bearing member via a gap tape, and a DC voltage and an AC voltage are superimposedly applied to the charging roller to carry the electrostatic latent image. Those that charge the body surface are preferred.

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

- Development process and development means -
The developing step is a step of developing the electrostatic latent image using the toner to form a visible image.
The formation of the visible image can be performed, for example, by developing the electrostatic latent image using the toner, and can be performed by the developing means.
The developing means preferably has, for example, a developing device that contains the toner and can apply the toner to the electrostatic latent image in a contact or non-contact manner. etc. are more preferable.

The developing device may be a monochromatic developing device or a multicolor developing device, and includes, for example, a stirrer that frictionally stirs and charges the toner, and a rotatable magnet roller. and the like are preferably exemplified.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image to a recording medium. After the visible image is primarily transferred onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. a first transfer step of transferring a visible image onto an intermediate transfer member to form a composite transfer image, and the composite A more preferred embodiment includes a second transfer step of transferring the transferred image onto the recording medium.

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

- Fixing process and fixing means -
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device. may be carried out at the same time in a laminated state.
The fixing device is not particularly limited and can be appropriately selected according to the purpose, but a known heating and pressurizing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller and an endless belt.

The charge removing step is a step of applying a charge removing bias to the electrostatic latent image carrier to remove charges, and can be preferably performed by a charge removing means.
The static elimination means is not particularly limited as long as it can apply a static elimination bias to the electrostatic latent image bearing member, and can be appropriately selected from known static eliminators. It is preferably mentioned.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image bearing member, and can be preferably carried out by cleaning means.
The cleaning means is not particularly limited as long as it can remove the toner remaining on the electrostatic latent image bearing member, and can be appropriately selected from known cleaners, such as a magnetic brush cleaner. , electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing means, and can be preferably carried out by the recycling means. The recycling means is not particularly limited, and includes known conveying means and the like.
The control step is a step of controlling each of the steps, and each step can be suitably performed by control means.
The control means is not particularly limited as long as it can control the movement of each means, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

FIG. 4 shows a first example of the image forming apparatus of the present invention. The image forming apparatus 100A includes a photosensitive drum 10, a charging roller 20, an exposure device, a developing device 40, an intermediate transfer belt 50, a cleaning device 60 having a cleaning blade, and a static elimination lamp .

The intermediate transfer belt 50 is an endless belt stretched by three rollers 51 arranged inside, and can move in the direction of the arrow in FIG. Some of the three rollers 51 also function as transfer bias rollers capable of applying a transfer bias (primary transfer bias) to the intermediate transfer belt 50 . A cleaning device 90 having a cleaning blade is arranged near the intermediate transfer belt 50 . Further, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) for transferring the toner image onto the transfer paper 95 is arranged to face the intermediate transfer belt 50 .

In addition, around the intermediate transfer belt 50 , a corona charging device 58 for applying electric charge to the toner image transferred to the intermediate transfer belt 50 is arranged with respect to the rotation direction of the intermediate transfer belt 50 as the photosensitive drum 10 . It is arranged between the contact portion of the intermediate transfer belt 50 and the contact portion of the intermediate transfer belt 50 and the transfer paper 95 .

The developing device 40 is composed of a developing belt 41 and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M and a cyan developing unit 45C arranged side by side around the developing belt 41 . The developing unit 45 for each color includes a developer container 42 , a developer supply roller 43 and a developing roller (developer carrier) 44 . The developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can move in the direction of the arrow in FIG. Furthermore, a portion of the developing belt 41 is in contact with the photoreceptor drum 10 .

Next, a method of forming an image using the image forming apparatus 100A will be described. First, the charging roller 20 is used to uniformly charge the surface of the photoreceptor drum 10, and then an exposure device (not shown) is used to expose the photoreceptor drum 10 to exposure light L to form an electrostatic latent image. to form Next, the electrostatic latent image formed on the photosensitive drum 10 is developed with toner supplied from the developing device 40 to form a toner image. Further, the toner image formed on the photosensitive drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, and then transferred by the transfer bias applied from the transfer roller 80. , is transferred (secondary transfer) onto the transfer paper 95 . On the other hand, the photosensitive drum 10 with the toner image transferred onto the intermediate transfer belt 50 is neutralized by the neutralization lamp 70 after residual toner on the surface is removed by the cleaning device 60 .

FIG. 5 shows a second example of the image forming apparatus used in the present invention. The image forming apparatus 100B does not have a developing belt 41, and has a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C arranged around the photosensitive drum 10 so as to directly face each other. Other than that, it has the same configuration as the image forming apparatus 100A.

FIG. 6 shows a third example of the image forming apparatus used in the present invention. The image forming apparatus 100C is a tandem-type color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400. FIG.

The intermediate transfer belt 50 provided in the central portion of the copying apparatus main body 150 is an endless belt stretched around three rollers 14, 15 and 16, and can move in the direction of the arrow in FIG. . A cleaning device 17 having a cleaning blade for removing toner remaining on the intermediate transfer belt 50 on which the toner image has been transferred to the recording paper is arranged near the roller 15 . Yellow, cyan, magenta, and black image forming units 120Y, 120C, 120M, and 120K are arranged side by side in the conveying direction while facing the intermediate transfer belt 50 stretched by rollers 14 and 15 .

An exposure device 21 is arranged near the image forming unit 120 . Further, the secondary transfer belt 24 is arranged on the side of the intermediate transfer belt 50 opposite to the side where the image forming unit 120 is arranged. The secondary transfer belt 24 is an endless belt stretched around a pair of rollers 23 . can be contacted.

In the vicinity of the secondary transfer belt 24, a fixing device 25 is provided with a fixing belt 26, which is an endless belt stretched between a pair of rollers, and a pressure roller 27 that is pressed against the fixing belt 26. are placed. A sheet reversing device 28 is arranged near the secondary transfer belt 24 and the fixing device 25 for reversing the recording paper when images are formed on both sides of the recording paper.

