Toner, toner storage unit, and image forming apparatus

Abstract

To provide a toner that is excellent in low temperature fixability, heat-resistant storage property, cleaning property, and transferability.SOLUTION: A toner has a toner base particle containing a binder resin, and resin fine particles on the surface of the toner base particle. The glass-transition temperature of the toner during the first heating obtained by differential scanning calorimetry (DSC) is 20°C or more and 50°C or less. The glass-transition temperature of a component insoluble in tetrahydrofuran (THF) of the toner during the first heating obtained by DSC is -40°C or more and 10°C or less. The average circularity of the toner is 0.970 or more and 0.985 or less. The standard deviation of the average circularity is 0.020 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to toner, a toner storage unit, and an image forming apparatus. [Background technology]

[0002] In recent years, toners have been required to have small particle size and high-temperature offset resistance for high-quality output images, low-temperature fixing properties for energy saving, and heat-resistant storage properties to withstand high temperatures and humidity during storage and transportation after manufacturing. In particular, since power consumption during fixing accounts for a large portion of the power consumption in the image forming process, improving the low-temperature fixing properties of toners is extremely important. To improve the low-temperature fixing properties of toner, it is necessary to use materials with a low melting point in the toner. However, toner manufactured using materials with a low melting point has poor heat resistance for storage, and there is a trade-off between low-temperature fixing properties and heat resistance for storage.

[0003] Traditionally, toner produced by the kneading and grinding method has been used. However, toner produced by this method has several problems: it is difficult to reduce the particle size, its shape is irregular and the particle size distribution is broad, resulting in insufficient image quality, and it has high fixing energy. Furthermore, when wax (release agent) is added to improve fixing properties, toner produced by the kneading and grinding method breaks at the wax interface during grinding, resulting in a large amount of wax remaining on the toner surface. As a result, while a release effect is achieved, toner adhesion (filming) to the carrier, photoreceptor, and blade becomes more likely, and the overall performance is not satisfactory.

[0004] As a means of improving cleaning performance, it has been proposed that controlling the shape of the toner to be an irregular shape rather than a spherical shape can suppress the effect of slipping through the cleaning material (see, for example, Patent Document 1). [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a toner with excellent low-temperature fixability, heat resistance for storage, cleaning properties, and transferability.

[0006] The toner of the present invention, as a means for solving the above-mentioned problems, Toner matrix particles containing a binder resin, A toner having resin fine particles on the surface of the toner matrix particles, The glass transition temperature of the toner during the first heating cycle, as determined by differential scanning calorimetry (DSC), is between 20°C and 50°C. The glass transition temperature of the tetrahydrofuran (THF)-insoluble component of the toner during the first DSC heating cycle is between -40°C and 10°C. The average circularity of the aforementioned toner is 0.970 or more and 0.985 or less. The standard deviation of the mean circularity is 0.020 or less. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability, heat resistance for storage, cleaning properties, and transferability. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a schematic diagram showing an example of an image forming apparatus according to the present invention. [Figure 2] Figure 2 is a schematic diagram showing an example of a process cartridge. [Figure 3] Figure 3 shows an example of the state of resin fine particles on the toner surface in the present invention.

[0009] (toner) This invention relates to toner matrix particles containing a binder resin, A toner having resin fine particles on the surface of the toner matrix particles, The glass transition temperature of the toner during the first heating cycle, as determined by differential scanning calorimetry (DSC), is between 20°C and 50°C. The glass transition temperature of the component insoluble in tetrahydrofuran (THF) of the toner in the first heating by DSC is -40°C or higher and 10°C or lower. The average circularity of the toner is 0.970 or higher and 0.985 or lower. The standard deviation of the average circularity is 0.020 or lower.

[0010] In the toner described in Patent Document 1, simply by making the shape irregular, there was a problem that the transferability of the toner deteriorated in the transfer process of transferring the image on the image carrier directly to the printing paper or indirectly through an intermediate transfer member in the image forming process. Therefore, as a result of intensive studies by the present inventor, by setting the glass transition temperature of the toner to 20°C or higher and 50°C or lower and setting the glass transition temperature of the THF (tetrahydrofuran) insoluble component of the toner to -40°C or higher and 10°C or lower, while the entire toner particles maintain heat-resistant storage properties, a part of the resin constituting the toner becomes easily deformable even at low temperatures, and it was found that adhesion to the recording medium by heat and pressure during fixing can be promoted. Also, by setting the average circularity of the toner to 0.970 or higher and 0.985 or lower, the heat-resistant storage property and transferability are improved, and by setting the standard deviation of the average circularity to 0.020 or lower, it was found that the heat-resistant storage property and cleaning property are improved.

[0011] <Average circularity> In the toner of the present invention, the average circularity of the toner is 0.970 or higher and 0.985 or lower, and preferably 0.975 or higher and 0.980 or lower. The average circularity represents the degree of unevenness on the toner surface. When the average circularity is 0.970 or higher, resin fine particles and external additives can be uniformly adhered to the toner surface, and the heat-resistant storage property and transferability are improved. When the average circularity is 0.985 or lower, the frictional force when the toner rolls increases, making it difficult for the cleaning blade to pass through, and the cleaning property is excellent.

[0012] <Standard deviation of average circularity> The toner in this invention has a standard deviation of average circularity of 0.020 or less, preferably 0.014 or less. When the standard deviation of average circularity is 0.020 or less, the variation in the surface condition of each toner can be reduced, resulting in excellent heat resistance for storage and cleaning performance.

[0013] There are no particular restrictions on the method for measuring the average circularity and the standard deviation of the average circularity, and a suitable method can be selected depending on the purpose. For example, it can be measured using a flow-type particle image analyzer ("FPIA-2100", manufactured by Sysmex Corporation) and analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). Specifically, 0.1 ml to 0.5 ml or less of 10% by mass surfactant (alkylbenzenesulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, 0.1 g to 0.5 g of toner is added and stirred with a micro spatula, and 80 ml of deionized water is added. The resulting dispersion is dispersed using an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.) for 3 minutes, and the shape and distribution of the toner are measured using the analysis software FPIA-2100 until the toner concentration reaches 5,000 particles / μL to 15,000 particles / μL. In the above measurement method, it is important to set the dispersion concentration to 5,000 particles / μL to 15,000 particles / μL in order to ensure reproducibility in measuring the average circularity. Similar to the measurement of toner particle size mentioned earlier, the required amount of surfactant varies depending on the hydrophobicity of the toner. Adding too much surfactant will cause noise due to bubbles, while adding too little will prevent the toner from being sufficiently wetted, resulting in insufficient dispersion. Furthermore, the amount of toner added varies depending on the particle size; less is needed for small particle sizes, and more for large particle sizes. For toner particle sizes of 3 μm to 10 μm, adding 0.1 g to 0.5 g of toner makes it possible to adjust the dispersion concentration to 5,000 particles / μL to 15,000 particles / μL.

[0014] As a means for controlling the average circularity of the toner and the standard deviation of the average circularity, the average circularity of the toner and the standard deviation of the average circularity of the toner can be controlled by adjusting the peripheral speed of the bead mill disk when mixing the constituent materials of the toner during the preparation of the oil phase in the production of toner matrix particles, the number of times the toner passes through the bead mill per unit volume, etc.

[0015] <Glass transition temperature (Tg)> The toner of the present invention has a glass transition temperature (Tg) determined from the DSC curve of the first heating step by differential scanning calorimetry (DSC) of the toner, which is 20°C or higher and 50°C or lower, preferably 40°C or higher and 50°C or lower. When the glass transition temperature is 20°C or higher, the toner becomes less prone to deformation due to heat, improving its heat resistance and storage properties. When the glass transition temperature is 50°C or lower, the toner flows appropriately due to heat during fixing, making it easier for the toner to fix even at low temperatures, thus providing excellent low-temperature fixing properties.

[0016] The toner of the present invention has a glass transition temperature (Tg) determined from the DSC curve of the first heating step of the THF-insoluble portion of the toner by DSC, which is between -40°C and 10°C, and preferably between -40°C and 5°C. If the glass transition temperature is above -40°C, there is less inhibition of heat resistance during storage. If the glass transition temperature is below 10°C, a part of the resin constituting the toner becomes more easily deformable even at low temperatures, resulting in excellent low-temperature fixation.

[0017] The toner of the present invention preferably has a glass transition temperature (Tg) of 20°C or higher and 65°C or lower, which can be determined from the DSC curve of the first heating step of the THF-soluble portion of the toner using DSC. If the glass transition temperature is 20°C or higher, excellent heat resistance for storage can be obtained. If the glass transition temperature is 65°C or lower, excellent low-temperature fixing properties can be obtained.

[0018] There are no particular restrictions on the method for measuring the glass transition temperature, and it can be appropriately selected depending on the purpose. For example, it can be determined from a DSC curve obtained by differential scanning calorimetry (DSC). Specifically, 1 g of toner was added to 100 mL of tetrahydrofuran (THF), and Soxhlet extraction was performed to obtain THF-insoluble and THF-soluble components from the toner. The obtained THF-insoluble and THF-soluble components were dried separately in a vacuum dryer for 24 hours to obtain a THF-insoluble polyester resin component and a THF-soluble polyester resin component, respectively. In the following, the THF-insoluble polyester resin component was used as the target sample for measuring the glass transition temperature of the THF-insoluble component of the toner, and the THF-soluble polyester resin component was used as the target sample for measuring the glass transition temperature of the THF-soluble component of the toner. In addition, toner was used as the target sample for measuring the glass transition temperature of the toner. Next, 5.0 mg of the target sample is placed in an aluminum sample container, the sample container is placed on a holder unit, and then set in the electric furnace. Next, under a nitrogen atmosphere, the mixture is heated from -80°C to 150°C at a heating rate of 1.0°C / min (first heating pass). Next, the mixture is cooled from 150°C to -80°C at a cooling rate of 1.0°C / min, and then heated from -80°C to 150°C at a heating rate of 1.0°C / min (second heating cycle). During the first and second heating cycles described above, DSC curves were measured using a differential scanning calorimeter (Q-200, TA Instruments Inc.). From the obtained DSC curves, the DSC curve from the first heating cycle was selected using the analysis program in the Q-200 system to determine the glass transition temperature Tg1st for the first heating cycle. Similarly, the DSC curve from the second heating cycle was selected to determine the glass transition temperature Tg2nd for the second heating cycle.

[0019] The toner of the present invention has toner matrix particles and, if necessary, also contains other components.

[0020] <Toner matrix particles> The toner matrix particles (hereinafter sometimes referred to as "toner matrix" or "matrix particles") preferably contain a binder resin, a colorant, and a wax, and may further contain other components as needed. Furthermore, the toner matrix particles have resin fine particles on their surface.

[0021] <<Binding resin>> The binder resin is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyester resin, styrene-acrylic resin, polyol resin, vinyl resin, polyurethane resin, epoxy resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin. These may be used individually or in combination of two or more. Among these, polyester resin is preferred because it can impart flexibility to the toner.

[0022] <<<Polyester resin>>> There are no particular restrictions on the polyester resin, and it can be appropriately selected depending on the purpose. Examples include crystalline polyester resins, amorphous polyester resins, modified polyester resins, amorphous hybrid resins, etc. These may be used individually or in combination of two or more.

[0023] -Amorphous polyester resin- The amorphous polyester resin (hereinafter sometimes referred to as "amorphous polyester," "amorphous polyester," "amorphous polyester resin," "unmodified polyester resin," or "polyester resin component A") is not particularly limited and can be appropriately selected depending on the purpose. Examples include amorphous polyester resins obtained by reacting a polyol with a polycarboxylic acid. In this invention, amorphous polyester resin refers to a resin obtained by reacting a polyol with a polycarboxylic acid, as described above. Modified polyester resins, such as prepolymers described later, and modified polyester resins obtained by crosslinking and / or stretching the prepolymers, are not included in the amorphous polyester resin in this invention and are treated as modified polyester resins. Furthermore, unmodified polyester resin refers to a polyester resin obtained using a polyhydric alcohol and a polyhydric acid such as a polyhydric carboxylic acid, polyhydric carboxylic acid anhydride, or polyhydric carboxylic acid ester, or its derivative, that has not been modified with isocyanate compounds or the like. The amorphous polyester is a polyester resin component soluble in tetrahydrofuran (THF). The amorphous polyester (polyester resin component A) is preferably a linear polyester resin.

[0024] Examples of the aforementioned polyols include diols. Examples of the aforementioned diols include alkylene (2-3 carbon atoms) oxide (average number of added moles 1-10) adducts of bisphenol A such as 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; and alkylene (2-3 carbon atoms) oxide (average number of added moles 1-10) adducts of hydrogenated bisphenol A. These may be used individually or in combination of two or more types. Among these, it is preferable that the polyol contains 40 mol% or more of alkylene glycol.

[0025] Examples of the polycarboxylic acid include dicarboxylic acids. Examples of the dicarboxylic acid include alkyl groups having 1 to 20 carbon atoms, such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, dodecenyl succinic acid, and octyl succinic acid; and succinic acid substituted with alkenyl groups having 2 to 20 carbon atoms. These can be used individually or in combination of two or more types. Among these, it is preferable that the polycarboxylic acid contains 50 mol% or more of terephthalic acid.

[0026] The amorphous polyester resin may contain trivalent or higher carboxylic acids and / or trivalent or higher alcohols, trivalent or higher epoxy compounds, etc., at the ends of its resin chains in order to adjust the acid value and hydroxyl value. Among these, it is preferable to include a trivalent or higher aliphatic alcohol, and more preferably a trivalent or tetravalent aliphatic polyhydric alcohol with 3 to 10 carbon atoms, from the viewpoint of being less prone to unevenness and obtaining sufficient gloss and image density. Examples of the carboxylic acids with a valency of 3 or higher include trimellitic acid, pyromellitic acid, or their acid anhydrides. Examples of trivalent or higher alcohols include glycerin, pentaerythritol, and trimethylolpropane.

[0027] Furthermore, it is preferable that the amorphous polyester resin component contains a crosslinking component. While trivalent or higher carboxylic acids and epoxy compounds can be used as crosslinking components for amorphous polyester resin components, it is more preferable to include trivalent or higher aliphatic alcohols as crosslinking components from the viewpoint of preventing unevenness and obtaining sufficient gloss and image density. The crosslinking component preferably contains a trivalent or higher aliphatic alcohol, and more preferably contains a trivalent or tetravalent aliphatic alcohol from the viewpoint of gloss and image density of the fixed image. The trivalent or tetravalent aliphatic alcohol is preferably a trivalent or tetravalent aliphatic polyhydric alcohol component having 3 to 10 carbon atoms. The crosslinking component may consist only of the trivalent or higher aliphatic alcohol. The aforementioned trivalent or higher aliphatic alcohols can be appropriately selected depending on the purpose, and examples include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and dipentaerythritol. These trivalent or higher aliphatic alcohols may be used individually or in combination of two or more.

[0028] The molecular weight of the amorphous polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably within the following range. The weight-average molecular weight (Mw) of the amorphous polyester resin is preferably 3,000 to 10,000, and more preferably 4,000 to 7,000. The number-average molecular weight (Mn) of the amorphous polyester resin is preferably 1,000 to 4,000, and more preferably 1,500 to 3,000. The molecular weight ratio (Mw / Mn) of the amorphous polyester resin is preferably 1.0 or more and 4.0 or less, and more preferably 1.0 or more and 3.5 or less. The aforementioned molecular weight can be measured by GPC (gel permeation chromatography). The reason why the molecular weight is preferably within the above range is that if the molecular weight is too low, the toner may have poor heat resistance for storage and durability against stress such as agitation in the developing machine. If the molecular weight is too high, the viscoelasticity of the toner when melted may increase, resulting in poor low-temperature fixing properties. Also, if there is too much of a component with a molecular weight of 600 or less, the toner may have poor heat resistance for storage and durability against stress such as agitation in the developing machine. If there is too little of a component with a molecular weight of 600 or less, the low-temperature fixing properties may be poor.

[0029] The THF-soluble components with a molecular weight of 600 or less are preferably present in an amount of 2% to 10% by mass. One method for adjusting the content of this component is to extract amorphous polyester resin with methanol, remove components with a molecular weight of 600 or less, and then purify it.

[0030] There are no particular restrictions on the acid value of the amorphous polyester resin, and it can be appropriately selected depending on the purpose, but it is preferably 1 mg KOH / g or more and 50 mg KOH / g or less, and more preferably 5 mg KOH / g or more and 30 mg KOH / g or less. When the acid value is 1 mg KOH / g or more, the toner tends to become negatively charged, and furthermore, the affinity between the paper and the toner improves when fixing to paper, and the low-temperature fixing performance can be improved. On the other hand, when the acid value is 50 mg KOH / g or less, it is possible to prevent problems such as a decrease in charge stability, especially charge stability against environmental fluctuations.