Next, a method of forming a full-color image using the image forming apparatus 100C will be described. First, a color document is set on the document table 130 of the automatic document feeder (ADF) 400, or the color document is set on the contact glass 32 of the scanner 300 by opening the automatic document feeder 400, and the document is automatically fed. Close the device 400 . When the start switch is pressed, when the original is set on the automatic document feeder 400, the original is conveyed and moved onto the contact glass 32. On the other hand, when the original is set on the contact glass 32, Immediately, the scanner 300 is driven, and the first traveling body 33 provided with the light source and the second traveling body 34 provided with the mirror travel. At this time, the reflected light from the document surface of the light emitted from the first traveling body 33 is reflected by the second traveling body 34, and then received by the reading sensor 36 via the imaging lens 35, whereby the document is read. It is read to obtain black, yellow, magenta and cyan image information.

Image information for each color is transmitted to each image forming means 18 in the image forming unit 120 for each color, and a toner image for each color is formed. As shown in FIG. 7, the image forming unit 120 for each color includes the photosensitive drum 10, the charging roller 160 for uniformly charging the photosensitive drum 10, and the photosensitive drum 10 based on the image information for each color. exposure light L to form an electrostatic latent image of each color; a developing device 61 that develops the electrostatic latent image with a developer of each color to form a toner image of each color; A transfer roller 62 for transferring onto the transfer belt 50 , a cleaning device 63 having a cleaning blade, and a charge removal lamp 64 are provided.

The toner images of each color formed by the image forming units 120 of each color are successively transferred (primary transfer) onto an intermediate transfer belt 50 that moves while being stretched by rollers 14, 15 and 16, and superimposed to form a composite toner image. It is formed.

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed recording paper from one of the paper feed cassettes 144 provided in the paper bank 143 in multiple stages. The sheet is separated and sent to the paper feed path 146, transported by the transport rollers 147, guided to the paper feed path 148 in the main body 150 of the copying apparatus, and stopped by being abutted against the registration roller 49. - 特許庁Alternatively, the recording paper on the manual feed tray 54 is fed out by rotating the paper feed roller, separated one by one by the separation roller 52 , guided to the manual paper feed path 53 , and stopped by being abutted against the registration roller 49 .

Although the registration roller 49 is generally grounded and used, it may be used with a bias applied to remove paper dust from the recording paper. Next, by rotating the registration roller 49 in synchronization with the composite toner image formed on the intermediate transfer belt 50, the recording paper is fed between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is formed. The toner image is transferred (secondary transfer) onto the recording paper. Toner remaining on the intermediate transfer belt 50 onto which the composite toner image has been transferred is removed by the cleaning device 17 .

After the recording paper onto which the composite toner image has been transferred is conveyed by the secondary transfer belt 24 , the composite toner image is fixed by the fixing device 25 . Next, the recording paper is switched to a conveying path by a switching claw 55 and discharged onto a paper discharge tray 57 by a discharge roller 56 . Alternatively, the recording paper is transferred to a conveying path by the switching claw 55, reversed by the sheet reversing device 28, similarly formed with an image on the back side, and then discharged onto the paper discharge tray 57 by the discharge rollers 56. .

According to the image forming apparatus and the image forming method of the present invention, since the toner of the present invention which is excellent in low-temperature fixability and causes extremely little occurrence of image fogging and photoreceptor filming is used, high-quality images can be provided for a long period of time. can do.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
"Melting point and glass transition temperature of resin (Tg)", "weight average molecular weight of resin (Mw)", "strength ratio (C/R)", "the above-mentioned The ratio (%) of the amount of the metal compound adhering to the surface of the mother particles with respect to the total amount of the metal compound and the "sphericity of the metal compound" were measured.

<Measurement of melting point and glass transition temperature (Tg) of resin>
The melting point and glass transition temperature were measured using a differential scanning calorimeter (Q-200, manufactured by TA Instruments). Specifically, after putting about 5.0 mg of the target sample into an aluminum sample container, the sample container was placed on a holder unit and set in an electric furnace. Next, the temperature was raised from −80° C. to 150° C. at a heating rate of 10° C./min in a nitrogen atmosphere.
From the obtained DSC curve, the glass transition temperature (Tg) of the target sample was determined using an analysis program in the differential scanning calorimeter.
Also, from the obtained DSC curve, the endothermic peak top temperature of the target sample was determined as the melting point using an analysis program in the differential scanning calorimeter.

<Measurement of weight average molecular weight (Mw) of resin>
The weight average molecular weight was measured using a GPC measuring device (HLC-8220GPC, manufactured by Tosoh Corporation) and a column TSKgel SuperHZM-H 15 cm triple (manufactured by Tosoh Corporation).
Specifically, the column was stabilized in a heat chamber at 40°C. Next, tetrahydrofuran (THF) was passed through the column at a flow rate of 1 mL/min, and 50 μL to 200 μL of a THF solution of 0.05 to 0.6% by mass of the sample was injected to measure the weight average molecular weight of the sample.
The standard polystyrene samples have weight average molecular weights of 6×10 ² , 2.1×10 ³ , 4×10 ³ , 1.75×10 ⁴ , 5.1×10 ⁴ , 1.1×10 ⁵ , Samples of 3.9×10 ⁵ , 8.6×10 ⁵ , 2×10 ⁶ and 4.48×10 ⁶ (manufactured by Pressure Chemical or Tosoh Corporation) were used. An RI (refractive index) detector was used as the detector.

<Method for measuring intensity ratio (C/R)>
The spectral intensity ratio C/R was calculated from the absorbance spectrum obtained by ATR method (total reflection method) measurement with FT-IR (Fourier transform infrared spectrometer, Avatar 370, manufactured by ThermoElectron).
Since the ATR method requires a smooth surface, the toner was molded under pressure to form a smooth surface. At this time, pressure molding was performed by applying a load of 1 t to 2.0 g of toner for 60 seconds to form a pellet having a diameter of 20 mm.
In the ATR method, a Ge crystal was used, and the incident angle was 41.5°, the resolution was 4 cm ⁻¹ , and the number of times of integration was 20.
The peak height of the characteristic spectrum of the crystalline state of the crystalline resin (1165 cm ^-1 in the case of polyester resin) is C (see FIG. 1, the baseline height is 1137 cm ^-1 to 1199 cm ^-1 ), and the amorphous The peak height of the characteristic spectrum of the resin (829 cm ^-1 for polyester resin) is R (see FIG. 2, the baseline height is 784 cm ^-1 to 889 cm ^-1 ), and C / R is the peak intensity. Calculated as a ratio. The peak intensity ratio in the present invention is obtained by converting the spectrum into absorbance and using the peak height.

<Percentage (%) of the amount of the metal compound adhering to the surface of the mother particle with respect to the total amount of the metal compound contained in the toner>
The adhesion amount (X1) of the metallic compound adhering to the surface of the mother particles and the total amount (Y=X1+X2) of the metallic compound contained in the toner can be measured as follows. By (X1/Y)×100, the ratio (%) of the amount of metal compound adhering to the surface of the base particles was determined.

-Amount of metal compound adhering to the surface of the mother particle (X1)-
(1) 5 g of polyoxyalkylene alkyl ether (Noigen ET-165, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was weighed into a 500 mL beaker. 300 mL of distilled water was added and sonicated to dissolve. It was transferred to a 1,000 mL volumetric flask and made up (if foaming occurs, leave it for a while). A 0.5% by mass dispersion of polyoxyalkylene alkyl ether (Noigen ET-165, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was prepared by ultrasonication.
(2) 3.75 g of a toner sample was dispersed in 50 mL of a 0.5 mass % polyoxyalkylene alkyl ether (Noigen ET-165, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) dispersion in a 110 mL vial.
(3) Using an ultrasonic homogenizer (trade name: homogenizer, model VCX750, CV33, manufactured by SONICS & MATERIALS), ultrasonic waves are applied at a frequency of 20 kHz, an output of 80 W, and an irradiation energy amount of 20 kJ for a certain period of time. The amount of irradiation energy given at this time was calculated from the product of the output and the irradiation time. At this time, the treatment was carried out while cooling the toner particle dispersion as appropriate so that the temperature of the toner particle dispersion did not reach 40° C. or higher.
(4) The resulting dispersion was suction-filtered with filter paper (trade name: qualitative filter paper (No. 2, 110 mm), manufactured by Advantec Toyo Co., Ltd.), washed again with ion-exchanged water twice, filtered, and separated. After removing the metal compound, the toner particles were dried.
(5) The intensity (or It was quantified by calculating mass% from the difference in strength before and after removal), and the adhesion amount (X1) of the metal compound adhering to the surface of the mother particles was determined.

<Fluorescent X-ray analysis>
3.00 g of the toner was molded into a pellet having a diameter of 3 mm and a thickness of 2 mm, and the toner was used as a sample toner for measurement.
Next, the content of the metal element derived from the metal compound in the pellet sample was measured by quantitative analysis using a fluorescent X-ray device.
For the measurement, a metal element standard sample (manufactured by Rigaku Corporation) was used to correct and calculate the content.
・Measuring device: ZSX-100e manufactured by Rigaku Corporation
・X-ray tube: Rh
・X-ray tube voltage: 50 kV
・X-ray tube current: 10mA

-Total Amount (Y) of Metal Compounds Contained in Toner-
The total amount (Y) of metal compounds contained in the toner was measured as follows.
Using an ultrasonic homogenizer, the amount of metal compounds in the toner particles irradiated with ultrasonic waves at 1,000 kJ and 1,500 kJ in the same manner as described above was measured by a fluorescent X-ray analyzer (manufactured by Rigaku Denki Co., Ltd., ZSX). -100e), it was confirmed that there was no decrease in the amount of metal compounds at 1,000 kJ and 1,500 kJ.
If there was no decrease, it was determined that all of the metal compound had been desorbed from the toner particles. Further, the surfaces of the toner particles after the treatment may be observed with a field emission scanning electron microscope (FE-SEM) to confirm that all the metal compounds are desorbed.
When a change was observed, the irradiation energy amount was further increased by 500 kJ and the same treatment was performed.
From the difference between the amount of the metal compound on the surface of the toner particles from which all the metal compounds have been removed as described above and the amount of the metal compound on the untreated toner particles from which no metal compound has been removed, the amount of the metal compound contained in the toner is determined. The total amount (Y) was calculated.
After all the metal compounds have been desorbed as described above, when "the amount of metal compounds in the mother particles from which all the metal compounds have been desorbed" is measured by fluorescent X-rays, the amount of metal compounds is either zero or the amount of metal in the mother particles is If a material containing a compound is included, it will be affected and have a certain value. On the other hand, when the amount of metal compound in the untreated toner is measured by fluorescent X-rays, the amount of metal compound is added by the amount of the metal compound and the material containing the metal compound in the mother particles as in the above case. The Rukoto.
Therefore, in order to calculate the total amount (Y) of the metal compound contained in the toner, the total amount of the metal compound in the toner and the amount of the metal compound on the surface of the mother particles from which all the metal compounds have been desorbed are calculated as described above. From the difference, the total amount (Y) of metal compounds contained in the toner was calculated.

<Sphericality of metal compound>
The sphericity of the metal compound was obtained by observing the primary particles of the metal compound after dispersing the metal compound in the toner with a scanning electron microscope (SEM) and analyzing the resulting primary particles of the metal compound. As image analysis software, image analysis software LMeye for OPTELICSC130 manufactured by Lasertech was used, and the following method was used.
(1) Capture an image observed at 5.0 kV by the SEM (2) Adjust calibration (scale) (3) Perform automatic contrast (4) Perform inversion (5) Perform edge extraction (Sobel) ( 6) Perform edge extraction (Sobel) again. (7) Perform binarization processing (discriminant analysis mode). (8) Calculate shape features (sphericity, absolute maximum length, diagonal width) by measurement. The sphericity of is the 50% sphericity in the cumulative frequency of equivalent circle diameters of 100 primary particles of the metal compound obtained by the above image analysis.

(Example 1)
-Preparation of Toner 1-
<Synthesis of Ketimine 1>
170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged into a reaction vessel equipped with a stirring rod and a thermometer, and reacted at 50° C. for 5 hours to obtain ketimine 1. The resulting ketimine 1 had an amine value of 418 mgKOH/g.