[0031] There are no particular restrictions on the hydroxyl value of the amorphous polyester resin, and it can be appropriately selected depending on the purpose, but 5 mg KOH / g or higher is preferred.

[0032] The Tg of the amorphous polyester resin is preferably 40°C to 65°C, more preferably 45°C to 65°C, and even more preferably 50°C to 60°C. When the Tg is 40°C or higher, the heat resistance of the toner during storage and its durability against stress such as agitation in the developing machine are improved, and its filming resistance is also improved. On the other hand, when the Tg is 65°C or lower, deformation due to heating and pressurization during toner fixing is improved, and low-temperature fixing performance is improved.

[0033] The content of the amorphous polyester resin is preferably 80 parts by mass or more and 90 parts by mass or less per 100 parts by mass of toner.

[0034] -Crystalline polyester resin- The crystalline polyester resin (hereinafter also referred to as "crystalline polyester" or "polyester resin component D") is not particularly limited and can be appropriately selected depending on the purpose. For example, a crystalline polyester resin obtained by reacting a polyol with a polycarboxylic acid can be used.

[0035] The aforementioned crystalline polyester resin exhibits thermal melting properties, showing a rapid decrease in viscosity near the fixing start temperature, due to its high crystallinity. By using the crystalline polyester resin having these characteristics together with the amorphous polyester resin, the toner exhibits good heat resistance due to its crystalline properties until just before the melting temperature. At the melting temperature, the crystalline polyester resin undergoes a rapid decrease in viscosity (sharp melt) due to melting, and consequently becomes miscible with the amorphous polyester resin. As a result, both materials rapidly decrease in viscosity and fix, thus providing a toner that combines good heat resistance and low-temperature fixation properties. Furthermore, the release width (the difference between the fixing lower limit temperature and the high-temperature offset occurrence temperature) also shows favorable results.

[0036] The crystalline polyester resin is obtained using a polyhydric alcohol (polyol) and a polyhydric carboxylic acid or its derivative, such as a polyhydric carboxylic acid, polyhydric carboxylic acid anhydride, or polyhydric carboxylic acid ester. In this invention, crystalline polyester resin refers to a resin obtained by reacting a polyol with a polycarboxylic acid, as described above. Modified polyester resins, such as the prepolymer and resins obtained by crosslinking and / or stretching the prepolymer, do not belong to the category of crystalline polyester resin.

[0037] --Polyhydric alcohols (polyols)-- There are no particular restrictions on the polyhydric alcohol (polyol) mentioned above, and it can be appropriately selected depending on the purpose. Examples include diols and alcohols with a hydride of three or more.

[0038] Examples of the aforementioned diols include saturated aliphatic diols. Examples of the saturated aliphatic diols include linear saturated aliphatic diols and branched saturated aliphatic diols. These may be used individually or in combination of two or more. Among these, linear saturated aliphatic diols are preferred because they improve crystallinity and prevent a decrease in the melting point, and linear saturated aliphatic diols with 2 to 12 carbon atoms are more preferred. If the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin may decrease, and the melting point may be lowered. Furthermore, if the number of carbon atoms in the saturated aliphatic diol exceeds 12, it may become difficult to obtain practical materials. It is more preferable that the number of carbon atoms be 12 or less.

[0039] Examples of the saturated aliphatic diols 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, and 1,14-eicosanediol. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred because they exhibit high crystallinity and excellent sharp-melt properties in the crystalline polyester resin.

[0040] Examples of trivalent or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

[0041] --Polycarboxylic acids-- There are no particular restrictions on the polycarboxylic acid (polycarboxylic acid) and it can be appropriately selected depending on the purpose. Examples include divalent carboxylic acids and trivalent or higher carboxylic acids.

[0042] Examples of the divalent carboxylic acids include saturated aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, superiric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, and 1,18-octadecanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, and mesaconic acid; their anhydrides; and their lower (1-3 carbon atoms) alkyl esters.

[0043] Examples of the carboxylic acids with a valency of 3 or higher include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and their anhydrides and lower (1-3 carbon atoms) alkyl esters.

[0044] The polycarboxylic acid may include, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, 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 also be included. These may be used individually or in combination of two or more.

[0045] The crystalline polyester resin is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester resin preferably has constituent units derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and constituent units derived from a saturated aliphatic diol having 2 to 12 carbon atoms. This is preferable because it exhibits high crystallinity and excellent sharp melt properties, thus providing excellent low-temperature fixability.

[0046] The presence or absence of crystallinity in the crystalline polyester resin used in this invention can be confirmed by a crystallographic X-ray diffractometer (e.g., X'Pert Pro MRD, manufactured by Philips). The measurement method is described below. First, the target sample is ground in a mortar to create a sample powder, and the resulting sample powder is uniformly applied to the sample holder. Then, the sample holder is set in the diffractometer, and measurements are taken to obtain the diffraction spectrum. Crystallinity is determined to exist if the peak with the highest peak intensity among the obtained diffraction peaks in the range of 20° < 2θ < 25° has a peak width at half maximum of 2.0 or less. In this invention, a polyester resin that does not exhibit the above-mentioned state, as opposed to a crystalline polyester resin, is referred to as an amorphous polyester resin. The measurement conditions for X-ray diffraction are described below. [Measurement conditions] Tension kV: 45kV Current: 40mA MPSS Upper Gonio Scanmode: continue Starting angle: 3° End angle: 35° Angle Step: 0.02° Lucident beam optics Divergence slit: Div slit 1 / 2 Difflection beam optics Anti scatter slit: As fixed 1 / 2 Receiving slit: Prog rec slit

[0047] There are no particular restrictions on the melting point of the crystalline polyester resin, and it can be appropriately selected depending on the purpose, but it is preferably 60°C or higher and 80°C or lower. If the melting point is 60°C or higher, the crystalline polyester resin melts easily at low temperatures, which prevents the problem of reduced heat resistance of the toner. If the melting point is 80°C or lower, the melting of the crystalline polyester resin due to heating during fixing is insufficient, which prevents the problem of reduced low-temperature fixing performance.

[0048] There are no particular restrictions on the molecular weight of the crystalline polyester resin, and it can be appropriately selected depending on the purpose. The soluble orthodichlorobenzene content of the crystalline polyester resin is preferably such that, in GPC measurement, the weight-average molecular weight (Mw) is 3,000 to 30,000, and more preferably 5,000 to 15,000. The soluble orthodichlorobenzene content of the crystalline polyester resin is preferably such that the number average molecular weight (Mn) is 1,000 to 10,000, and more preferably 2,000 to 10,000, as measured by GPC. The molecular weight ratio Mw / Mn of the crystalline polyester resin is preferably 1.0 to 10, and more preferably 1.0 to 5.0. This is because substances with a sharp molecular weight distribution and low molecular weight exhibit excellent low-temperature fixation properties, while a high proportion of low molecular weight components reduces heat resistance during storage.

[0049] There are no particular restrictions on the acid value of the crystalline polyester resin, and it can be appropriately selected depending on the purpose. However, from the viewpoint of affinity between paper and resin, a value of 5 mg KOH / g or more is preferred, and 10 mg KOH / g or more is more preferred, in order to achieve the desired low-temperature fixation. On the other hand, to improve high-temperature offset resistance, a value of 45 mg KOH / g or less is preferred.

[0050] There are no particular restrictions on the hydroxyl value of the crystalline polyester resin, and it can be appropriately selected depending on the purpose. However, in order to achieve the desired low-temperature fixability and good electrostatic properties, a value of 0 mg KOH / g to 50 mg KOH / g is preferred, and 5 mg KOH / g to 50 mg KOH / g is more preferred.

[0051] The molecular structure of the crystalline polyester resin can be confirmed by NMR measurements in solution or solid state, as well as by X-ray diffraction, GC / MS, LC / MS, IR measurements, etc. A simpler method is infrared absorption spectroscopy, which can be used to determine the structure at 965±10 cm⁻¹. -1 or 990±10cm -1 One method involves detecting crystalline polyester resins that exhibit absorption based on δCH (out-of-plane bending vibration) of olefins.

[0052] There are no particular restrictions on the content of the crystalline polyester resin, and it can be appropriately selected depending on the purpose, but it is preferably 3 parts by mass or more and 20 parts by mass or less, and more preferably 5 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of toner. If the content is 3 parts by mass or more, it is possible to prevent the problem of poor low-temperature fixing performance due to insufficient sharp melting by the crystalline polyester resin. If it is 20 parts by mass or less, it is possible to prevent problems such as reduced heat resistance for storage and increased likelihood of image fogging.

[0053] -Amorphous Hybrid Resin- The amorphous hybrid resin comprises one or more resins selected from the group consisting of composite resins containing a condensation polymer resin and a styrene resin, and is a resin in which two polymer resin components, each having an independent reaction pathway, are partially chemically bonded, and at least one of them is a polymer resin component of the same polymer system as the polyester resin. In this specification, amorphous hybrid resin may be simply referred to as hybrid resin. By including the amorphous hybrid resin, the dispersibility of the crystalline polyester resin in the toner can be improved. The amorphous hybrid resin controls the exposure of crystalline polyester to the toner surface and uniformly disperses void polyester within the toner, thereby contributing to achieving both low-temperature fixation and heat-resistant storage. As the amorphous hybrid resin, for example, a resin obtained by mixing a mixture of raw material monomers of two polymerization resins, each having an independent reaction pathway, with a monomer that can react with either of the raw material monomers of the two polymerization resins (a bireactive monomer) is preferred as one of the raw material monomers.

[0054] Preferably, the two reactive monomers are monomers having, for example, at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group, and a secondary amino group, and an ethylenically unsaturated bond within the molecule. By using such reactive monomers, the dispersibility of the resin that forms the dispersed phase can be improved. Specific examples of the two reactive monomers mentioned above include, for example, acrylic acid, fumaric acid, methacrylic acid, citraconic acid, and maleic acid. Among these, acrylic acid, methacrylic acid, and fumaric acid are preferred.

[0055] The content of the two reactive monomers is preferably 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the raw material monomer of the condensation polymerization resin. In this invention, due to the unique properties of the two reactive monomers, they are treated as monomers separate from the raw material monomers of the condensation polymerization resin and the raw material monomers of the addition polymerization resin.

[0056] In the present invention, when obtaining the amorphous hybrid resin by carrying out two polymerization reactions using the above raw material monomer mixture and the two reactive monomers, it is not necessary for the polymerization reactions to proceed and be completed simultaneously. The reaction temperature and time can be appropriately selected according to the respective reaction mechanisms to allow the reactions to proceed and be completed. As a method for producing the amorphous hybrid resin, for example, it is preferable to mix raw material monomers for a condensation polymer resin, raw material monomers for an addition polymer resin, both reactive monomers, a catalyst such as a polymerization initiator, etc., to first obtain an addition polymer resin component having functional groups capable of undergoing a condensation polymer reaction mainly by radical polymerization at 50°C to 180°C, and then raise the reaction temperature to 190°C to 270°C, after which the condensation polymer resin component is formed mainly by a condensation polymer reaction.

[0057] The softening point of the amorphous hybrid resin is preferably 80°C to 170°C, more preferably 90°C to 160°C, and even more preferably 95°C to 155°C.

[0058] There are no particular restrictions on the weight ratio of the crystalline polyester resin to the amorphous hybrid resin, and it can be appropriately selected depending on the purpose. For example, a weight ratio of 50 / 100 to 200 / 100 of the polyester resin to the amorphous hybrid resin is preferred.

[0059] As the raw material monomer for the aforementioned condensation polymer resin, succinic acid derivatives are preferably used as the carboxylic acid component.

[0060] Styrene, α-methylstyrene, vinyltoluene, and other styrene derivatives are used as raw material monomers for the styrene-based resin.

[0061] The content of the styrene derivative is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, in the raw material monomer of the styrene resin.

[0062] Examples of raw material monomers for styrene-based resins that can be used in addition to the aforementioned styrene derivatives include alkyl (meth)acrylates; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; esters of ethylenically monocarboxylic acids such as dimethylaminoethyl (meth)acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; and N-vinyl compounds such as N-vinylpyrrolidone. Among these, alkyl (meth)acrylate is preferred from the viewpoint of toner's low-temperature fixation and electrostatic stability. From the above viewpoint, the number of carbon atoms in the alkyl group of the (meth)acrylate alkyl ester is preferably 1 to 22, and more preferably 8 to 18. The number of carbon atoms in the alkyl ester refers to the number of carbon atoms derived from the alcohol component that makes up the ester. Specifically, examples include methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (iso or tertiary)butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, (iso)stearyl (meth)acrylate, and the like.

[0063] From the viewpoint of low-temperature fixability, heat resistance, and electrostatic stability of the toner, the content of the alkyl (meth)acrylate is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less in the raw material monomer of the styrene resin.

[0064] There are no particular restrictions on the content of the hybrid resin, and it can be appropriately selected depending on the purpose, but it is preferable that it be 15% by mass or more relative to the amount of crystalline polyester. If the content is less than 15% by mass, the effect of internally dispersing the crystalline polyester is weak, and the crystalline polyester may be excessively placed on the surface.

[0065] -Modified polyester resin- The modified polyester resin (hereinafter sometimes referred to as "modified polyester" or "polyester resin component C") is not particularly limited and can be appropriately selected depending on the purpose. Examples include reaction products of an active hydrogen group-containing compound and a polyester resin having a site that can react with the active hydrogen group-containing compound (hereinafter sometimes referred to as "prepolymer" or "polyester prepolymer"). The aforementioned modified polyester is a polyester resin insoluble in tetrahydrofuran (THF). The polyester resin component insoluble in tetrahydrofuran (THF) has a lower Tg and melt viscosity, ensuring low-temperature fixability, while having a branched structure in its molecular backbone and a three-dimensional network structure in its molecular chains. As a result, it has rubber-like properties, deforming at low temperatures but not flowing. The modified polyester resin has a structure represented by any of the following general formulas 1) to 3), and has a structure in which R2, which is a polyester or modified polyester portion, and R1, which corresponds to a branched structure, are bonded together by a urethane or urea group. General formula 1) R1-(NHCONH-R2)n- General formula 2) R1-(NHCOO-R2)n- General formula 3) R1-(OCONH-R2)n- (In the above formula, n=3, R1 represents an isocyanurate skeleton, and R2 represents a group derived from either a polyester containing polycarboxylic acid and polyol, or a modified polyester obtained by isocyanate modification of the polyester.) Since the modified polyester resin has at least one of urethane bonds and urea bonds in its branched structure, the urethane bonds or urea bonds behave like pseudo-crosslinking points, which enhances the rubber-like properties of the modified polyester resin, making it possible to produce a toner with excellent heat resistance, storage resistance, and high-temperature offset resistance. The modified polyester resin contains a diol component as a constituent component, and more preferably a dicarboxylic acid component as a constituent component.

[0066] The modified polyester resin is not particularly limited as long as it is formed by bonding R2, which corresponds to polyester or a modified polyester portion, and R1, which corresponds to a branched structure portion, with a urethane or urea group, and can be appropriately selected depending on the purpose. There are no particular restrictions on how R1 and R2 are coupled, but for example, the following methods can be used. a) A method of producing a polyester polyol (R2) with hydroxyl groups at its terminals by esterifying a diol component and a dicarboxylic acid component, and then reacting the obtained polyester polyol with isocyanurates (R1). b) A method comprising esterifying a diol component with a dicarboxylic acid component to produce a polyester polyol (R2) with hydroxyl groups at its ends, reacting the obtained polyester polyol with a divalent polyisocyanate to produce an isocyanate-modified polyester (R2), and reacting the obtained isocyanate-modified polyester with isocyanurates (R1) in the presence of pure water. The hydroxyl groups remaining in the polyol obtained by either a) or b) above can be further reacted with a divalent or higher polyisocyanate to form a polyester prepolymer, which can then be used in the toner manufacturing process by reacting it with a curing agent. During the toner manufacturing process, the reaction with the curing agent generates urethane and urea bonds, exhibiting behavior similar to strong crosslinking points. This enhances the rubber-like properties of the modified polyester, resulting in superior heat resistance, storage resistance, and high-temperature offset resistance. Therefore, it is even more preferable to use a modified polyester resin in which the R2 portion is modified with isocyanate.

[0067] In order to lower the Tg of the modified polyester resin and make it easier to impart the property of deforming at low temperatures, the modified polyester preferably contains a diol component as a constituent, wherein the diol component has an odd number of carbon atoms in the main chain portion, which is between 3 and 9, and has an alkyl group in the side chain, and more preferably contains an aliphatic diol with 4 to 12 carbon atoms.