<Synthesis of amorphous polyester prepolymer A>
3-Methyl-1,5-pentanediol, adipic acid, and trimellitic anhydride were charged into a reaction vessel equipped with a condenser, stirrer, and nitrogen inlet tube. At this time, the molar ratio of hydroxyl groups to carboxyl groups was set to 1.5, the content of trimellitic anhydride in all monomers was set to 1 mol%, and 1,000 ppm of titanium tetraisopropoxide was added to all monomers. .
Next, the temperature is raised to 200° C. in about 4 hours, and the temperature is further raised to 230° C. in 2 hours, and the reaction is performed until water stops flowing out. A non-crystalline polyester A having

A reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube was charged with the amorphous polyester A having a hydroxyl group and isophorone diisocyanate. At this time, the molar ratio of isocyanate groups to hydroxyl groups was set to 2.0. Next, after diluting with ethyl acetate, the mixture was reacted at 100° C. for 5 hours to obtain a 50% by mass ethyl acetate solution of amorphous polyester prepolymer A.
A reaction vessel equipped with a heating device, a stirrer, and a nitrogen inlet tube was charged with a 50% by mass ethyl acetate solution of amorphous polyester prepolymer A and stirred, and then ketimine 1 was added dropwise. At this time, the molar ratio of amino groups to isocyanate groups was 1. Next, after stirring at 45° C. for 10 hours, the mixture was dried under reduced pressure at 50° C. until the residual amount of ethyl acetate was 100 ppm or less, and amorphous polyester A was obtained.
The obtained amorphous polyester A had a glass transition temperature (Tg) of −55° C. and a weight average molecular weight (Mw) of 130,000.

<Synthesis of Amorphous Polyester B>
A nitrogen inlet tube, a dehydration tube, a stirrer, and a reaction vessel equipped with a thermocouple were charged with a 2 mol ethylene oxide adduct of bisphenol A (BisA-EO), a 3 mol propylene oxide adduct of bisphenol A (BisA-PO), Terephthalic acid and adipic acid were charged. At this time, the molar ratio of BisA-EO to BisA-PO was 40/60, the molar ratio of terephthalic acid to adipic acid was 93/7, and the molar ratio of hydroxyl group to carboxyl group was 1.2. Then 500 ppm of titanium tetraisopropoxide was added.
Next, after reacting at 230° C. for 8 hours, reacting under reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Further, 1 mol % of trimellitic anhydride was added to all the monomers, and the mixture was reacted at 180° C. for 3 hours to obtain non-crystalline polyester B. The obtained amorphous polyester B had a glass transition temperature (Tg) of 67° C. and a weight average molecular weight (Mw) of 10,000.

<Synthesis of crystalline polyester C>
Sebacic acid and 1,6-hexanediol were charged into a reaction vessel equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple. At this time, the molar ratio of hydroxyl groups to carboxyl groups was set to 0.9, and 500 ppm of titanium tetraisopropoxide was added to the total amount of monomers.
Next, after reacting at 180° C. for 10 hours, the temperature was raised to 200° C. and reaction was continued for 3 hours. Furthermore, the reaction was carried out under a reduced pressure of 8.3 kPa for 2 hours to obtain a crystalline polyester C. The obtained crystalline polyester C had a melting point of 67° C. and a weight average molecular weight (Mw) of 25,000.

<Preparation of Masterbatch 1>
Using a Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.), 1,200 parts by weight of water, DBP oil absorption of 42 mL / 100 mg, pH of 9.5 carbon black (Printex 35, manufactured by Dexa) 500 parts by weight, and 500 After mixing parts by mass of amorphous polyester B, the mixture was kneaded at 150° C. for 30 minutes using two rolls. Next, after rolling and cooling, the powder was pulverized using a pulperizer to obtain a masterbatch 1.

<Synthesis of Wax Dispersant 1>
In an autoclave reactor equipped with a thermometer and a stirrer, 480 parts by mass of xylene, 100 masses of polyethylene Sanwax 151P (manufactured by Sanyo Chemical Industries, Ltd.) having a melting point of 108°C and a weight average molecular weight (Mw) of 1,000. After charging the parts, the polyethylene was dissolved and the atmosphere was replaced with nitrogen.
Next, a mixture of 805 parts by mass of styrene, 50 parts by mass of acrylonitrile, 45 parts by mass of butyl acrylate, 36 parts by mass of di-t-butyl peroxide, and 100 parts by mass of xylene was added dropwise over 3 hours at 170 ° C. Polymerize and hold for 30 minutes. Further, the solvent was removed to obtain a wax dispersant 1. The obtained wax dispersant 1 had a glass transition temperature of 65° C. and a weight average molecular weight (Mw) of 18,000.

<Preparation of Wax Dispersion 1>
In a container equipped with a stirring rod and a thermometer, 300 parts by mass of paraffin wax (HNP-9, manufactured by Nippon Seiro Co., Ltd.) having a melting point of 75 ° C., 150 parts by mass of wax dispersant 1, and 1,800 parts by mass of ethyl acetate. The mass part was charged.
Next, the temperature was raised to 80° C. with stirring, held for 5 hours, and then cooled to 30° C. in 1 hour. Furthermore, using a bead mill, Ultra Visco Mill (manufactured by Imex), 80% by volume of zirconia beads with a diameter of 0.5 mm were filled and dispersed under the conditions of 3 passes to obtain a wax dispersion 1. At this time, the liquid feeding speed was set to 1 kg/h, and the peripheral speed of the disk was set to 6 m/s.

<Preparation of Crystalline Polyester Dispersion 1>
A container equipped with a stirring rod and a thermometer was charged with 308 parts by mass of crystalline polyester C and 1,900 parts by mass of ethyl acetate. Next, the temperature was raised to 80° C. with stirring, held for 5 hours, and then cooled to 30° C. in 1 hour. Furthermore, using a bead mill, Ultra Viscomil (manufactured by Imex), 80% by volume of zirconia beads with a diameter of 0.5 mm were filled and dispersed under conditions of 3 passes to obtain a crystalline polyester dispersion liquid 1. At this time, the liquid feeding speed was set to 1 kg/h, and the peripheral speed of the disk was set to 6 m/s.