[0068] In the modified polyester resin, it is preferable to contain 50 mol% or more of the aliphatic diol having 3 to 12 carbon atoms, more preferably 80 mol% or more, and even more preferably 90 mol% or more.

[0069] Examples of the aliphatic diols having 3 to 12 carbon atoms include 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol. In particular, in the modified polyester resin, it is even more preferable that the diol component is an aliphatic diol having 3 to 9 carbon atoms, the number of carbon atoms in the main chain portion of the diol component is odd, and the diol component has an alkyl group in its side chain. Examples of aliphatic diols with an odd number of carbon atoms in the main chain and an alkyl group in the side chain, having 4 to 12 carbon atoms, include aliphatic diols represented by the following general formula (1). HO-(CR1R2)n-OH General formula (1) However, in the general formula (1) above, R1 and R2 each independently represent a hydrogen atom and an alkyl group having 1 to 3 carbon atoms. n represents an odd number from 3 to 9. In n repeating units, R1 may be the same or different. Also, in n repeating units, R2 may be the same or different.

[0070] Furthermore, in order to lower the Tg of the modified polyester resin and facilitate the imparting of properties that allow it to deform at low temperatures, it is preferable that the amorphous polyester resin C contains 50 mol% or more of aliphatic diols having 3 to 12 carbon atoms in the total alcohol components.

[0071] In order to lower the Tg of the modified polyester resin and facilitate the imparting of properties that allow it to deform at low temperatures, it is preferable that the amorphous polyester resin C contains a dicarboxylic acid component, and that the dicarboxylic acid component contains an aliphatic dicarboxylic acid having 4 to 12 carbon atoms.

[0072] In the polyester resin, it is preferable that it contains 30 mol% or more of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms. Examples of the aliphatic dicarboxylic acids having 4 to 12 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanediic acid.

[0073] -Diol component- The aforementioned diol component is not particularly limited and can be appropriately selected depending on the purpose. Examples include aliphatic diols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol; diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene Examples include diols having oxyalkylene groups such as ethylene glycol and polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols to which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide have been added; bisphenols such as bisphenol A, bisphenol F, and bisphenol S; and alkylene oxide adducts of bisphenols to which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide have been added. Among these, aliphatic diols having 4 to 12 carbon atoms are preferred. These diols may be used individually or in combination of two or more.

[0074] -Dicarboxylic acid components- The dicarboxylic acid component is not particularly limited and can be appropriately selected depending on the purpose. Examples include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. In addition, anhydrides of these compounds may be used, as well as lower (1-3 carbon atoms) alkyl esters or halides. The aliphatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples include succinic acid, adipic acid, sebacic acid, dodecanediic acid, maleic acid, and fumaric acid. The aromatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, but aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferred. The aforementioned aromatic dicarboxylic acid having 8 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose. Examples 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 or in combination of two or more.

[0075] -Alcohols with a hydride of 3 or higher- There are no particular restrictions on the alcohols with a valency of 3 or higher, and they can be appropriately selected depending on the purpose. Examples include aliphatic alcohols with a valency of 3 or higher, polyphenols with a valency of 3 or higher, and alkylene oxide adducts of polyphenols with a valency of 3 or higher. Examples of trivalent or higher aliphatic alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol. Examples of trivalent or higher polyphenols include trisphenol PA, phenol novolac, and cresol novolac. Examples of alkylene oxide adducts of polyphenols with a valency of 3 or higher include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to polyphenols with a valency of 3 or higher.

[0076] -Polyisocyanate- There are no particular restrictions on the polyisocyanate, and it can be appropriately selected depending on the purpose. Examples include diisocyanates and isocyanates with a valentity of 3 or higher. Examples of the diisocyanates include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aromatic aliphatic diisocyanates, isocyanurates, and those obtained by blocking these with phenol derivatives, oximes, caprolactams, etc. Examples of the isocyanates with a valency of 3 or higher include lysine triisocyanate, or those obtained by reacting a trivalent or higher alcohol with a diisocyanate, or by reacting a polyisocyanate to produce an isocyanurate. Among these, it is even more preferable to use polyisocyanates having an isocyanurate skeleton because they act as stronger crosslinking points and offer even better heat resistance, storage resistance, and high-temperature offset resistance.

[0077] The trivalent isocyanate component is preferably present in an amount of 0.2 mol% to 1.0 mol% relative to the resin component in the THF-insoluble portion of the toner. When a crosslinked structure is formed using a trivalent isocyanate component, the cohesive force of the molecular chain is increased by pseudo-crosslinking by urethane or urea bonds at the crosslinking points. This improves heat resistance and storage properties even with a low crosslinking density, and enables high-level low-temperature fixation. If the trivalent isocyanate component is less than 0.2 mol%, the formation of the branched structure may be insufficient, and the resulting uneven network structure may become the starting point for deterioration of heat resistance and filming resistance. If the amount of trivalent isocyanate component exceeds 1.0 mol%, the low-temperature fixation properties may deteriorate due to the formation of a dense cross-linking structure. There are no particular restrictions on the aliphatic diisocyanate, and it can be appropriately selected depending on the purpose. Examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate. There are no particular restrictions on the alicyclic diisocyanate, and it can be appropriately selected depending on the purpose. Examples include isophorone diisocyanate and cyclohexylmethane diisocyanate. The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4'-diisocyanatodiphenyl, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 4,4'-diisocyanato-3-methyldiphenylmethane, and 4,4'-diisocyanato-diphenyl ether. The aromatic aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples include α,α,α',α'-tetramethylxylylene diisocyanate. The isocyanurates mentioned above are not particularly limited and can be appropriately selected depending on the purpose. Examples include tris(isocyanatoalkyl)isocyanurate and tris(isocyanatocycloalkyl)isocyanurate. These polyisocyanates may be used individually or in combination of two or more.

[0078] <Resin fine particles> The aforementioned resin fine particles are present on the surface of the toner matrix particles.

[0079] The resin fine particles preferably consist of a core resin (core portion) and a shell resin (outer shell portion) that covers at least a part of the surface of the core resin, more preferably consist of a core resin (hereinafter also referred to as "resin (b2)") and a shell resin (hereinafter also referred to as "resin (b1)"), and even more preferably the shell resin (b1) and core resin (b2) have vinyl units. The vinyl-based units in the shell resin and the core resin are preferably polymers obtained by homopolymerizing or copolymerizing vinyl monomers.

[0080] Examples of the vinyl monomers include the following (1) to (10). (1) Vinyl hydrocarbons Examples of vinyl hydrocarbons include (1-1) aliphatic vinyl hydrocarbons, (1-2) alicyclic vinyl hydrocarbons, and (1-3) aromatic vinyl hydrocarbons.

[0081] (1-1) Aliphatic vinyl hydrocarbons Examples of aliphatic vinyl hydrocarbons include alkenes and alkadienes. Specific examples of the aforementioned alkenes include ethylene, propylene, and α-olefins. Specific examples of the aforementioned alkadienes include butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, and 1,7-octadiene.

[0082] (1-2) Alicyclic vinyl hydrocarbons Examples of alicyclic vinyl hydrocarbons include mono- or di-cycloalkenes and alkadienes, with specific examples including (di)cyclopentadiene and terpenes.

[0083] (1-3) Aromatic vinyl hydrocarbons Examples of aromatic vinyl hydrocarbons include styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl, and / or alkenyl) substituted derivatives, specifically α-methylstyrene, 2,4-dimethylstyrene, and vinylnaphthalene.

[0084] (2) Carboxyl group-containing vinyl monomers and salts thereof Examples of the carboxyl group-containing vinyl monomers and their salts include unsaturated monocarboxylic acids (salts), unsaturated dicarboxylic acids (salts), and their anhydrides (salts), and their monoalkyl (1-24 carbon atoms) esters or salts thereof. Specifically, examples include (meth)acrylic acid, (anhydride) maleic acid, maleic acid monoalkyl esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, carboxyl group-containing vinyl monomers such as cinnamic acid, and metal salts thereof.

[0085] In this invention, "(salt)" means an acid or a salt thereof. For example, "unsaturated monocarboxylic acid (salt) with 3 to 30 carbon atoms" means an unsaturated monocarboxylic acid or its salt. In this invention, "(meth)acrylic" means methacrylic acid or acrylic acid. In this invention, "(meth)acryloyl" means methacryloyl or acryloyl. In this invention, "(meth)acrylate" means methacrylate or acrylate.

[0086] (3) Sulfonic acid group-containing vinyl monomers, vinyl sulfate monoesters, and salts thereof Examples of the sulfonic acid group-containing vinyl monomers, vinyl sulfate monoesters, and salts thereof include C2-C14 alkene sulfonic acid (salt), C2-C24 alkyl sulfonic acid (salt), sulfo(hydroxy)alkyl-(meth)acrylate (salt), or (meth)acrylamide (salt), alkylallyl sulfosuccinate (salt), and so on. Specifically, examples of alkene sulfonic acids having 2 to 14 carbon atoms include vinyl sulfonic acid (salt), examples of alkyl sulfonic acids having 2 to 24 carbon atoms include α-methylstyrene sulfonic acid (salt), and examples of sulfo(hydroxy)alkyl-(meth)acrylate (salt) or (meth)acrylamide (salt) include sulfopropyl (meth)acrylate (salt), sulfate ester (salt), or sulfonic acid group-containing vinyl monomer (salt).

[0087] (4) Phosphate group-containing vinyl monomers and their salts Examples of phosphate-containing vinyl monomers and their salts include (meth)acryloyloxyalkyl (1-24 carbon atoms) phosphate monoester (salt) and (meth)acryloyloxyalkyl (1-24 carbon atoms) phosphonic acid (salt). Specific examples of the (meth)acryloyloxyalkyl (1-24 carbon atoms) phosphate monoester (salt) mentioned above include 2-hydroxyethyl (meth)acryloyl phosphate (salt) and phenyl-2-acryloyloxyethyl phosphate (salt). Specific examples of the (meth)acryloyloxyalkyl (1-24 carbon atoms) phosphonic acid (salt) mentioned above include 2-acryloyloxyethylphosphonic acid (salt).

[0088] Examples of the salts in (2) to (4) above include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, and quaternary ammonium salts.

[0089] (5) Hydroxyl group-containing vinyl monomer Examples of the hydroxyl group-containing vinyl monomers include hydroxystyrene, N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, (meth)allyl alcohol, clotyl alcohol, isoclotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-buten-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, and sucrose allyl ether.

[0090] (6) Nitrogen-containing vinyl monomer Examples of the nitrogen-containing vinyl monomers include (6-1) amino group-containing vinyl monomers, (6-2) amide group-containing vinyl monomers, (6-3) nitrile group-containing vinyl monomers, (6-4) quaternary ammonium cation group-containing vinyl monomers, and (6-5) nitro group-containing vinyl monomers.

[0091] (6-1) Examples of amino group-containing vinyl monomers include aminoethyl (meth)acrylate.

[0092] (6-2) Examples of amide group-containing vinyl monomers include (meth)acrylamide and N-methyl(meth)acrylamide.

[0093] (6-3) Examples of nitrile group-containing vinyl monomers include (meth)acrylonitrile, cyanostyrene, and cyanoacrylate.

[0094] (6-4) Examples of vinyl monomers containing quaternary ammonium cation groups include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, and quaternary amine group-containing vinyl monomers such as diallylamine (quaternized using quaternizing agents such as methyl chloride, dimethyl sulfate, benzyl chloride, and dimethyl carbonate).

[0095] (6-5) Examples of nitro group-containing vinyl monomers include nitrostyrene.

[0096] (7) Epoxy group-containing vinyl monomer Examples of the epoxy group-containing vinyl monomers include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and p-vinylphenylphenyl oxide.

[0097] (8) Halogen-containing vinyl monomers Examples of the halogen-containing vinyl monomers include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, and chloroprene.

[0098] (9) Vinyl esters, vinyl (thio) ethers, vinyl ketones Examples of the vinyl esters include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth)acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxyacrylate, alkyl (meth)acrylate having an alkyl group with 1 to 50 carbon atoms [methyl ( (Meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, etc.), dialkyl fumarate (the two alkyl groups are linear, branched, or alicyclic groups with 2 to 8 carbon atoms), diary Lumaleates (the two alkyl groups are linear, branched, or alicyclic groups with 2 to 8 carbon atoms), poly(meth)allyloxyalkanes [diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc.], vinyl monomers having polyalkylene glycol chains [polyethylene glycol (molecular weight 300) mono(meth)acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl Examples include [10-mol ethylene oxide adduct (meth)acrylate, 30-mol lauryl alcohol ethylene oxide adduct (meth)acrylate, etc.], and poly(meth)acrylates [poly(meth)acrylates of polyhydric alcohols: ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyethylene glycol di(meth)acrylate, etc.]. Examples of vinyl (thio) ethers include vinyl methyl ether. Examples of vinyl ketones include vinyl methyl ketone.

[0099] (10) Other vinyl monomers Other vinyl monomers include, for example, tetrafluoroethylene, fluoroacrylate, isocyanatoethyl (meth)acrylate, and m-isopropenyl-α,α-dimethylbenzyl isocyanate.

[0100] For the synthesis of the shell resin (b1), one of the vinyl monomers (1) to (10) above may be used alone, or two or more may be used in combination. From the viewpoint of low-temperature fixation properties, the shell resin (b1) is preferably styrene-(meth)acrylic acid ester copolymer and (meth)acrylic acid ester copolymer, and more preferably styrene-(meth)acrylic acid ester copolymer. The presence of a carboxylic acid in the shell resin (b1) imparts an acid value to the resin, making it easier for resin fine particles to adhere to the surface of toner particles and form toner particles.

[0101] The vinyl monomer used in the core resin (b2) is the same as that used in the shell resin (b1). For the synthesis of the core resin (b2), one of the vinyl monomers (1) to (10) listed above for the shell resin (b1) may be used alone, or two or more may be used in combination. From the viewpoint of low-temperature fixation properties, the core resin (b2) is preferably a styrene-(meth)acrylic acid ester copolymer and a (meth)acrylic acid ester copolymer, with the styrene-(meth)acrylic acid ester copolymer being more preferred.

[0102] The viscoelastic loss modulus G'' of the shell resin (b1) at a frequency of 1 Hz and 100°C is preferably 1.5 MPa or more and 100 MPa or less, more preferably 1.7 MPa or more and 30 MPa or less, and even more preferably 2.0 MPa or more and 10 MPa or less. The loss modulus of elasticity G'' of the viscoelastic properties of the resin (b2) at a frequency of 1 Hz and 100°C is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.02 MPa or more and 0.5 MPa or less, and even more preferably 0.05 MPa or more and 0.3 MPa or less. If the viscoelastic property loss modulus G'' is within this range, resin fine particles containing shell resin (b1) and core resin (b2) as constituent components within the same particle are likely to form toner particles that adhere to the surface of toner particles.

[0103] The loss modulus G'' of the viscoelastic properties of the shell resin (b1) and core resin (b2) at 100°C at a frequency of 1 Hz can be adjusted by changing the type and proportion of constituent monomers, or by adjusting the polymerization conditions (type and amount of initiator and chain transfer agent, and reaction temperature, etc.). Specifically, by using a composition such as the following, it becomes possible to adjust each G'' to the aforementioned range. (1) The glass transition temperature (Tg1) calculated from the constituent monomers of the shell resin (b1) and the glass transition temperature (Tg2) calculated from the constituent monomers of the core resin (b2) are set such that Tg1 is preferably 0°C to 150°C, more preferably 50°C to 100°C, and Tg2 is preferably -30°C to 100°C, more preferably 0°C to 80°C, and most preferably 30°C to 60°C. The glass transition temperature (Tg) calculated from the constituent monomers is a value that can be calculated using the Fox method. Here, the Fox method [TGFox, Phys. Rev., 86, 652 (1952)] is a method for estimating the Tg of a copolymer from the Tg of individual homopolymers, as shown by the following formula. 1 / Tg=W1 / Tg1+W2 / Tg2++Wn / Tgn [In the formula, Tg is the glass transition temperature of the copolymer (expressed in absolute temperature), Tg1, Tg2...Tgn are the glass transition temperatures of the homopolymers of each monomer component (expressed in absolute temperature), and W1, W2...Wn represent the weight fraction of each monomer component.] (2) For the calculated acid value (AV1) of the shell resin (b1) and the calculated acid value (AV2) of the core resin (b2), (AV1) is preferably 75 mg KOH / g or more and 400 mg KOH / g or less, more preferably 150 mg KOH / g or more and 300 mg KOH / g or less, and (AV2) is preferably 0 mg KOH / g or more and 50 mg KOH / g or less, more preferably 0 mg KOH / g or more and 20 mg KOH / g or less, and most preferably 0 mg KOH / g. The calculated acid value is a theoretical acid value calculated from the molar amount of acidic groups contained in the constituent monomers and the total weight of the constituent monomers.