<Preparation of oil phase 1>
225 parts by weight of wax dispersion 1, 40 parts by weight of a 50% by weight ethyl acetate solution of amorphous polyester prepolymer A, 390 parts by weight of amorphous polyester B, 225 parts by weight of crystalline polyester dispersion 1, 60 parts by weight Part masterbatch 1 and 285 parts by mass of ethyl acetate were placed in a container and then mixed at 7,000 rpm for 60 minutes using a TK homomixer (manufactured by Primix Co., Ltd.) to obtain an oil phase 1.

<Synthesis of Vinyl Resin Dispersion Liquid 1>
In a reaction vessel equipped with a stirring rod and a thermometer, 683 parts by mass of water, sodium salt of sulfate ester of ethylene oxide adduct of methacrylic acid (Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.) 11 parts by mass, styrene 138 Parts by mass, 138 parts by mass of methacrylic acid, and 1 part by mass of ammonium persulfate were charged, and stirred at 400 rpm for 15 minutes to obtain a white emulsion.
Next, the temperature in the system was raised to 75° C. and the reaction was allowed to proceed for 5 hours. got The obtained vinyl resin dispersion liquid 1 had a volume average particle diameter of 0.14 μm.
The volume average particle diameter of vinyl resin dispersion liquid 1 was measured using a laser diffraction/scattering particle size distribution analyzer (LA-920, manufactured by HORIBA, Ltd.).

<Preparation of aqueous phase 1>
990 parts by mass of water, 83 parts by mass of vinyl resin dispersion 1, 48.5% by mass aqueous solution of sodium dodecyldiphenyl ether disulfonate (eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) 37 parts by mass, and 90 parts by mass of ethyl acetate The parts were mixed and stirred to obtain a milky white aqueous phase 1.

<Emulsification and solvent removal>
After adding 0.2 parts by mass of ketimine 1 and 1,200 parts by mass of aqueous phase 1 to a container containing oil phase 1, TK homomixer (manufactured by Primix Co., Ltd.) was used at 13,000 rpm. After mixing for 20 minutes, emulsified slurry 1 was obtained.
Emulsified slurry 1 was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed at 30° C. for 8 hours.

<Washing, heat treatment, drying>
100 parts by mass of dispersion slurry 1 was filtered under reduced pressure. Next, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed for 10 minutes at 12,000 rpm using a TK homomixer (manufactured by Primix Co., Ltd.), and then filtered (hereinafter referred to as washing step (1). ). Furthermore, 100 parts by mass of a 10% by mass sodium hydroxide aqueous solution was added to the filter cake, and after mixing for 30 minutes at 12,000 rpm using a TK homomixer, the mixture was filtered under reduced pressure (hereinafter referred to as washing step (2)). Next, 100 parts by mass of 10% by mass hydrochloric acid was added to the filter cake, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered (hereinafter referred to as washing step (3)). Furthermore, 300 parts by mass of ion-exchanged water was added to the filter cake, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered (hereinafter referred to as washing step (4)). At this time, the washing steps (1) to (4) were repeated twice.
100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer at 12,000 rpm for 10 minutes, heat-treated at 50° C. for 4 hours, and then filtered.
After drying the filter cake at 45° C. for 48 hours using a circulation dryer, the filter cake was sieved through a mesh with an opening of 75 μm to obtain mother particles 1 .

<Mixing process>
In a 20 L Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.), 100 parts by mass of the obtained mother particles 1 and alumina (AEROXIDE Alu65, manufactured by Nippon Aerosil Co., Ltd., sphericity: 0.7, electronegativity: 9.9) 0.5 part by mass was added and mixed for 3 minutes at a peripheral speed of 40 m/s. After that, 2 parts by mass of silica (AEROSIL NX90G, manufactured by Nippon Aerosil Co., Ltd., electronegativity: 16.7) was added, mixed for 17 minutes at a peripheral speed of 40 m/s, and passed through a sieve with an opening of 500 mesh. Toner 1 was obtained as described above.

(Example 2)
-Preparation of Toner 2-
Toner 2 was obtained in the same manner as in Example 1, except that aluminum oxide as the metal compound was replaced with cerium oxide (sphericity: 0.7, electronegativity: 11.6). .

(Example 3)
-Preparation of Toner 3-
In Example 1, aluminum oxide as the metal compound was replaced with zinc oxide (trade name: MZ-506X, manufactured by Tayca Corporation, sphericity: 0.7, electronegativity: 8.3). Toner 3 was obtained in the same manner as in Example 1.

(Example 4)
-Preparation of Toner 4-
Toner 4 was obtained in the same manner as in Example 1, except that the amount of aluminum oxide added as the metal compound was changed from 0.5 parts by mass to 0.1 parts by mass.

(Example 5)
-Preparation of Toner 5-
Toner 5 was obtained in the same manner as in Example 1, except that the amount of aluminum oxide added as the metal compound was changed from 0.5 parts by mass to 0.3 parts by mass.

(Example 6)
-Preparation of Toner 6-
Toner 6 was obtained in the same manner as in Example 1, except that the amount of aluminum oxide added as the metal compound was changed from 0.5 parts by mass to 0.9 parts by mass.

(Example 7)
-Preparation of Toner 7-
Toner 7 was obtained in the same manner as in Example 1, except that the amount of aluminum oxide added as the metal compound was changed from 0.5 parts by mass to 1.1 parts by mass.

(Example 8)
-Preparation of Toner 8-
Mother particles 2 were prepared in the same manner as in Example 1, except that the amount of crystalline polyester dispersion 1 added in <Preparation of oil phase 1> was changed from 225 parts by mass to 310 parts by mass. .
Next, Toner 8 was obtained in the same manner as in Example 1 except that the mother particles 1 were replaced with the mother particles 2 .

(Example 9)
-Preparation of Toner 9-
Mother particles 3 were prepared in the same manner as in Example 1, except that the amount of crystalline polyester dispersion 1 added in <Preparation of oil phase 1> was changed from 225 parts by mass to 115 parts by mass. .
Next, Toner 9 was obtained in the same manner as in Example 1 except that the mother particles 1 were replaced with the mother particles 3 .

(Example 10)
-Preparation of Toner 10-
Toner 10 was obtained in the same manner as in Example 1, except that aluminum oxide as the metal compound was replaced with zirconium oxide (sphericity: 0.8, electronegativity: 13.2). .

(Example 11)
-Preparation of Toner 11-
Toner 11 was obtained in the same manner as in Example 1, except that the <mixing step> was changed as follows.
<Mixing process>
In a 20 L Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.), 100 parts by mass of mother particles 1 and alumina (AEROXIDE Alu65, manufactured by Nippon Aerosil Co., Ltd., sphericity: 0.7, electronegativity: 9.9) 0.5 Part by weight and 2 parts by weight of silica (AEROSIL NX90G, manufactured by Nippon Aerosil Co., Ltd., electronegativity: 16.7) were added and mixed together at a peripheral speed of 40 m/s for 20 minutes. After that, it was passed through a sieve with an opening of 500 mesh.

(Example 12)
-Preparation of Toner 12-
Toner 12 was obtained in the same manner as in Example 1, except that the <mixing step> was changed as follows.
<Mixing process>
100 parts by mass of the obtained mother particles 1 and 2 parts by mass of silica (AEROSIL NX90G, manufactured by Nippon Aerosil Co., Ltd., electronegativity: 16.7) are added to a 20 L Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.), Mixed for 3 minutes at a peripheral speed of 40 m/s. After that, 0.5 parts by mass of alumina (AEROXIDE Alu65, manufactured by Nippon Aerosil Co., Ltd., sphericity: 0.7, electronegativity: 9.9) was added, mixed for 17 minutes at a peripheral speed of 40 m / s, and opened. It was passed through a 500 mesh sieve.

(Example 13)
-Preparation of Toner 13-
Mother particles 4 were produced in the same manner as in Example 1, except that the amount of crystalline polyester dispersion 1 added in <Preparation of oil phase 1> was changed from 225 parts by mass to 350 parts by mass. .
Next, Toner 13 was obtained in the same manner as in Example 1 except that the base particles 1 were replaced with the base particles 4 .

(Example 14)
-Preparation of Toner 14-
Mother particles 5 were produced in the same manner as in Example 1, except that the amount of crystalline polyester dispersion 1 added in <Preparation of oil phase 1> was changed from 225 parts by mass to 125 parts by mass. .
Next, Toner 14 was obtained in the same manner as in Example 1, except that the base particles 1 were replaced with the base particles 5 .

(Comparative example 1)
-Preparation of Toner 15-
Mother particles 6 were prepared in the same manner as in Example 1, except that the amount of crystalline polyester dispersion 1 added in <Preparation of oil phase 1> was changed from 225 parts by mass to 85 parts by mass. .
Next, Toner 15 was obtained in the same manner as in Example 1 except that the base particles 1 were replaced with the base particles 6 .

(Comparative example 2)
-Preparation of Toner 16-
In Example 1, aluminum oxide as the metal compound was replaced with titanium oxide (trade name: JMT-150IB, manufactured by Tayca, sphericity: 0.4, electronegativity: 14.8). Toner 16 was obtained in the same manner as in 1.

(Comparative Example 3)
-Preparation of Toner 17-
In Example 1, aluminum oxide as a metal compound was replaced with titanium oxide (trade name: JMT-150IB, manufactured by Tayca Corporation, sphericity: 0.4, electronegativity: 14.8), and the amount of titanium oxide added was changed. Toner 17 was obtained in the same manner as in Example 1, except that the was changed to 0.8 parts by mass.

(Comparative Example 4)
-Preparation of Toner 18-
Toner 18 was obtained in the same manner as in Example 1, except that aluminum oxide as the metal compound was replaced with magnesium oxide (sphericity: 0.7, electronegativity: 7.2). .

(Comparative Example 5)
-Preparation of Toner 19-
Mother particles 7 were prepared in the same manner as in Example 1, except that the amount of crystalline polyester dispersion 1 added in <Preparation of oil phase 1> was changed from 225 parts by mass to 400 parts by mass. .
Next, Toner 19 was obtained in the same manner as in Example 1 except that the mother particles 1 were replaced with the mother particles 7 .

(Comparative Example 6)
-Preparation of Toner 20-
Toner 20 was obtained in the same manner as in Example 1, except that the amount of aluminum oxide added as the metal compound was changed from 0.5 parts by mass to 0.3 parts by mass.

(Comparative Example 7)
-Preparation of Toner 21-
Toner 21 was obtained in the same manner as in Example 1, except that the amount of aluminum oxide added as the metal compound was changed from 0.5 parts by mass to 0.8 parts by mass.

(Comparative Example 8)
-Preparation of Toner 22-
Toner 22 was obtained in the same manner as in Example 1, except that the <mixing step> was changed as follows.
<Mixing process>
In a 20 L Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.), 100 parts by mass of mother particles 1 and alumina (AEROXIDE Alu65, manufactured by Nippon Aerosil Co., Ltd., sphericity: 0.7, electronegativity: 9.9) 2.5 Parts by mass were added and mixed together at a peripheral speed of 40 m/s for 20 minutes. After that, it was passed through a sieve with an opening of 500 mesh.

(Comparative Example 9)
-Preparation of Toner 23-
Toner 23 was obtained in the same manner as in Example 1, except that the <mixing step> was changed as follows.
<Mixing process>
100 parts by mass of mother particles 1 and 2.5 parts by mass of silica (AEROSIL NX90G, manufactured by Nippon Aerosil Co., Ltd., electronegativity: 16.7) are added to a 20 L Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.). It was collectively mixed for 20 minutes at a speed of 40 m/s. After that, it was passed through a sieve with an opening of 500 mesh.