[0104] Examples of constituent monomers that satisfy conditions (1) and (2) include, for the shell resin (b1), a resin that, based on the total mass of the shell resin (b1), preferably contains styrene as a constituent monomer in an amount of 10% to 80% by mass, more preferably 30% to 60% by mass, and preferably contains methacrylic acid and / or acrylic acid in a total amount of 10% to 60% by mass, more preferably 30% to 50% by mass. Furthermore, as for the core resin (b2), for example, based on the total mass of the core resin (b2), examples include a resin that preferably contains styrene as a constituent monomer in an amount of 10% to 100% by mass, more preferably 30% to 90% by mass, and methacrylic acid and / or acrylic acid in an amount of 0% to 7.5% by mass, more preferably 0% to 2.5% by mass, based on the total mass of the resin (b2).

[0105] (3) Adjust the polymerization conditions (type and amount of initiator and chain transfer agent, and reaction temperature, etc.). Specifically, for the number average molecular weights (Mn1) and (Mn2) of the shell resin (b1) and core resin (b2), (Mn1) is preferably 2,000 to 2,000,000, more preferably 20,000 to 200,000, and (Mn2) is preferably 1,000 to 1,000,000, more preferably 10,000 to 100,000.

[0106] The loss modulus G'' of the viscoelastic properties in this invention is measured, for example, using the following viscoelasticity measuring device. Equipment: ARES-24A (manufactured by Rheometric Corporation) Jig: 25mm parallel plate Frequency: 1Hz Distortion rate: 10% Heating rate: 5°C / min

[0107] The acid value (AVb1) of the shell resin (b1) is preferably 75 mg KOH / g or more and 400 mg KOH / g or less, and more preferably 150 mg KOH / g or more and 300 mg KOH / g or less. If the acid value is within this range, resin microparticles containing vinyl-based units that include shell resin (b1) and core resin (b2) as constituent components within the same particle are likely to form particles that adhere to the surface of the toner. The shell resin (b1) in which the acid value is within this range is a resin that contains methacrylic acid and / or acrylic acid in an amount of 10% to 60% by mass, and more preferably 30% to 50% by mass, based on the total mass of the shell resin (b1).

[0108] From the viewpoint of low-temperature fixation, the acid value (AVb2) of the core resin (b2) is preferably 0 mg KOH / g or more and 50 mg KOH / g or less, more preferably 0 mg KOH / g or more and 20 mg KOH / g or less, and even more preferably 0 mg KOH / g. The core resin (b2) in which the acid value is within this range is a resin that contains methacrylic acid and / or acrylic acid in an amount of 0% to 7.5% by mass, and more preferably 0% to 2.5% by mass, based on the total mass of the core resin (b2). The acid value in this invention is measured by the method specified in JIS K0070:1992.

[0109] The glass transition temperature of the shell resin (b1) is preferably higher than the glass transition temperature of the core resin (b2), more preferably 10°C or more higher, and even more preferably 20°C or more higher. Within this range, the resin fine particles offer an excellent balance between the ease with which toner particles are formed when they adhere to the surface of the toner, and the low-temperature fixation properties of the toner particles according to the present invention.

[0110] The glass transition temperature (hereinafter abbreviated as Tg) of the shell resin (b1) is preferably 0°C or higher and 150°C or lower, and more preferably 50°C or higher and 100°C or lower. If the glass transition temperature is 0°C or higher, the heat resistance for storage can be improved, and if it is 150°C or lower, there is less inhibition of low-temperature fixation. The Tg of the core resin (b2) is preferably -30°C to 100°C, more preferably 0°C to 80°C, and even more preferably 30°C to 60°C. If the glass transition temperature is -30°C or higher, the heat resistance for storage can be improved, and if it is 100°C or lower, there is less inhibition of low-temperature fixation.

[0111] In this invention, Tg is measured using the method (DSC) specified in ASTM D3418-82 with a "DSC20, SSC / 580" [manufactured by Seiko Electronics Industries, Ltd.].

[0112] The solubility parameter (hereinafter abbreviated as SP value) of the aforementioned shell resin (b1) is set to 9 (cal / cm³) from the viewpoint of ease of toner particle formation. 3 ) 1 / 2 More than 13(cal / cm 3 ) 1 / 2 The following is preferable: 9.5 (cal / cm³)3 ) 1 / 2 12.5 (cal / cm or less is more preferable, and 10.5 (cal / cm or less is even more preferable. 3 ) 1 / 2 10.5 (cal / cm or less is more preferable, and 10.5 (cal / cm or less is even more preferable. 3 ) 1 / 2 11.5 (cal / cm or more and 12 (cal / cm or less is even more preferable. 3 ) 1 / 2 Even more preferably, it is 11.5 (cal / cm or more and 12 (cal / cm or less. The SP value of the shell resin (b1) can be adjusted by changing the types of monomers constituting it and their composition ratios. As the SP value of the core resin (b2), from the viewpoint of the ease of forming toner particles, 8.5 (cal / cm or more and 12.5 (cal / cm or less is preferable, 9 (cal / cm or more and 12 (cal / cm or less is more preferable, 10 (cal / cm or more and 11 (cal / cm or less is even more preferable. 3 ) 1 / 2 12.5 (cal / cm or more and 12.5 (cal / cm or less is preferable, 9 (cal / cm or more and 12 (cal / cm or less is more preferable, 10 (cal / cm or more and 11 (cal / cm or less is even more preferable. 3 ) 1 / 2 9 (cal / cm or more and 12 (cal / cm or less is preferable, 10 (cal / cm or more and 11 (cal / cm or less is more preferable, 10 (cal / cm or more and 11 (cal / cm or less is even more preferable. 3 ) 1 / 2 12 (cal / cm or more and 12 (cal / cm or less is more preferable, 10 (cal / cm or more and 11 (cal / cm or less is even more preferable. 3 ) 1 / 2 10 (cal / cm or more and 11 (cal / cm or less is more preferable, 10 (cal / cm or more and 11 (cal / cm or less is even more preferable. 3 ) 1 / 2 11 (cal / cm or more and 11 (cal / cm or less is even more preferable. 3 ) 1 / 2 Even more preferably, it is 11 (cal / cm or more and 11 (cal / cm or less. The SP value of the core resin (b2) can be adjusted by changing the types of monomers constituting it and their composition ratios.

[0113] The SP value in the present invention is calculated by the method by Fedors [Polym. Eng. Sci. 14(2) 152, (1974)].

[0114] From the viewpoints of the Tg of the shell resin (b1) and its copolymerizability with other monomers, in the shell resin (b1), it is preferable to contain styrene as a constituent monomer in an amount of 10% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 60% by mass or less, based on the total mass of the shell resin (b1). From the viewpoint of the Tg of the core resin (b2) and copolymerizability with other vinyl monomers, it is preferable that the core resin (b2) contains 10% to 100% by mass of styrene as a constituent monomer, based on the total mass of the core resin (b2), and more preferably 30% to 90% by mass.

[0115] The number-average molecular weight (Mn) of the shell resin (b1) is preferably 2,000 or more and 2,000,000 or less, and more preferably 20,000 or more and 200,000 or less. If the number-average molecular weight is 2,000 or more, the heat-resistant storage properties are improved, and if it is 2,000,000 or less, there is less inhibition on the low-temperature fixing properties of the toner.

[0116] The weight-average molecular weight of the shell resin (b1) is preferably greater than that of the core resin (b2), more preferably 1.5 times greater than that of the core resin (b2), and even more preferably 2.0 times greater than that of the core resin (b2). Within this range, an excellent balance is achieved between the ease of toner particle formation and low-temperature fixation.

[0117] The weight-average molecular weight (Mw) of the shell resin (b1) is preferably 20,000 or more and 20,000,000 or less, and more preferably 200,000 or more and 2,000,000 or less. If the weight-average molecular weight is 20,000 or more, the heat-resistant storage properties are improved, and if it is 20,000,000 or less, there is less inhibition of low-temperature fixation properties.

[0118] The Mn of the core resin (b2) is preferably 1,000 to 1,000,000, and more preferably 10,000 to 100,000. If Mn is 1,000 or more, the heat resistance of the toner is improved, and if it is 1,000,000 or less, there is less inhibition of the toner's low-temperature fixing properties.

[0119] The Mw of the core resin (b2) is preferably 10,000 or more and 10,000,000 or less, and more preferably 100,000 or more and 1,000,000 or less. If Mw is 10,000 or more, the heat resistance of the toner is improved, and if it is 10,000,000 or less, there is less inhibition of the toner's low-temperature fixing properties.

[0120] Among these, it is preferable that the Mw of the shell resin (b1) is 200,000 or more and 2,000,000 or less, the Mw of the core resin (b2) is 100,000 or more and 500,000 or less, and that "(b1)'s Mw" > "(b2)'s Mw".

[0121] In this invention, Mn and Mw can be measured using gel permeation chromatography (GPC) under the following conditions. Device (example): "HLC-8120" [Manufactured by Tosoh Corporation] Column (example): "TSK GEL GMH6" [manufactured by Tosoh Corporation] 2 pieces Measurement temperature: 40℃ Sample solution: 0.25% by mass tetrahydrofuran solution (undissolved components filtered out using a glass filter) Solution injection volume: 100μl Detection device: Refractive index detector Reference material: Standard polystyrene (TSKstandard POLYSTYRENE) 12 samples (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) [Manufactured by Tosoh Corporation]

[0122] The weight ratio (shell resin (b1) / core resin (b2)) of the shell resin (b1) to the core resin (b2) in the resin fine particles is preferably 5 / 95 or more and 95 / 5 or less, more preferably 25 / 75 or more and 75 / 25 or less, and even more preferably 40 / 60 or more and 60 / 40 or less. If the weight ratio of the shell resin (b1) to the core resin (b2) is 5 / 95 or more, the toner has excellent heat resistance for storage, and if the weight ratio of the shell resin (b1) to the core resin (b2) is 95 / 5 or less, the resin fine particles are more likely to form toner particles that adhere to the surface of the toner resin particles.

[0123] Furthermore, while the resin fine particles can be used alone, the toner of the present invention can be obtained by using a combination of resin fine particles made of two types of styrene-acrylic resin (resins b1 and b2) and resin fine particles made of one type of styrene-acrylic resin. During emulsification, the pre-mixed resin fine particles adhere uniformly to the toner surface, and in the subsequent cleaning process, all or part of the resin fine particles and resin b1 adhering to the toner surface are removed, creating gaps that allow the resin fine particles to adhere uniformly.

[0124] Known manufacturing methods can be used to produce the aforementioned resin fine particles, including, for example, the following manufacturing methods (I) to (V). (I) A method of seed polymerization of constituent monomers of a core resin (b2) using fine particles of a shell resin (b1) in an aqueous dispersion as seeds. (II) A method of seed polymerization of constituent monomers of a shell resin (b1) using fine particles of core resin (b2) in an aqueous dispersion as seeds. (III) A method for obtaining an aqueous dispersion of resin fine particles by emulsifying a mixture of shell resin (b1) and core resin (b2) in an aqueous medium. (IV) A method for obtaining an aqueous dispersion of resin fine particles by emulsifying a mixture of shell resin (b1) and constituent monomers of core resin (b2) in an aqueous medium, and then polymerizing the constituent monomers of core resin (b2). (V) A method of obtaining an aqueous dispersion of resin fine particles by emulsifying a mixture of core resin (b2) and shell resin (b1) constituent monomers in an aqueous medium, and then polymerizing the shell resin (b1) constituent monomers.

[0125] The fact that the resin microparticles contain a shell resin (b1) and a core resin (b2) as constituent components within the same particle can be confirmed by observing elemental mapping images of the cross-section of the resin microparticles using a known surface elemental analyzer (TOF-SIMSEDX-SEM, etc.), and by observing electron microscope images of the cross-section of the resin microparticles stained with a dye corresponding to the functional groups contained in the shell resin (b1) and core resin (b2). Furthermore, the resin fine particles obtained by this method may be a mixture containing resin fine particles in which the shell resin (b1) and the core resin (b2) are constituent components within the same particle, as well as resin fine particles in which only the shell resin (b1) is a constituent resin component and resin fine particles in which only the core resin (b2) is a constituent resin component. In the compounding process described later, the mixture may be used as is, or only the resin fine particles may be isolated and used.

[0126] Specific examples of (I) include a method in which the constituent monomers of (b1) are polymerized dropwise to produce an aqueous dispersion of resin fine particles containing (b1), and then the constituent monomers of (b2) are polymerized using this as a seed, and a method in which (b1) produced in advance by solution polymerization or the like is emulsified and dispersed in water, and then the constituent monomers of (b2) are polymerized using this as a seed.

[0127] Specific examples of (II) include a method in which the constituent monomers of (b2) are polymerized dropwise to produce an aqueous dispersion of resin fine particles containing (b2), and then the constituent monomers of (b1) are polymerized using this as a seed, and a method in which (b2) produced in advance by solution polymerization or the like is emulsified and dispersed in water, and then the constituent monomers of (b1) are polymerized using this as a seed.

[0128] Specific examples of (III) include a method in which solutions or melts of (b1) and (b2) prepared in advance by solution polymerization, etc., are mixed, and then the mixture is emulsified and dispersed in an aqueous medium.

[0129] Specific examples of (IV) include a method in which (b1), which has been produced in advance by solution polymerization, is mixed with constituent monomers of (b2), the mixture is emulsified and dispersed in an aqueous medium, and then the constituent monomers of (b2) are polymerized; and a method in which (b1) is produced in constituent monomers of (b2), the mixture is emulsified and dispersed in an aqueous medium, and then the constituent monomers of (b2) are polymerized.

[0130] Specific examples of (V) include a method in which (b2), which has been produced in advance by solution polymerization, is mixed with the constituent monomers of (b1), the mixture is emulsified and dispersed in an aqueous medium, and then the constituent monomers of (b1) are polymerized; and a method in which (a2) is produced in the constituent monomers of (b1), the mixture is emulsified and dispersed in an aqueous medium, and then the constituent monomers of (b1) are polymerized.

[0131] In the present invention, any of the above manufacturing methods (I) to (V) is preferred.

[0132] The resin fine particles are preferably used as an aqueous dispersion of resin fine particles. The volume-average particle size of the resin microparticles in the resin microparticle dispersion is preferably 10 nm or more and 40 nm or less. If the volume-average primary particle size is 10 nm or more, the heat resistance of the toner is improved, and if it is 40 nm or less, the low-temperature fixation is improved.

[0133] <Measurement of resin particle size on toner surface> The particle size of the resin microparticles present on the toner surface can be determined as follows. -Method for releasing external additives- [1] 50 ml of a 5% by mass aqueous solution containing a surfactant (product name Neugen ET-165, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a 100 ml screw tube, and 3 g of toner was added to the mixture and gently moved up and down and side to side. Then, the mixture was stirred with a ball mill for 30 minutes to allow the toner to blend into the dispersion solution. [2] Subsequently, ultrasonic homogenizer (product name homogenizer, model VCX750, CV33, manufactured by SONICS&MATERIALS Co., Ltd.) was used to apply ultrasonic energy for 60 minutes at an output of 40W. -Ultrasonic Conditions- • Vibration time: 60 minutes continuous ·Amplitude: 40W ·Vibration start temperature: 23±1.5℃ ·Temperature during vibration: 23±1.5℃ [3](1) The dispersion was filtered by suction using filter paper (product name: Qualitative filter paper (No. 2, 110 mm), manufactured by Advantec Toyo Co., Ltd.), washed twice again with deionized water and filtered to remove the freed additives, and then the toner particles were dried. (2) The toner obtained in (1) was observed using a scanning electron microscope (SEM). First, the Si-containing additives and fillers were detected by observing the backscattered electron image. (3) The image from (1) was binarized using image processing software (ImageJ) to remove the external additive and filler. Next, a secondary electron image is observed at the same position as in (1). Since organic microparticles (OMS) and resin microparticles are not observed in the backscattered electron image but only in the secondary electron image, they are compared with the image obtained in (3), and the microparticles present in the parts other than the residual additive and filler (the parts other than those excluded in (3)) are considered to be resin microparticles. The particle size of the resin microparticles is then calculated using the aforementioned image processing software.