(Example of manufacturing a carrier)
-Preparation of Coating Film Forming Solution-
The following composition was dispersed with a homomixer for 10 minutes to obtain a coating film-forming solution containing a silicone resin.
[composition]
・ Silicone resin solution ... 132.2 parts by mass [Solid content 23% by mass, SR2410, manufactured by Dow Corning Toray Silicone Co., Ltd.]
· Aminosilane ... 0.66 parts by mass [solid content 100% by mass, SH6020, manufactured by Dow Corning Toray Silicone Co., Ltd.]
· Conductive particles 1 ... 31 parts by mass [Substrate: alumina, surface treatment; lower layer = tin dioxide / upper layer = indium oxide containing tin dioxide, particle size: 0.35 µm, particle powder specific resistance: 3.5 Ω cm]
・Toluene: 300 parts by mass

-Production of carrier-
Using a sintered ferrite powder with a volume average particle diameter of 70 μm as a core material, the above coating film forming solution was applied to the surface of the core material so that the film thickness was 0.15 μm with a Spira coater (manufactured by Okada Seiko Co., Ltd.). °C and dried.
The obtained carrier was left in an electric furnace at 300° C. for 1 hour to be sintered. After cooling, the ferrite powder bulk was pulverized using a sieve with an opening of 125 μm to prepare a carrier.

<Production of developer>
8% by mass of the toners of Examples 1 to 14 and Comparative Examples 1 to 9 and 92% by mass of the carrier were mixed to prepare two-component developers.
Using each obtained developer, image formation was carried out as follows, and various properties were evaluated. The results are shown in Tables 1-5.

<Image formation>
Using an image forming apparatus (Ricoh Pro C751ex, manufactured by Ricoh Co., Ltd.) modified so that the contact charging means, process linear velocity, and development gap of the developing means can be changed, image formation was carried out under the following conditions.
Unless otherwise specified, the linear process speed was 500 mm/s, and the development gap between the contact charging means and the developing means was 0.3 mm.
50% RH at 23°C for 0 to less than 10,000 sheets, 85% RH at 28°C for 10,000 to less than 20,000 sheets, 15°C for 20,000 to less than 30,000 sheets An image with an image area ratio of 5% and an image with an image area ratio of 20% were alternately output every 1,000 sheets under the condition of 30% RH. This actual image formation was carried out with three sets up to 90,000 sheets.

<Low temperature fixability>
A temperature condition of 150° C. and a Ricoh full color PPC paper type 6000 were used. The image density retention rate was measured with X-Rite 938 (manufactured by X-RITE) to determine the image density retention rate, and the low-temperature fixability was evaluated according to the following criteria. "△" or more is a level acceptable for practical use.
[Evaluation criteria]
A: No image peeling, residual image density of 90% or more ○: No image peeling, residual image density of 75% or more and less than 90% △: No image peeling, residual image density of 60% More than or equal to less than 75% ×: There is image peeling, and the residual rate of image density is less than 60%

<Image fog>
After the completion of image formation on the 90,000 sheets, the toner was forcibly replenished, a solid white image was output, and the number and size of black spots generated on the background were evaluated according to rank. evaluated. "△" or more is a level acceptable for practical use.
[Evaluation criteria]
◎: Very good ○: Good △: Slightly inferior ×: Very bad

<Photoreceptor filming>
After the completion of image formation on the 90,000 sheets, the photoreceptor was observed and occurrence of abnormal images in solid images was confirmed and evaluated according to the following criteria. "△" or more is a level acceptable for practical use.
Photoreceptor filming means a state in which mother particles, a metal compound and a silicon compound adhere to the photoreceptor due to the pressure of a cleaning blade or the like, making development impossible.
[Evaluation criteria]
◎: Very good ○: No sticking on the photoreceptor △: Slight sticking on the photoreceptor, but no white spots in the solid image ×: Sticking on the photoreceptor, and White spots occur in the solid image

<Comprehensive judgment>
The evaluation criteria for comprehensive judgment are as follows. "⊚" is extremely good, "∘" is good, "Δ" is a level acceptable for practical use, and "x" is a level not acceptable for practical use. In addition, "◎", "◯", and "△" were regarded as pass, and "×" was regarded as unacceptable.
[Evaluation criteria]
◎: Two or more "◎" and no "△" or "×" ○: Up to one "◎", but no "△" or "×" △: One or more "△" and " No x: One or more x

＊表１中の混合方式における「分割／先添」は金属化合物とシリカを２分割して金属化合物を先に混合することを意味する。

* "Split/pre-add" in the mixing method in Table 1 means that the metal compound and silica are divided into two and the metal compound is first mixed.

＊表２中の混合方式における「分割／先添」は金属化合物とシリカを２分割して金属化合物を先に混合することを意味する。

* "Split/pre-add" in the mixing method in Table 2 means that the metal compound and silica are divided into two and the metal compound is first mixed.

＊表３中の混合方式における「分割／先添」は金属化合物とシリカを２分割して金属化合物を先に混合することを意味する。「一括」は金属化合物とシリカを一緒に混合することを意味し、金属化合物とシリカが１種の場合も含まれる。「分割／後添」は金属化合物とシリカを２分割して金属化合物を後に混合することを意味する。

* "Split/pre-add" in the mixing method in Table 3 means that the metal compound and silica are divided into two and the metal compound is first mixed. "Batch" means mixing the metal compound and silica together, including the case where the metal compound and silica are one. "Split/post-add" means dividing the metal compound and silica into two and mixing the metal compound later.

＊表４中の混合方式における「分割／先添」は金属化合物とシリカを２分割して金属化合物を先に混合することを意味する。

* "Split/pre-add" in the mixing method in Table 4 means that the metal compound and silica are divided into two and the metal compound is first mixed.

＊表５中の混合方式における「分割／先添」は金属化合物とシリカを２分割して金属化合物を先に混合することを意味する。「一括」は金属化合物とシリカを一緒に混合することを意味し、金属化合物とシリカが１種の場合も含まれる。

* "Split/pre-add" in the mixing method in Table 5 means that the metal compound and silica are divided into two and the metal compound is first mixed. "Batch" means mixing the metal compound and silica together, including the case where the metal compound and silica are one.