[0134] The aqueous dispersion (aqueous medium) used is not particularly limited as long as it is soluble in water, and can be appropriately selected according to the purpose. Examples include surfactants (D), buffers, and protective colloids. These may be used individually or in combination of two or more. The aqueous medium used in the aforementioned aqueous dispersion can be any liquid that requires water; there are no particular restrictions on its use, and examples include aqueous solutions containing water. The resin fine particles are preferably used as an aqueous dispersion. Any liquid containing water as an essential component can be used as the aqueous medium for the dispersion, such as an aqueous solution containing a surfactant (D) in water.

[0135] Examples of the surfactant (D) include nonionic surfactants (D1), anionic surfactants (D2), cationic surfactants (D3), amphoteric surfactants (D4), and other emulsifying dispersants (D5).

[0136] Examples of the nonionic surfactant (D1) include AO (alkylene oxide)-added nonionic surfactants and polyhydric alcohol-type nonionic surfactants. Examples of the AO-addition type nonionic surfactant include EO adducts of aliphatic alcohols having 10 to 20 carbon atoms, EO adducts of phenols, EO (ethylene oxide) adducts of nonylphenols, EO adducts of alkylamines having 8 to 22 carbon atoms, and EO adducts of poly(oxypropylene) glycols. Examples of the polyhydric alcohol-type nonionic surfactant include polyhydric (3-8 or more hydric) alcohol (2-30 carbon atoms) fatty acid (8-24 carbon atoms) esters (e.g., glycerin monostearate, glycerin monooleate, sorbitan monolaurate, sorbitan monooleate, etc.), alkyl (4-24 carbon atoms) poly(degree of polymerization 1-10) glycosides, and the like.

[0137] Examples of the anionic surfactant (D2) include ether carboxylic acids or salts thereof having a hydrocarbon group having 8 to 24 carbon atoms, sulfate esters or ether sulfate esters and salts thereof having a hydrocarbon group having 8 to 24 carbon atoms, sulfonates having a hydrocarbon group having 8 to 24 carbon atoms, sulfosuccinates having one or two hydrocarbon groups having 8 to 24 carbon atoms, phosphate esters or ether phosphate esters and salts thereof having a hydrocarbon group having 8 to 24 carbon atoms, fatty acid salts having a hydrocarbon group having 8 to 24 carbon atoms, and acylated amino acid salts having a hydrocarbon group having 8 to 24 carbon atoms. Examples of ether carboxylic acids or salts thereof having hydrocarbon groups with 8 to 24 carbon atoms include sodium lauryl ether acetate and sodium (poly)oxyethylene (additional moles 1 to 100) lauryl ether acetate. Examples of sulfate esters or ether sulfate esters having hydrocarbon groups with 8 to 24 carbon atoms and their salts include sodium lauryl sulfate, (poly)oxyethylene (1 to 100 moles added) sodium lauryl sulfate, (poly)oxyethylene (1 to 100 moles added) triethanolamine lauryl sulfate, and (poly)oxyethylene (1 to 100 moles added) coconut oil fatty acid monoethanolamide sulfate sodium. Examples of sulfonates having hydrocarbon groups with 8 to 24 carbon atoms include sodium dodecylbenzenesulfonate. Examples of phosphate esters or ether phosphate esters having hydrocarbon groups with 8 to 24 carbon atoms, and their salts, include sodium lauryl phosphate and sodium (poly)oxyethylene (additional moles 1 to 100) lauryl ether phosphate. Examples of fatty acid salts having hydrocarbon groups with 8 to 24 carbon atoms include sodium laurate and triethanolamine laurate. Examples of acylated amino acid salts having hydrocarbon groups with 8 to 24 carbon atoms include sodium methyl taurate, sodium sarcosinate, triethanolamine sarcosinate, triethanolamine acyl-L-glutamate, sodium acyl-L-glutamate, and sodium lauroyl methyl-β-alanine.

[0138] Examples of the cationic surfactant (D3) include quaternary ammonium salts and amine salts. Examples of the quaternary ammonium salt type include stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, and aminopropylethyldimethylammonium ethyl sulfate. Examples of the amine salt type include diethylaminoethyl stearate lactate, dilaurylamine hydrochloride, and oleylamine lactate.

[0139] Examples of amphoteric surfactants (D4) include betaine-type amphoteric surfactants and amino acid-type amphoteric surfactants. Examples of the betaine-type amphoteric surfactants include coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and lauryl hydroxysulfobetaine. Examples of amino acid-type amphoteric surfactants include sodium β-laurylaminopropionate.

[0140] Other emulsifying and dispersing agents (D5) include, for example, reactive surfactants. The reactive activator is not particularly limited as long as it has radical reactivity and can be appropriately selected according to the purpose. For example, Adekarya Soap (registered trademark) SE-10N, SR-10, SR-20, SR-30, ER-20, ER-30 (all manufactured by ADEKA Corporation), Aqualon (registered trademark) HS-10, KH-05, KH-10, KH-1025 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Eleminor (registered trademark) JS-20 (manufactured by Sanyo Chemical Industries, Ltd.), Latemul (registered trademark) D-104, PD-420, PD-430 (all, Examples include Kao Corporation's Ionet (registered trademark) MO-200 (manufactured by Sanyo Chemical Industries, Ltd.), polyvinyl alcohol, starch and its derivatives, cellulose derivatives such as carboxymethylcellulose, methylcellulose and hydroxyethylcellulose, and carboxyl group-containing (co)polymers such as sodium polyacrylate, and emulsifying dispersants having urethane groups or ester groups as described in U.S. Patent No. 5,906,704 (for example, polycaprolactone polyol and polyetherdiol linked with polyisocyanate).

[0141] As for the surfactant (D), (D1), (D2), (D5), and combinations thereof are preferred from the viewpoint of stabilizing oil droplets and obtaining the desired shape while sharpening the particle size distribution during emulsification and dispersion, and combinations of (D1) and (D5), and combinations of (D2) and (D5) are more preferred.

[0142] Examples of the buffering agent include sodium acetate, sodium citrate, sodium bicarbonate, and the like. Examples of the protective colloid include water-soluble cellulose compounds and alkali metal salts of polymethacrylic acid.

[0143] The resin fine particles may contain, in addition to the shell resin (b1) and core resin (b2), other resin components, initiators (and their residues), chain transfer agents, antioxidants, plasticizers, preservatives, reducing agents, organic solvents, and the like.

[0144] Other resin components include vinyl resins other than those used in the shell resin (b1) and core resin (b2), polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenolic resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins.

[0145] Examples of the initiator (and its residue) include known radical polymerization initiators, specifically persulfate initiators such as potassium persulfate and ammonium persulfate; azo initiators such as azobisisobutyronitrile; organic peroxides such as benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, tert-butyl peroxyisopropyl monocarbonate, and tert-butyl peroxybenzoate; and hydrogen peroxide.

[0146] Examples of chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid, and α-methylstyrene dimer.

[0147] Examples of antioxidants include phenol compounds, paraphenylenediamine, hydroquinone, organosulfur compounds, and organophosphorus compounds.

[0148] Examples of phenolic compounds include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2′-methylene-bis-(4-methyl-6-t-butylphenol), 2,2′-methylene-bis-(4-ethyl-6-t-butylphenol), 4,4′-thiobis-(3-methyl-6-t-butylphenol), and 4,4′-butylidenebis-(3-methyl-6-t-butylphenol). Examples include tris(6-t-butylphenol), 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane, bis[3,3′-bis(4′-hydroxy-3′-t-butylphenyl)butyric acid]glycol ester, and tocopherol.

[0149] Examples of paraphenylenediamines include N-phenyl-N′-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N,N′-di-isopropyl-p-phenylenediamine, and N,N′-dimethyl-N,N′-di-t-butyl-p-phenylenediamine.

[0150] Examples of hydroquinones include 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, and 2-(2-octadecenyl)-5-methylhydroquinone.

[0151] Examples of organosulfur compounds include dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and ditetradecyl-3,3′-thiodipropionate.

[0152] Examples of organophosphorus compounds include triphenylphosphine, tri(nonylphenyl)phosphine, tri(dinonylphenyl)phosphine, tricresylphosphine, and tri(2,4-dibutylphenoxy)phosphine.

[0153] Examples of the aforementioned plasticizers include phthalate esters, aliphatic dibasic acid esters, trimellitic acid esters, phosphate esters, and fatty acid esters. Examples of phthalate esters include dibutyl phthalate, dioctyl phthalate, butylbenzyl phthalate, and diisodecyl phthalate. Examples of aliphatic dibasic acid esters include di-2-ethylhexyl adipate and 2-ethylhexyl sebacate. Examples of trimellitic acid esters include tri-2-ethylhexyl trimellitic acid and trioctyl trimellitic acid. Examples of phosphate esters include triethyl phosphate, tri-2-ethylhexyl phosphate, and tricresyl phosphate. Examples of fatty acid esters include butyl oleate.

[0154] Examples of the aforementioned preservatives include organic nitrogen sulfur compound preservatives and organic sulfur halide preservatives.

[0155] Examples of the reducing agents include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose, and formaldehyde sulfoxylate metal salts; and reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite.

[0156] Examples of the aforementioned organic solvents include ketone solvents such as acetone and methyl ethyl ketone (hereinafter abbreviated as MEK); ester solvents such as ethyl acetate and γ-butyrolactone; ether solvents such as THF (tetrahydrofuran); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam; alcohol solvents such as isopropyl alcohol; and aromatic hydrocarbon solvents such as toluene and xylene.

[0157] The content of the aforementioned resin fine particles is preferably 0.2% by mass or more and 5% by mass or less relative to the toner. When the sum of the shell resin (b1) and core resin (b2) is within this range, both low-temperature fixability and heat-resistant storage properties are improved. If the content is 0.2% by mass or more relative to the toner, the problem of deterioration in heat-resistant storage properties can be prevented, and if it is 5% by mass or less, the problem of decreased low-temperature fixability can be prevented.

[0158] <Other ingredients> The aforementioned other components are not particularly limited and can be appropriately selected depending on the purpose. Examples include mold release agents, colorants, charge control agents, external additives, fluidity enhancers, cleaning properties enhancers, and magnetic materials.

[0159] -Release agent- There are no particular restrictions on the mold release agent, and it can be appropriately selected depending on the purpose. Examples include plant-based waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal-based waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cerucine; natural waxes such as paraffin, microcrystalline, and petrolatum; synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene, and polypropylene; and synthetic waxes such as esters, ketones, and ethers. Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax are preferred.

[0160] As the mold release agent, other options may be used, such as fatty acid amide compounds like 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride, and chlorinated hydrocarbons; homopolymers or copolymers of polyacrylates such as poly-n-stearyl methacrylate and poly-n-lauryl methacrylate, which are low molecular weight crystalline polymer resins (for example, a copolymer of n-stearyl acrylate and ethyl methacrylate); and crystalline polymers having long alkyl groups in their side chains.

[0161] There are no particular restrictions on the melting point of the release agent, and it can be appropriately selected depending on the purpose, but a melting point of 60°C or higher and 80°C or lower is preferred. If the melting point is below 60°C, the release agent may melt easily at low temperatures, resulting in poor heat resistance during storage. If the melting point exceeds 80°C, even if the resin has melted and is in the fixing temperature range, the release agent may not melt sufficiently, causing a fixing offset and resulting in image defects.

[0162] There are no particular restrictions on the content of the release agent, and it can be appropriately selected depending on the purpose, but it is preferably 2 to 10 parts by mass, and more preferably 3 to 8 parts by mass, per 100 parts by mass of toner.

[0163] -Coloring agent- There are no particular restrictions on the aforementioned colorants, and they can be appropriately selected according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, yellow ochre, 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 BG L, Isoindolinone Yellow, Bengara, Red Lead, Red Lead, Cadmium Red, Cadmium Mercury Red, Antimony Red, Permanent Red 4R, Para Red, Faise Red, Parachloro-orthonitroaniline Red, Risol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risol Rubin GX, Permanent Red F5R, Brilli Antcarmine 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, Perinon 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, Navy Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chromium Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake,Examples include malachite green lake, phthalocyanine green, anthraquinone green, titanium dioxide, zinc oxide, and lithobone.

[0164] There are no particular restrictions on the content of the coloring agent, and it can be appropriately selected depending on the purpose, but it is preferably 1 to 15 parts by mass, and more preferably 3 to 10 parts by mass, per 100 parts by mass of toner.

[0165] The aforementioned coloring agent can also be used as a masterbatch compounded with resin. Examples of resins used in the production of a masterbatch or mixed with a masterbatch include, in addition to the other polyester resins mentioned above, polymers of styrene or its substituted derivatives such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; 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, and styrene-α-chloromethacrylate copolymer. Examples include styrene copolymers such as styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, and 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, and paraffin wax. These may be used individually or in combination of two or more.

[0166] -External additives- Oxide microparticles, inorganic microparticles, and hydrophobized inorganic microparticles can be used in combination as the external additive, but the average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, and inorganic microparticles of 5 nm to 70 nm are more preferred.

[0167] Furthermore, it is preferable that the mixture contains at least one type of inorganic fine particles with an average particle size of 20 nm or less, and at least one type of inorganic fine particles with an average particle size of 30 nm or more. Furthermore, the specific surface area calculated using the BET method is 20m². 2 / g~500m 2 It is preferable that it be / g.

[0168] The aforementioned external additives are not particularly limited and can be appropriately selected depending on the purpose. Examples include silica nanoparticles, hydrophobic silica, fatty acid metal salts (e.g., zinc stearate, aluminum stearate, etc.), metal oxides (e.g., titania, alumina, tin oxide, antimony oxide, etc.), and fluoropolymers.

[0169] Suitable additives include hydrophobized silica, titania, titanium dioxide, and alumina microparticles. Examples of silica microparticles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.). Examples of titania microparticles include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), MT-150W, MT-500B, MT-600B, and MT-150A (all manufactured by Teika Co., Ltd.).

[0170] Examples of hydrophobized titanium oxide nanoparticles include T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Industry Co., Ltd.), TAF-500T, TAF-1500T (both manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (both manufactured by Teika Co., Ltd.), and IT-S (manufactured by Ishihara Sangyo Co., Ltd.).

[0171] Examples of the silicone oils mentioned above include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, methacrylic-modified silicone oil, and α-methylstyrene-modified silicone oil.

[0172] Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferred.

[0173] There are no particular restrictions on the content of the external additive, and it can be appropriately selected depending on the purpose, but it is preferably 0.1 to 5 parts by mass, and more preferably 0.3 to 3 parts by mass, per 100 parts by mass of toner.

[0174] There are no particular restrictions on the average particle size of the primary particles of the inorganic fine particles, and it can be appropriately selected depending on the purpose, but it is preferably 100 nm or less, and more preferably 3 nm to 70 nm.

[0175] - Fluidity improver - The aforementioned fluidity improver is not particularly limited as long as it can be surface-treated to increase its hydrophobicity and prevent deterioration of fluidity and electrostatic properties even under high humidity conditions. It can be appropriately selected according to the purpose, and examples include silane coupling agents, silylation agents, silane coupling agents having alkyl fluoride compounds, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. It is particularly preferable to surface-treat the silica and titanium oxide with such a fluidity improver and use them as hydrophobic silica and hydrophobic titanium oxide.

[0176] -Cleaning performance enhancer- The cleaning agent is not particularly limited as long as it is added to the toner to remove residual post-transfer developer from the photoreceptor and primary transfer medium, and can be appropriately selected depending on the purpose. Examples include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, polymer microparticles produced by soap-free emulsion polymerization such as polymethyl methacrylate microparticles and polystyrene microparticles. The polymer fine particles are preferably those with a relatively narrow particle size distribution, and those with a volume-average particle size of 0.01 μm to 1 μm are preferred.

[0177] -Magnetic materials- The magnetic material is not particularly limited and can be appropriately selected depending on the purpose. Examples include iron powder, magnetite, and ferrite. Among these, white is preferred in terms of color.

[0178] <Toner manufacturing method> There are no particular restrictions on the toner manufacturing method, and it can be appropriately selected depending on the purpose. However, it is preferable to granulate the toner by dispersing an oil phase containing the polyester resin component, and optionally containing the crystalline polyester resin, a release agent, a colorant, etc., in an aqueous medium. Furthermore, it is even more preferable to granulate by dispersing an oil phase containing the modified polyester, curing agent, release agent, colorant, etc., in an aqueous medium, if necessary.

[0179] One known method for manufacturing such toner is the dissolution and suspension method. As an example, a method is presented in which toner matrix particles are formed while generating a polyester resin by at least one of the extension reaction and crosslinking reaction between the prepolymer and the curing agent. This method involves preparing an aqueous medium, preparing an oil phase containing toner material, emulsifying and dispersing the toner material, and removing organic solvents.