Embodiments of the present invention are, for example, as follows.
<1> A toner comprising base particles containing at least a resin, a metal compound, and a silicon compound,
Among the peaks observed at 1137 cm ⁻¹ to 1199 cm ⁻¹ of the toner obtained by FTIR-ATR (Total Reflection Absorption Infrared Spectroscopy) method, the highest peak intensity C and observed at 784 cm ⁻¹ to 889 cm ⁻¹ The ratio (C/R) to the intensity R of the highest peak among the peaks obtained satisfies the following formula, 0.05 ≤ C / R ≤ 0.20,
The metal compound contains at least one selected from an aluminum compound, a zinc compound, a cerium compound, and a zirconium compound,
The toner is characterized in that the amount of the metal compound adhering to the surface of the base particles is 60% or more and 90% or less with respect to the total amount of the metal compound contained in the toner.
<2> A toner comprising base particles containing at least a resin, a metal compound, and a silicon compound,
Among the peaks observed at 1137 cm ⁻¹ to 1199 cm ⁻¹ of the toner obtained by FTIR-ATR (Total Reflection Absorption Infrared Spectroscopy) method, the highest peak intensity C and observed at 784 cm ⁻¹ to 889 cm ⁻¹ The ratio (C/R) to the intensity R of the highest peak among the peaks obtained satisfies the following formula, 0.05 ≤ C / R ≤ 0.20,
The ratio [X(A)/X(Si)] of the electronegativity X(A) of the metal compound to the electronegativity X(Si) of the silicon compound is 0.5≦[X(A ) / X (Si)] ≤ 0.8,
The toner is characterized in that the amount of the metal compound adhering to the surface of the base particles is 60% or more and 90% or less with respect to the total amount of the metal compound contained in the toner.
<3> The toner according to any one of <1> and <2>, wherein the metallic compound has a sphericity of 0.5 or more, as represented by the following formula (1).
Sphericality = 4πA/L ² Expression (1)
However, in the formula (1), π represents the circular constant, A represents the projected area of the metal compound, and L represents the peripheral length of the projected image of the metal compound.
<4> the metal compound is aluminum oxide,
The toner according to any one of <1> to <3>, wherein the silicon compound is silicon oxide.
<5> the resin includes a crystalline resin and a non-crystalline resin, and the crystalline resin is a crystalline polyester resin;
The toner according to any one of <1> to <4>, wherein the amorphous resin is an amorphous polyester resin.
<6> A toner containing unit containing the toner according to any one of <1> to <5>.
<7> A developer comprising the toner according to any one of <1> to <5> and a carrier.
<8> A developer containing unit containing the developer according to <7> in a container.
<9> an electrostatic latent image carrier;
electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner according to any one of <1> to <5> to form a visible image. An image forming apparatus characterized by
<10> an electrostatic latent image carrier;
electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier with the developer according to <7> to form a visible image. It is a device.
<11> an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier;
and a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner according to any one of <1> to <5> to form a visible image. An image forming method characterized by
<12> an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier;
and a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with the developer according to <7> to form a visible image. The method.

The toner according to any one of <1> to <5>, the toner containing unit according to <6>, the developer according to <7>, the developer containing unit according to <8>, According to the image forming apparatus according to any one of <9> to <10> and the image forming method according to any one of <11> to <12>, various problems in the conventional art are solved, and the object of the present invention is can be achieved.

REFERENCE SIGNS LIST 10 electrostatic latent image carrier 10K electrostatic latent image carrier for black 10Y electrostatic latent image carrier for yellow 10M electrostatic latent image carrier for magenta 10C electrostatic latent image carrier for cyan 18 image forming means 40 developing device 61 developing device 100A image forming device 100B image forming device 100C image forming device

JP-A-2002-214833 JP 2005-338814 A JP 2007-206097 A

Claims (10)

A toner comprising base particles containing at least a resin, a metal compound, and a silicon compound,
1137 cm ⁻
The intensity C of the highest peak among the peaks observed at ¹ to 1199 cm ^-1 and 784 cm ^-1 to
The ratio (C/R) of the intensity R of the highest peak among the peaks observed at 889 cm ⁻¹ is given by the following formula,
satisfying 0.15 ≤ C/R ≤ 0.19 ,
The metal compound contains at least one selected from an aluminum compound and a cerium compound , and the adhesion amount of the metal compound adhering to the surface of the mother particles is equal to the total amount of the metal compound contained in the toner. A toner having a ratio of 70 % or more and 85 % or less. A toner comprising base particles containing at least a resin, a metal compound, and a silicon compound,
1137 cm ⁻
The intensity C of the highest peak among the peaks observed at ¹ to 1199 cm ^-1 and 784 cm ^-1 to
The ratio (C/R) to the intensity R of the highest peak observed at 889 cm ^-1 satisfies the following formula: 0.15 ≤ C/R ≤ 0.19 ,
The ratio [X
(A)/X(Si)] satisfies the following formula: 0.6 ≤ [X(A)/X(Si)] ≤ 0.7 ,
A toner, wherein the ratio of the amount of the metal compound adhering to the surface of the base particles to the total amount of the metal compound contained in the toner is 70 % or more and 85 % or less. 3. The toner according to claim 1, wherein the metal compound has a sphericity represented by the following formula (1) of 0.5 or more.
Sphericality=4πA/L2 Expression (1)
However, in the formula (1), π represents the circular constant, A represents the projected area of the metal compound, and L represents the peripheral length of the projected image of the metal compound. the metal compound is aluminum oxide,
4. The toner according to claim 1, wherein said silicon compound is silicon oxide. the resin comprises a crystalline resin and a non-crystalline resin, the crystalline resin being a crystalline polyester resin;
5. The toner according to any one of claims 1 to 4, wherein the amorphous resin is an amorphous polyester resin. A toner containing unit containing the toner according to any one of claims 1 to 5. A developer comprising the toner according to claim 1 and a carrier. 8. A developer containing unit comprising a container containing the developer according to claim 7. an electrostatic latent image carrier;
electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner according to any one of claims 1 to 5 to form a visible image. image forming device. an electrostatic latent image carrier;
electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier with the developer according to claim 7 to form a visible image. .

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