[0180] -Preparation of aqueous media (aqueous phase)- The aqueous medium can be prepared, for example, by dispersing resin particles in the aqueous medium. There are no particular restrictions on the amount of resin particles added to the aqueous medium, and it can be appropriately selected depending on the purpose, but 0.5 to 10 parts by mass per 100 parts by mass of the aqueous medium is preferred. There are no particular restrictions on the aqueous medium, and it can be appropriately selected depending on the purpose. Examples include water, a solvent miscible with water, and mixtures thereof. These may be used individually or in combination of two or more. Among these, water is preferred.

[0181] There are no particular restrictions on the solvent that can be miscible with water, and it can be appropriately selected depending on the purpose. Examples include alcohols, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. Examples of alcohols include methanol, isopropanol, and ethylene glycol. Examples of lower ketones include acetone and methyl ethyl ketone.

[0182] - Preparation of the oil phase - The oil phase containing the toner material in this embodiment can be prepared by dissolving and dispersing the toner material, which includes polyester resins A and B, which are prepolymers having urethane bonds and / or urea bonds, and polyester resin C, which does not have urethane bonds and / or urea bonds, in an organic solvent, and further optionally includes the crystalline polyester resin, curing agent, mold release agent, colorant, etc.

[0183] There are no particular restrictions on the organic solvent, and it can be appropriately selected depending on the purpose, but an organic solvent with a boiling point of less than 150°C is preferred because it is easy to remove.

[0184] Examples of organic solvents with a boiling point of less than 150°C include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. These can be used individually or in combination of two or more types. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferred, with ethyl acetate being more preferred.

[0185] -Emulsification and dispersion- The emulsification and dispersion of the toner material can be carried out by dispersing the oil phase containing the toner material in the aqueous medium. During the emulsification and dispersion of the toner material, at least one of the following can be performed: an extension reaction and a crosslinking reaction between the curing agent and the prepolymer.

[0186] There are no particular restrictions on the reaction conditions (reaction time, reaction temperature) for producing the prepolymer, and they can be appropriately selected depending on the combination of the curing agent and the prepolymer. The reaction time is preferably 10 minutes to 40 hours, and more preferably 2 to 24 hours. The reaction temperature is preferably 0°C to 150°C, and more preferably 40°C to 98°C.

[0187] There are no particular limitations on the method for stably forming the dispersion containing the prepolymer in the aqueous medium, and a suitable method can be selected depending on the purpose. Examples include adding an oil phase prepared by dissolving and dispersing toner material in a solvent to an aqueous medium phase, and dispersing it by shear force.

[0188] There are no particular restrictions on the disperser used for the aforementioned dispersion, and it can be appropriately selected according to the purpose. Examples include low-speed shear dispersers, high-speed shear dispersers, friction dispersers, high-pressure jet dispersers, and ultrasonic dispersers. Among these, high-speed shear dispersers are preferred because they can control the particle size of the dispersion (oil droplets) to 2 to 20 μm.

[0189] When using the high-speed shear type disperser, conditions such as rotation speed, dispersion time, and dispersion temperature can be appropriately selected according to the purpose. The rotation speed is preferably 1,000 to 30,000 rpm, and more preferably 5,000 to 20,000 rpm. The dispersion time is preferably 0.1 to 5 minutes in the case of a batch system. The dispersion temperature under pressure is preferably 0°C to 150°C, and more preferably 40°C to 98°C. Generally speaking, dispersion is easier at higher dispersion temperatures.

[0190] There is no particular limitation on the amount of the aqueous medium used when emulsifying and dispersing the toner material, and it can be appropriately selected according to the purpose. However, with respect to 100 parts by mass of the toner material, 50 to 2,000 parts by mass is preferable, and 100 to 1,000 parts by mass is more preferable. If the amount of the aqueous medium used is less than 50 parts by mass, the dispersion state of the toner material may deteriorate, and toner base particles having a predetermined particle diameter may not be obtained. If it exceeds 2,000 parts by mass, the production cost may increase.

[0191] When emulsifying and 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 making the particle size distribution sharp. There is no particular limitation on the dispersant, and it can be appropriately selected according to the purpose. Examples thereof include surfactants, poorly water-soluble inorganic compound dispersants, polymer-based protective colloids, and the like. These may be used alone or in combination of two or more. Among these, surfactants are preferable.

[0192] There is no particular limitation on the surfactant, and it can be appropriately selected according to the purpose. For example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and the like can be used. Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and the like. Among these, those having a fluoroalkyl group are preferable.

[0193] -Removal of organic solvent- There is no particular limitation on the method for removing the organic solvent from the dispersion liquid such as the emulsion slurry, and it can be appropriately selected according to the purpose. Examples thereof include a method of gradually raising the temperature of the entire reaction system to evaporate the organic solvent in the oil droplets, a method of spraying the dispersion liquid into a dry atmosphere to remove the organic solvent in the oil droplets, and the like. When the organic solvent is removed, toner mother particles are formed. For the toner mother particles, washing, drying, etc. can be performed, and further classification, etc. can be performed. The classification may be performed by removing fine particle portions by means of a cyclone, a decanter, centrifugation, etc. in a liquid, or a classification operation may be performed after drying.

[0194] In the washing step, as a method for removing part or all of the resin (b1), there is a method for removing part or all of (b1) by a chemical method. Among the removal steps by a chemical method, a preferable one is a method in which an alkaline aqueous solution is added to and mixed with the toner mother particles to dissolve part or all of the resin (b1).

[0195] Examples of the alkali in the alkaline aqueous solution include hydroxides of alkali metals such as potassium hydroxide and sodium hydroxide, and ammonia. From the viewpoint of being easy to dissolve the resin (a1), potassium hydroxide and sodium hydroxide are preferable.

[0196] The pH of the alkali contained in the alkaline aqueous solution is preferably 8 to 14, and more preferably 10 to 12.

[0197] The mixing of the toner mother particles and the alkaline aqueous solution in the washing step can be performed by a method such as dropping the alkaline aqueous solution into the toner mother slurry under stirring. Furthermore, an acidic aqueous solution may be dropped to neutralize.

[0198] The obtained toner mother particles may be mixed with particles such as the external additive and the charge control agent. At this time, by applying a mechanical impact force, it is possible to suppress the desorption of particles such as the external additive from the surface of the toner mother particles. There are no particular restrictions on the method of applying the aforementioned mechanical impact force, and it can be appropriately selected depending on the purpose. Examples include a method of applying impact force to a mixture using a blade rotating at high speed, and a method of introducing a mixture into a high-speed airflow, accelerating it, and causing particles to collide with each other or with a suitable impact plate.

[0199] There are no particular restrictions on the equipment used in the above method, and it can be appropriately selected according to the purpose. Examples include an Ongmill (manufactured by Hosokawa Micron Corporation), a modified I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) with reduced grinding air pressure, a hybridization system (manufactured by Nara Machine Works Co., Ltd.), a cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar and pestle.

[0200] (Developer) The developer of the present invention contains at least the toner of the present invention, and optionally other components such as a carrier, as appropriate. Therefore, it has excellent transferability and electrostatic properties, and can stably form high-quality images. The developer may be a one-component or two-component developer, but when used in high-speed printers that can handle the recent increase in information processing speed, a two-component developer is preferred because it extends the lifespan.

[0201] When the aforementioned developer is used as a single-component developer, even when toner is balanced, there is little variation in the toner particle size, resulting in less toner filming onto the developing roller and less toner fusion to components such as blades that thin the toner layer. This allows for good and stable development and image quality even during long-term agitation in the developing apparatus.

[0202] When the aforementioned developer is used as a two-component developer, even with long-term toner balance cycles, the toner particle size remains stable, and good and stable developability and images can be obtained even with long-term agitation in the developing device.

[0203] <Career> There are no particular restrictions on the carrier, and it can be appropriately selected according to the purpose, but one having a core material and a resin layer covering the core material is preferred.

[0204] -Core material- There are no particular restrictions on the material of the core material, and it can be appropriately selected according to the purpose. Examples include manganese-strontium materials with a magnetization of 50-90 emu / g and manganese-magnesium materials with a magnetization of 50-90 emu / g. Furthermore, in order to ensure image density, it is preferable to use highly magnetized materials such as iron powder with a magnetization of 100 emu / g or more and magnetite with a magnetization of 75-120 emu / g. In addition, it is preferable to use low magnetized materials such as copper-zinc materials with a magnetization of 30-80 emu / g, as this can mitigate the impact of the developer in a condensed state on the photoreceptor and is advantageous for improving image quality. These can be used individually or in combination of two or more types.

[0205] There are no particular restrictions on the volume-average particle diameter of the core material, and it can be appropriately selected depending on the purpose, but 10 to 150 μm is preferred, and 40 to 100 μm is more preferred. If the volume-average particle diameter is less than 10 μm, there will be a large amount of fine powder in the carrier, which may reduce the magnetization per particle and cause carrier scattering. On the other hand, if it exceeds 150 μm, the specific surface area will decrease, which may cause toner scattering, and in full-color printing with many solid areas, the reproduction of solid areas may be particularly poor.

[0206] The toner of the present invention can be mixed with the carrier and used in a two-component developer. There are no particular restrictions on the amount of the carrier in the two-component developer, and it can be appropriately selected depending on the purpose, but 90 to 98 parts by mass and more preferably 93 to 97 parts by mass per 100 parts by mass of the two-component developer is preferred. The developer of the present invention can be suitably used for image formation by various known electrophotographic methods, such as magnetic one-component development methods, non-magnetic one-component development methods, and two-component development methods.

[0207] (Toner storage unit) The toner storage unit of the present invention is not particularly limited and can be appropriately selected from known types. For example, one that has a container body and a cap can be used. Furthermore, the size, shape, structure, and material of the container body are not particularly limited, but a cylindrical shape is preferred. In particular, it is preferable that spiral-shaped irregularities are formed on the inner surface, allowing the developer contents to move towards the discharge port side by rotating the container, and that some or all of the spiral irregularities have a bellows function. In addition, it is preferable that the material has good dimensional accuracy. Examples of such materials include polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin component ABS resin, and polyacetal resin.

[0208] The toner storage unit is easy to store and transport, and offers excellent handling, so it can be detachably attached to process cartridges, image forming apparatuses, etc., as described later, and used for replenishing developer.

[0209] The toner storage unit is molded to be detachable from various image forming apparatuses and comprises at least an electrostatic latent image carrier that carries an electrostatic latent image, and a developing means that develops the electrostatic latent image carried on the electrostatic latent image carrier with the developer of the present invention to form a toner image. The toner storage unit may further comprise other means as needed.

[0210] The developing means includes at least a developer storage section for containing the developer of the present invention, and a developer carrier for carrying and transporting the developer contained in the developer storage section. The developing means may further include a regulating member or the like to regulate the thickness of the carried developer.

[0211] (Image forming apparatus and image forming method) The image forming apparatus of the present invention comprises at least an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further comprises other means as necessary. The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.

[0212] <Electrostatic latent image carrier> The material, structure, and size of the electrostatic latent image carrier are not particularly limited and can be appropriately selected from known ones. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life. The linear speed of the electrostatic latent image carrier is preferably 300 mm / s or more.

[0213] <Electrostatic latent image forming means and electrostatic latent image forming step> The electrostatic latent image forming means is not particularly limited as long as it is means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples include means having at least a charging member for charging the surface of the electrostatic latent image carrier and an exposure member for imagewise exposing the surface of the electrostatic latent image carrier.

[0214] The electrostatic latent image forming step is not particularly limited as long as it is a step for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. For example, it can be performed by charging the surface of the electrostatic latent image carrier and then imagewise exposing it, and can be performed using the electrostatic latent image forming means.

[0215] <<Charging member and charging>> The charging member is not particularly limited and can be appropriately selected according to the purpose. Examples include known contact chargers provided with conductive or semiconductive rollers, brushes, films, rubber blades, etc., and non-contact chargers using corona discharge such as corotrons and scorotrons.

[0216] The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member. The shape of the charging member can be any form other than a roller, such as a magnetic brush or a fur brush, and can be selected according to the specifications and configuration of the image forming apparatus.

[0217] The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because it reduces the amount of ozone generated from the charging member, thus providing an image forming apparatus.

[0218] <<Exposure component and exposure>> The exposure member is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier, which has been charged by the charging member, in the manner of the image to be formed, and can be appropriately selected according to the purpose. Examples of exposure members include various types such as copying optical systems, rod lens array systems, laser optical systems, and liquid crystal shutter optical systems.

[0219] There are no particular restrictions on the light source used in the exposure member, and it can be appropriately selected according to the purpose. Examples include fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light-emitting diodes (LEDs), semiconductor lasers (LDs), electroluminescent devices (ELs), and other light-emitting materials in general.

[0220] Furthermore, various filters such as sharp-cut filters, band-pass filters, near-infrared cut filters, dichroic filters, interference filters, and color temperature conversion filters can be used to illuminate only the desired wavelength range.

[0221] The exposure can be performed, for example, by exposing the surface of the electrostatic latent image carrier in an image-like manner using the exposure member. In addition, in the present invention, a back-facing method may be employed in which the electrostatic latent image carrier is exposed in an image-like manner from the back side.

[0222] <Developing means and developing process> The developing means is not particularly limited as long as it is a developing means equipped with toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a toner image which is a visible image, and can be appropriately selected according to the purpose. The development step is not particularly limited as long as it is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a toner image, which is a visible image. It can be appropriately selected according to the purpose, for example, by the development means. The preferred developing means is a developing apparatus that includes an agitator that frictionally agitates and charges the toner, and a developer carrier that has a magnetic field generating means fixed inside and a rotatable developer carrier on which the developer containing the toner is carried.

[0223] <Other means and other processes> Other means include, for example, transfer means, fixing means, cleaning means, static elimination means, recycling means, and control means. Other processes include, for example, a transfer process, a fixing process, a cleaning process, a static elimination process, a recycling process, and a control process.

[0224] <<Transfer means and transfer process>> The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, a configuration having a first transfer means for transferring a visible image onto an intermediate transfer body to form a composite transfer image, and a second transfer means for transferring the composite transfer image onto a recording medium is preferred. The aforementioned transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, a preferred method is to use an intermediate transfer medium, first transfer the visible image onto the intermediate transfer medium, and then second transfer the visible image onto the recording medium. The transfer step can be performed, for example, by charging the photoreceptor using a transfer charger to create the visible image, and can be carried out by the transfer means.

[0225] In this configuration, if the image to be secondarily transferred onto the recording medium is a color image consisting of multiple toners, the transfer means can sequentially superimpose each toner onto the intermediate transfer body to form an image on the intermediate transfer body, and the intermediate transfer means can then secondarily transfer the image on the intermediate transfer body onto the recording medium in one go. There are no particular restrictions on the intermediate transfer material, and it can be appropriately selected from known transfer materials depending on the purpose. For example, a transfer belt is a suitable example.

[0226] The transfer means (the primary transfer means, the secondary transfer means) preferably includes at least a transfer device that exfoliates the visible image formed on the photoreceptor toward the recording medium. Examples of the transfer device include a corona discharge transfer device, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. While plain paper is a typical recording medium, there are no particular restrictions as long as it can transfer the unfixed image after development. It can be appropriately selected according to the purpose, and PET bases for OHPs can also be used.

[0227] <<Fixing means and fixing process>> The fixing means is not particularly limited as long as it is a means for fixing the transferred image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, a known heating and pressing member is preferred. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller and an endless belt. The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, it may be performed for each color of toner after it has been transferred to the recording medium, or it may be performed simultaneously for each color of toner in a stacked state.

[0228] The fixing process can be carried out by the fixing means. The heating temperature in the aforementioned heating and pressurizing member is preferably 80°C to 200°C. In addition, in the present invention, depending on the purpose, a known optical fuser may be used together with or in place of the fixing means, for example. There are no particular restrictions on the surface pressure in the fixing process, and it can be appropriately selected according to the purpose, but 10 N / cm is recommended. 2 ~80 N / cm 2 It is preferable that this be the case.

[0229] <<Cleaning Methods and Cleaning Processes>> The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. Examples include magnetic brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, and web cleaners. The cleaning process is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, it can be carried out by the cleaning means.

[0230] <<Static elimination means and static elimination process>> The static elimination means is not particularly limited as long as it is a means of eliminating static electricity by applying a static elimination bias to the photoreceptor, and can be appropriately selected according to the purpose, for example, a static elimination lamp. The static elimination step is not particularly limited as long as it is a step of eliminating static electricity by applying a static elimination bias to the photoreceptor, and can be appropriately selected according to the purpose, for example, it can be carried out by the static elimination means.

[0231] <<Recycling methods and recycling processes>> The recycling means is not particularly limited as long as it is a means of recycling the toner removed by the cleaning process to the developing device, and can be appropriately selected according to the purpose, for example, known transport means. The recycling process is not particularly limited as long as it is a process of recycling the toner removed by the cleaning process to the developing device, and can be appropriately selected according to the purpose, for example, by the recycling means.

[0232] Next, one embodiment of the method for forming an image using the image forming apparatus of the present invention will be described with reference to Figure 2. In this embodiment, a printer is shown as an example of the image forming apparatus, but the image forming apparatus is not particularly limited as long as it is capable of forming an image using toner, such as a copier, facsimile, or multifunction device. The image forming apparatus comprises a paper feeding unit 210, a transport unit 220, an image forming unit 230, a transfer unit 240, and a fuser unit 250. The paper feeding unit 210 includes a paper feed cassette 211 on which the paper to be fed P is stacked, and a paper feed roller 212 that feeds the paper P from the paper feed cassette 211 one sheet at a time.

[0233] The transport unit 220 includes a roller 221 that transports the paper P fed by the paper feed roller 212 toward the transfer unit 240, a pair of timing rollers 222 that hold the leading edge of the paper P transported by the roller 221 and wait, and send the paper to the transfer unit 240 at a predetermined timing, and a paper discharge roller 223 that discharges the paper P on which the color toner image has been fixed toward the paper discharge tray 224.

[0234] The image-forming unit 230 comprises, at predetermined intervals and arranged sequentially from left to right in the figure, an image-forming unit Y that forms an image using a developer containing yellow toner, an image-forming unit C that uses a developer containing cyan toner, an image-forming unit M that uses a developer containing magenta toner, an image-forming unit K that uses a developer containing black toner, and an exposure unit 233. Furthermore, when referring to any of the image forming units (Y, C, M, K), the term "image forming unit" is used.

[0235] Furthermore, the developer contains toner and carrier. The four image forming units (Y, C, M, K) are virtually identical in their mechanical configuration, differing only in the developer they use.

[0236] The transfer unit 240 includes a drive roller 241 and a driven roller 242, an intermediate transfer belt 243 that can rotate counterclockwise in the figure as the drive roller 241 is driven, primary transfer rollers (244Y, 244C, 244M, 244K) provided opposite the photoreceptor drum 231 with the intermediate transfer belt 243 in between, and secondary opposing rollers 245 and secondary transfer rollers 246 provided opposite the intermediate transfer belt 243 at the position where the toner image is transferred to the paper.

[0237] The fuser unit 250 has a heater inside and is equipped with a pressure roller 252 that rotatably applies pressure to the fuser belt 251, which heats the paper P, to form a nip. This applies heat and pressure to the color toner image on the paper P, fixing the color toner image. The paper P with the fixed color toner image is ejected to the paper output tray 224 by the paper output roller 223, completing the image forming process. [Examples]

[0238] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0239] <Example 1 of synthesis of amorphous polyester resin> In a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide side 2 molar adduct, bisphenol A propylene oxide 3 molar adduct, terephthalic acid, adipic acid, and trimethylolpropane were added, with the molar ratio of bisphenol A ethylene oxide side 2 molar adduct to bisphenol A propylene oxide 3 molar adduct being 85 / 15 (bisphenol A ethylene oxide side 2 molar adduct / bisphenol A propylene oxide 3 molar adduct), and terephthalic acid and adipic acid... The mixture was prepared with a molar ratio (terephthalic acid / adipic acid) of 75 / 25, a trimethylolpropane content of 1 mol% in the total monomer, and a molar ratio of hydroxyl groups to carboxyl groups (OH / COOH) of 1.2. It was then reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at atmospheric pressure at 230°C for 8 hours, followed by a further reaction under reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Finally, trimellitic anhydride was added to the reaction vessel at a concentration of 1 mol% relative to the total resin component, and the mixture was reacted at 180°C and atmospheric pressure for 3 hours to obtain amorphous polyester resin 1.

[0240] <Example 2 of Amorphous Polyester Resin Synthesis> In a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide side 2 molar adduct, bisphenol A propylene oxide 3 molar adduct, terephthalic acid, adipic acid, and trimethylolpropane were added, with the molar ratio of bisphenol A ethylene oxide side 2 molar adduct to bisphenol A propylene oxide 3 molar adduct being 85 / 15 (bisphenol A ethylene oxide side 2 molar adduct / bisphenol A propylene oxide 3 molar adduct), and the terephthalic acid and adipic acid being... The molar ratio (terephthalic acid / adipic acid) was 85 / 15, the amount of trimethylolpropane in the total monomer was 1 mol%, and the molar ratio of hydroxyl groups to carboxyl groups (OH / COOH) was 1.04. The mixture was charged with titanium tetraisopropoxide (500 ppm relative to the resin component) at atmospheric pressure at 230°C for 8 hours, and then reacted for 4 hours under reduced pressure of 10 mmHg to 15 mmHg. Finally, trimellitic anhydride was added to the reaction vessel at a concentration of 1 mol% relative to the total resin component, and the mixture was reacted at 180°C and atmospheric pressure for 3 hours to obtain amorphous polyester resin 2.

[0241] <Example 3 of Amorphous Polyester Resin Synthesis> In a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide side 2 molar adduct, bisphenol A propylene oxide 3 molar adduct, terephthalic acid, adipic acid, and trimethylolpropane were added, with the molar ratio of bisphenol A ethylene oxide side 2 molar adduct to bisphenol A propylene oxide 3 molar adduct being 85 / 15 (bisphenol A ethylene oxide side 2 molar adduct / bisphenol A propylene oxide 3 molar adduct), and the terephthalic acid and adipic acid being... The molar ratio (terephthalic acid / adipic acid) was 30 / 70, the amount of trimethylolpropane in the total monomer was 1 mol%, and the molar ratio of hydroxyl groups to carboxyl groups (OH / COOH) was 1.26. The mixture was charged with titanium tetraisopropoxide (500 ppm relative to the resin component) at atmospheric pressure at 230°C for 8 hours, and then reacted for 4 hours under reduced pressure of 10 mmHg to 15 mmHg. Finally, trimellitic anhydride was added to the reaction vessel at a concentration of 1 mol% relative to the total resin component, and the mixture was reacted at 180°C and atmospheric pressure for 3 hours to obtain amorphous polyester resin 3.

[0242] <Examples of crystalline polyester resin synthesis> In a 5L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, sebaciic acid and 1,6-hexanediol were charged so that the molar ratio of hydroxyl groups to carboxyl groups (OH / COOH) was 0.9. These were reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at 180°C for 10 hours, then the temperature was raised to 200°C and the reaction was continued for 3 hours, followed by a reaction at a pressure of 8.3 kPa for 2 hours to obtain crystalline polyester resin 1.

[0243] <Example of preparation of crystalline polyester resin dispersion> 60 parts by mass of [crystalline polyester resin 1] and 400 parts by mass of ethyl acetate were placed in a container equipped with a stirring rod and a thermometer, the temperature was raised to 80°C under stirring, and the temperature was maintained at 80°C for 5 hours, then cooled to 30°C in 1 hour, and dispersion was performed using a bead mill (Ultraviscomill, manufactured by AIMEX) under the conditions of a liquid transfer rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80 volume% of 0.5 mm diameter zirconia beads packed into the mixture in 3 passes to obtain crystalline polyester resin dispersion 1.

[0244] <Example of prepolymer synthesis 1> In a reaction vessel equipped with a condenser, a stirrer, and nitrogen inlet tube, 3-methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimellitic anhydride were added together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) such that the molar ratio of hydroxyl groups to carboxyl groups (OH / COOH) was 1.5, the diol component consisted of 100 mol% 3-methyl-1,5-pentanediol, the dicarboxylic acid component consisted of 40 mol% isophthalic acid and 60 mol% adipic acid, and the amount of trimellitic anhydride in the total monomer was 1 mol%. Subsequently, the temperature was raised to 200°C over approximately 4 hours, and then to 230°C over 2 hours, and the reaction continued until all the effluent was gone. Subsequently, the reaction was carried out under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [intermediate polyester 1]. Next, [Intermediate Polyester 1] and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI / hydroxyl groups of intermediate polyester) of 2.0. After diluting with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100°C for 5 hours to obtain [Prepolymer 1].

[0245] <Example of prepolymer synthesis 2> In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 3-methyl-1,5-pentanediol, isophthalic acid, and trimellitic anhydride were added together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) such that the molar ratio of hydroxyl groups to carboxyl groups (OH / COOH) was 1.5, the diol component consisted of 100 mol% 3-methyl-1,5-pentanediol, the dicarboxylic acid component consisted of 100 mol% isophthalic acid, and the amount of trimellitic anhydride in the total monomer was 1 mol%. Subsequently, the temperature was raised to 200°C over approximately 4 hours, and then to 230°C over 2 hours, and the reaction continued until all the effluent was gone. Subsequently, the reaction was carried out under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [intermediate polyester 2]. Next, [Intermediate Polyester 2] and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI / hydroxyl groups of intermediate polyester) of 2.0. After diluting with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100°C for 5 hours to obtain [Prepolymer 2].

[0246] <Example of prepolymer synthesis 3> In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 3-methyl-1,5-pentanediol, decanodiic acid, and trimellitic anhydride were added together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) such that the molar ratio of hydroxyl groups to carboxyl groups (OH / COOH) was 1.5, the diol component consisted of 100 mol% 3-methyl-1,5-pentanediol, the dicarboxylic acid component consisted of 100 mol% decanodiic acid, and the amount of trimellitic anhydride in the total monomer was 1 mol%. Subsequently, the temperature was raised to 200°C over approximately 4 hours, and then to 230°C over 2 hours, and the reaction continued until all the effluent was gone. Subsequently, the reaction was carried out under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [intermediate polyester 3]. Next, [Intermediate Polyester 3] and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI / hydroxyl groups of intermediate polyester) of 2.0. After diluting with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100°C for 5 hours to obtain [Prepolymer 3].

[0247] <Example 1 of the synthesis of a dispersion of resin microparticles> In a reaction vessel equipped with a stirrer, heating / cooling device, and thermometer, 3,710 parts by mass of water and 200 parts by mass of polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium (Aqualon KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were charged and stirred at 200 revolutions per minute to homogenize the mixture. After raising the temperature to 75°C, a mixture consisting of 90 parts by mass of 10% ammonium persulfate aqueous solution, 450 parts by mass of styrene, 250 parts by mass of butyl acrylate, and 300 parts by mass of methacrylic acid was added dropwise over 4 hours. After dropwise addition, the mixture was aged at 75°C for 4 hours to obtain a [microparticle dispersion (W0-1)] containing a resin (a1-1), which is a polymer copolymerized with the monomer and polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium. The volume-average particle size of the resin microparticles in the [microparticle dispersion (W0-1)] was measured by dynamic light scattering (light scattering electrophoresis apparatus: Otsuka Electronics Co., Ltd., ELS-8000) and found to be 15 nm. Furthermore, when a portion of the [microparticle dispersion (W0-1)] was dried and the resin (a1-1) was isolated, the Tg of the resin component was 53°C and the acid value was 195 mgKOH / g. Next, 667 parts by mass of [fine particle dispersion (W0-1)] and 248 parts by mass of water were charged into a reaction vessel equipped with a stirrer, a heating and cooling device, and a thermometer. 0.267 parts by mass of tert-butyl hydroperoxide (manufactured by NOF Corporation, Perbutyl H) was added, and the mixture was heated to raise the system temperature to 70°C. Then, 43.3 parts by mass of styrene, 23.3 parts by mass of butyl acrylate, and 18.0 parts by mass of 1% by mass aqueous ascorbic acid solution were added dropwise over 2 hours. After dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a fine particle dispersion of resin fine particles (A-1) containing resin (a2-1), which is a polymer copolymerized from the monomer using resin (a1-1) in (W0-1) as a seed, and resin (a1-1) as constituent components within the same particle. Water was added to the obtained fine particle dispersion to a solid content concentration of 20% to obtain resin fine particle dispersion (W-1). The volume-average particle size of [resin fine particles (A-1)] was measured by dynamic light scattering (light scattering electrophoresis apparatus: Otsuka Electronics Co., Ltd., ELS-8000) and was found to be 17.3 nm. Furthermore, after neutralizing [resin fine particle dispersion (W-1)] with a 10% by mass aqueous ammonia solution to pH 9.0, the precipitate obtained by centrifugation was dried to isolate resin (a2-1), and the Tg of the resin component was 53°C, and the acid value was 195 mgKOH / g.

[0248] <Example 2 of the synthesis of a dispersion of resin microparticles> In a reaction vessel equipped with a stirrer, a heating and cooling device, and a thermometer, 3,760 parts by mass of water and 150 parts by mass of polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium (Aqualon KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were charged and stirred at 200 rpm to homogenize the mixture. After raising the temperature to 75°C, a mixture consisting of 90 parts by mass of 10% ammonium persulfate aqueous solution, 430 parts by mass of styrene, 270 parts by mass of butyl acrylate, and 300 parts by mass of methacrylic acid was added dropwise over 4 hours. After dropwise addition, the mixture was aged at 75°C for 4 hours to obtain a [microparticle dispersion (W0-2)] containing a resin (a2-1), which is a polymer copolymerized with the monomer and polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium. The volume-average particle size of the resin microparticles in the [microparticle dispersion (W0-2)] was measured by dynamic light scattering (light scattering electrophoresis apparatus: Otsuka Electronics Co., Ltd., ELS-8000) and found to be 30 nm. Furthermore, when a portion of the [microparticle dispersion (W0-2)] was dried and resin (a2-1) was isolated, the Tg of the resin component was 53°C and the acid value was 195 mgKOH / g. Next, 667 parts by mass of [fine particle dispersion (W0-2)] and 248 parts by mass of water were charged into a reaction vessel equipped with a stirrer, a heating and cooling device, and a thermometer. 0.267 parts by mass of tert-butyl hydroperoxide (manufactured by NOF Corporation, Perbutyl H) was added, and the mixture was heated to raise the system temperature to 70°C. Then, 43.3 parts by mass of styrene, 23.3 parts by mass of butyl acrylate, and 18.0 parts by mass of 1% by mass aqueous ascorbic acid solution were added dropwise over 2 hours. After dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a fine particle dispersion of resin microparticles (A-2) containing resin (a2-1) as a constituent component within the same particle. This dispersion was formed by copolymerizing the monomers using resin (a2-1) in (W0-2) as a seed. Water was added to the obtained fine particle dispersion to a solid content concentration of 20% to obtain resin microparticle dispersion (W-2). The volume-average particle size of [resin microparticles (A-2)] was measured by dynamic light scattering (light scattering electrophoresis apparatus: Otsuka Electronics Co., Ltd., ELS-8000) and found to be 34.3 nm. Furthermore, after neutralizing [resin microparticle dispersion (W-2)] with a 10% by mass aqueous ammonia solution to pH 9.0, the precipitate obtained by centrifugation was dried to isolate resin (a2-2). The Tg of the resin component was 53°C and the acid value was 195 mgKOH / g.

[0249] <Example 3 of the synthesis of a dispersion of resin microparticles> In a reaction vessel equipped with a stirrer, heating / cooling device, and thermometer, 3,810 parts by mass of water and 100 parts by mass of polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium (Aqualon KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were charged and stirred at 200 rpm to homogenize the mixture. After raising the temperature to 75°C, a mixture consisting of 90 parts by mass of 10% ammonium persulfate aqueous solution, 400 parts by mass of styrene, 300 parts by mass of butyl acrylate, and 300 parts by mass of methacrylic acid was added dropwise over 4 hours. After dropwise addition, the mixture was aged at 75°C for 4 hours to obtain a [microparticle dispersion (W0-3)] containing a resin (a3-1), which is a polymer copolymerized with the monomer and polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium. The volume-average particle size of the resin microparticles in the [microparticle dispersion (W0-3)] was measured by dynamic light scattering (light scattering electrophoresis apparatus: Otsuka Electronics Co., Ltd., ELS-8000) and found to be 45 nm. Furthermore, when a portion of the [microparticle dispersion (W0-3)] was dried and resin (a3-1) was isolated, the Tg of the resin component was 53°C and the acid value was 195 mgKOH / g. Next, 667 parts by mass of [fine particle dispersion (W0-3)] and 248 parts by mass of water were charged into a reaction vessel equipped with a stirrer, a heating and cooling device, and a thermometer. 0.267 parts by mass of tert-butyl hydroperoxide (manufactured by NOF Corporation, Perbutyl H) was added, and the mixture was heated to raise the system temperature to 70°C. Then, 43.3 parts by mass of styrene, 23.3 parts by mass of butyl acrylate, and 18.0 parts by mass of 1% by mass aqueous ascorbic acid solution were added dropwise over 2 hours. After dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a fine particle dispersion of resin microparticles (A-3) containing resin (a3-1) as a constituent component within the same particle. This dispersion contained resin (a3-2), a polymer copolymerized from the monomer using resin (a3-1) in (W0-3) as a seed, and resin (a3-1). Water was added to the obtained fine particle dispersion to a solid content concentration of 20% to obtain resin microparticle dispersion (W-3). The volume-average particle size of [resin microparticles (A-3)] was measured by dynamic light scattering (light scattering electrophoresis apparatus: Otsuka Electronics Co., Ltd., ELS-8000) and found to be 51.5 nm. Furthermore, resin (a3-2) was isolated by neutralizing [resin microparticle dispersion (W-3)] with a 10% by mass aqueous ammonia solution to pH 9.0, and then drying the precipitate obtained by centrifugation. The Tg of the resin component was 53°C and the acid value was 195 mgKOH / g.

[0250] <Example of preparation of wax dispersion> In a pressure-resistant reaction vessel equipped with a stirrer, heating / cooling device, thermometer, and dropping cylinder, 454 parts by mass of xylene and 150 parts by mass of low molecular weight polyethylene (Sanyo Chemical Industries, Ltd., Sanwax LEL-400) were added. After purging with nitrogen, the temperature was raised to 170°C under stirring. At the same temperature, a mixture of 595 parts by mass of styrene, 255 parts by mass of methyl methacrylate, 34 parts by mass of di-t-butyl peroxyhexahydroterephthalate, and 119 parts by mass of xylene was added dropwise over 3 hours, and the mixture was held at the same temperature for another 30 minutes. Then, the xylene was removed by distillation under reduced pressure of 0.039 MPa to obtain a modified wax. The sp value of the graft chain of the modified wax is 10.35 (cal / cm²). 3 ) 1 / 2 The values ​​were Mn 1,900, Mw 5,200, and Tg 57°C. In a container equipped with a stirring rod and a thermometer, 50 parts by mass of paraffin wax (manufactured by Nippon Seiro Co., Ltd., HNP-9, hydrocarbon wax, melting point 75°C, SP value 8.8), 5 parts by mass of the modified wax, and 165 parts by mass of ethyl acetate were charged. The mixture was heated to 80°C under stirring and maintained at 80°C for 5 hours, then cooled to 30°C in 1 hour. Subsequently, a bead mill (UltraViscomill, manufactured by AIMEX) was used to disperse the mixture under the following conditions: liquid transfer rate of 1 kg / hr, disk peripheral speed of 6 m / sec, and 0.5 mm diameter zirconia beads packed at 80 volume%, in 3 passes, to obtain a wax dispersion.

[0251] <Masterbatch Preparation Example 1> 1,200 parts by mass of water, 500 parts by mass of carbon black (Printex35, manufactured by Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5], and 500 parts by mass of [amorphous polyester resin 1] were added and mixed in a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The resulting mixture was kneaded at 150°C for 30 minutes using two rolls, then rolled and cooled, and pulverized in a pulperizer to obtain masterbatch 1.

[0252] <Masterbatch Preparation Example 2> 100 parts by mass of montmorillonite were thoroughly dispersed in 200 mL of water, and 38.1 parts by mass of dimethylstearylbenzylammonium chloride (423.5 g / mol), which had been thoroughly dissolved in water beforehand, were added and mixed. The mixture was then washed, dehydrated, and dried to prepare an organically modified layered inorganic mineral with a 100% organic ion modification rate. 2,400 parts by mass of water, 1,919 parts by mass of the organically modified layered inorganic mineral, and 1,570 parts by mass of [amorphous polyester resin 1] were mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The resulting mixture was kneaded with a two-roller at 150°C for 30 minutes, then cooled and pulverized with a pulperizer (manufactured by Hosokawa Micron Corporation) to obtain masterbatch 2.

[0253] (Example 1) <Example of oil phase preparation> 21 parts by mass of [wax dispersion], 47 parts by mass of [crystalline polyester dispersion], 49 parts by mass of [amorphous polyester resin 1], 17 parts by mass of [masterbatch 1], 17 parts by mass of [masterbatch 2], and 30 parts by mass of ethyl acetate were placed in a container and mixed at 5,000 rpm for 60 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.). Then, using a bead mill (Ultra Viscomill, manufactured by AIMEX), the mixture was dispersed with 0.5 mm diameter zirconia beads at a disk peripheral speed of 7 m / s, filling the container with 70% by volume, and passing the mixture 6 times (number of passes through the bead mill per unit volume) to obtain the [oil phase]. At this time, the liquid delivery speed was adjusted so that the entire oil phase was dispersed for an average of 0.5 minutes per pass.

[0254] <Example of aqueous phase preparation> 256 parts by mass of water, 15 parts by mass of [fine particle dispersion (W-1)], 26 parts by mass of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 24 parts by mass of ethyl acetate were mixed and stirred to obtain the [aqueous phase].

[0255] 181 parts by mass of the oil phase, 14 parts by mass of the prepolymer 1, and 0.2 parts by mass of isophorone diamine as a curing agent were added and stirred to obtain a mixture. 306 parts by mass of the aqueous phase were added to the obtained mixture and mixed in a TK homomixer at a rotation speed of 13,000 rpm for 20 minutes. Next, the mixture was desolvented at 30°C for 8 hours and then aged at 45°C for 4 hours to obtain a dispersion slurry.

[0256] <Washing and drying> After filtering 100 parts by mass of the aforementioned [dispersed slurry] under reduced pressure, the following operations were performed. (1): 100 parts of deionized water were added to the filter cake, mixed with a TK homomixer (rotating at 12,000 rpm for 10 minutes), and then filtered. (2): Add a 10% sodium hydroxide solution to the filtered cake from (1) until the pH reaches 11, mix with a TK homomixer (at 12,000 rpm for 30 minutes), and then filter under reduced pressure. (3): Add 10% hydrochloric acid to the filtered cake from (2) until the pH reaches 4-5, mix with a TK homomixer (at 12,000 rpm for 10 minutes), and then filter. (4): The above operations (1) to (4) were repeated twice to obtain a filter cake by adding 300 parts by mass of deionized water to the filter cake from (3), mixing with a TK homomixer (rotating at 12,000 rpm for 10 minutes), and then filtering. The filtered cake was dried in a circulating air dryer at 45°C for 48 hours, and then sieved with a 75 μm mesh to obtain toner matrix particles.

[0257] <External processing> [Toner 1] was obtained by mixing 100 parts by mass of [Toner matrix particles 1] with 0.6 parts by mass of hydrophobic silica with an average particle size of 100 nm, 1.0 part by mass of titanium oxide with an average particle size of 20 nm, and 0.8 parts by mass of hydrophobic silica fine powder with an average particle size of 15 nm using a Henschel mixer. The average circularity of the obtained toner was 0.98, and the standard deviation of the circularity was 0.016. Furthermore, the glass transition temperature of the obtained toner was 42°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, the glass transition temperature of the THF-soluble components of the toner was 53°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 1]. Figure 3 shows an example of the state of resin fine particles on the surface of toner 1.

[0258] <Method for measuring mean circularity and the standard deviation of mean circularity> 0.1 ml of 10% by mass surfactant (alkylbenzenesulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 0.1 g of [Toner 1], and 80 ml of deionized water were added to a 100 ml glass beaker and stirred with a micro spatula to obtain a toner dispersion. The obtained toner dispersion was then dispersed for 3 minutes using an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.), and the mean circularity and standard deviation of the toner were measured using a flow-type particle image analyzer ("FPIA-2100", manufactured by Sysmex Corporation) and analysis software FPIA-2100 until the toner concentration was 5,000 particles / μL to 15,000 particles / μL.

[0259] <Career Creation> To 100 parts by mass of toluene, 100 parts by mass of straight silicone resin consisting only of organosiloxane bonds, 5 parts by mass of γ-(2-aminoethyl)aminopropyltrimethoxysilane, and 10 parts by mass of carbon black were added and dispersed in a homomixer for 20 minutes to prepare a resin layer coating solution. Using a fluidized bed coating apparatus, the resin layer coating solution was applied to the surface of 1,000 parts by mass of spherical magnetite with an average particle size of 50 μm to prepare a [carrier].

[0260] <Preparation of developer> Using a ball mill, 5 parts by mass of [toner 1] and 95 parts by mass of [carrier] were mixed to prepare a developer.

[0261] <Method for measuring glass transition temperature> 1 g of toner was added to 100 mL of tetrahydrofuran (THF), and Soxhlet extraction was performed to obtain THF-insoluble and THF-soluble components from the toner. The obtained THF-insoluble and THF-soluble components were dried separately in a vacuum dryer for 24 hours to obtain a THF-insoluble polyester resin component and a THF-soluble polyester resin component, respectively. In the following, the THF-insoluble polyester resin component was used as the target sample for measuring the glass transition temperature of the THF-insoluble component of the toner, and the THF-soluble polyester resin component was used as the target sample for measuring the glass transition temperature of the THF-soluble component of the toner. In addition, toner was used as the target sample for measuring the glass transition temperature of the toner. Next, 5.0 mg of the target sample was placed in an aluminum sample container, which was then placed on a holder unit and set in an electric furnace. Next, under a nitrogen atmosphere, the sample was heated from -80°C to 150°C at a heating rate of 1.0°C / min (first heating pass). Next, the mixture was cooled from 150°C to -80°C at a cooling rate of 1.0°C / min, and then heated from -80°C to 150°C at a heating rate of 1.0°C / min (second heating cycle). During the first and second heating cycles described above, DSC curves were measured using a differential scanning calorimeter (Q-200, TA Instruments Inc.). From the obtained DSC curves, the DSC curve from the first heating cycle was selected using the analysis program in the Q-200 system, and the glass transition temperature Tg1st for the first heating cycle was determined. Similarly, the DSC curve from the second heating cycle was selected, and the glass transition temperature Tg2nd for the second heating cycle was determined.

[0262] (Example 2) Toner 2 was prepared in the same manner as in Example 1, except that [fine particle dispersion (W-1)] in the aqueous phase preparation was changed to [fine particle dispersion (W-2)]. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.98, and the standard deviation of the average circularity was 0.016. Furthermore, the glass transition temperature of the obtained toner was 42°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, the glass transition temperature of the THF-soluble components of the toner was 53°C, and the content of [resin fine particles (A-2)] was 3.0% by mass relative to [toner 2].

[0263] (Example 3) Toner 3 was prepared in the same manner as in Example 1, except that [fine particle dispersion (W-1)] in the aqueous phase preparation was changed to [fine particle dispersion (W-3)]. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.98, and the standard deviation of the average circularity was 0.016. Furthermore, the glass transition temperature of the obtained toner was 42°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, the glass transition temperature of the THF-soluble components of the toner was 53°C, and the content of [resin fine particles (A-3)] was 3.0% by mass relative to [toner 3].

[0264] (Example 4) In Example 1, toner 4 was prepared in the same manner as in Example 1, except that the peripheral speed of the bead mill disk during oil phase preparation was changed to 9 m / second. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.972, and the standard deviation of the average circularity was 0.017. Furthermore, the glass transition temperature of the obtained toner was 42°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, the glass transition temperature of the THF-soluble components of the toner was 53°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 4].

[0265] (Example 5) In Example 1, toner 5 was prepared in the same manner as in Example 1, except that the peripheral speed of the bead mill disk during oil phase preparation was set to 7 m / second and the number of passes (number of times the beads passed through the bead mill per unit volume) was changed to 10. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.976, and the standard deviation of the average circularity was 0.014. Furthermore, the glass transition temperature of the obtained toner was 42°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, the glass transition temperature of the THF-soluble components of the toner was 53°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 5].

[0266] (Example 6) In Example 1, toner 6 was prepared in the same manner as in Example 1, except that the peripheral speed of the bead mill disk during oil phase preparation was changed to 6 m / second. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.983, and the standard deviation of the average circularity was 0.019. Furthermore, the glass transition temperature of the obtained toner was 42°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, the glass transition temperature of the THF-soluble components of the toner was 53°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 6].

[0267] (Example 7) In Example 1, toner 7 was prepared in the same manner as in Example 1, except that 300 parts by mass of deionized water were added to the filtration cake after washing and drying, mixed in a TK homomixer (rotating at 12,000 rpm for 10 minutes), heated to 68°C using a plate heat exchanger and held for 20 minutes, and then cooled to 25°C using a plate heat exchanger. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.982, and the standard deviation of the average circularity was 0.016. Furthermore, the glass transition temperature of the obtained toner was 42°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, the glass transition temperature of the THF-soluble components of the toner was 53°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 7].

[0268] (Example 8) In Example 1, toner 8 was prepared in the same manner as in Example 1, except that the content of [fine particle dispersion (W-1)] in the preparation of the aqueous phase was changed to 21 parts by mass. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.981, and the standard deviation of the average circularity was 0.019. Furthermore, the glass transition temperature of the obtained toner was 42°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, the glass transition temperature of the THF-soluble components of the toner was 53°C, and the content of [resin fine particles (A-1)] was 4.1% by mass relative to [toner 8].

[0269] (Comparative Example 1) In Example 1, [toner 9] was obtained in the same manner as in Example 1, except that the bead milling process was omitted in the preparation of the oil phase. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.982, and the standard deviation of the average circularity was 0.026. Furthermore, the glass transition temperature of the obtained toner was 42°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, the glass transition temperature of the THF-soluble components of the toner was 53°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 9].

[0270] (Comparative Example 2) In Example 1, the bead milling process was omitted in the preparation of the oil phase. Instead, 300 parts by mass of deionized water were added to the filtration cake after washing and drying, mixed in a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes), heated to 75°C using a plate heat exchanger, held for 80 minutes, and then cooled to 25°C using a plate heat exchanger. [Toner 10] was prepared in the same manner as in Example 1. The average circularity and the standard deviation of the average circularity were measured using the same method as in Example 1. The average circularity of the obtained toner was 0.986, and the standard deviation of the average circularity was 0.019. Furthermore, the glass transition temperature of the obtained toner was 42°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, the glass transition temperature of the THF-soluble components of the toner was 53°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 10].

[0271] (Comparative Example 3) In Example 1, toner 11 was prepared in the same manner as in Example 1, except that the peripheral speed of the bead mill disk during oil phase preparation was set to 9 m / s and the number of passes (number of times the beads passed through the mill per unit volume) was changed to 30. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.968, and the standard deviation of the average circularity was 0.018. Furthermore, the glass transition temperature of the obtained toner was 42°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, the glass transition temperature of the THF-soluble components of the toner was 53°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 11].

[0272] (Comparative Example 4) In Example 1, toner 12 was obtained in the same manner as in Example 1, except that [amorphous polyester 1] was replaced with [amorphous polyester 2]. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.981, and the standard deviation of the average circularity was 0.016. Furthermore, the glass transition temperature of the obtained toner was 55°C, the glass transition temperature of the THF-insoluble components of the toner was -37°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 12].

[0273] (Comparative Example 5) In Example 1, toner 13 was obtained in the same manner as in Example 1, except that [amorphous polyester 1] was replaced with [amorphous polyester 3] and 14 parts by mass of [prepolymer 1] was replaced with 21 parts by mass of [prepolymer 1]. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.980, and the standard deviation of the average circularity was 0.016. Furthermore, the glass transition temperature of the obtained toner was 18°C, the glass transition temperature of the THF-insoluble components of the toner was -39°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 13].

[0274] (Comparative Example 6) Toner 14 was obtained in the same manner as in Example 1, except that 14 parts by mass of [prepolymer 1] was replaced with 7 parts by mass of [prepolymer 2]. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.980, and the standard deviation of the average circularity was 0.016. Furthermore, the glass transition temperature of the obtained toner was 48°C, the glass transition temperature of the THF-insoluble components of the toner was 13°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 14].

[0275] (Comparative Example 7) In Example 1, toner 15 was obtained in the same manner as in Example 1, except that prepolymer 1 was replaced with prepolymer 3. The average circularity and the standard deviation of the average circularity were measured in the same manner as in Example 1, and the average circularity of the obtained toner was 0.981, and the standard deviation of the average circularity was 0.016. Furthermore, the glass transition temperature of the obtained toner was 35°C, the glass transition temperature of the THF-insoluble components of the toner was -55°C, and the content of [resin fine particles (A-1)] was 3.0% by mass relative to [toner 15].

[0276] The toners obtained in Examples 1-8 and Comparative Examples 1-7 were evaluated for their low-temperature fixability, heat resistance, cleaning properties, and transferability. The evaluation results are shown in Tables 1 to 3 below.

[0277] <Low temperature retention> Using a color multifunction printer (imagio MP C4500, manufactured by Ricoh Co., Ltd.) with the thermal fuser removed, toner was applied to the paper surface (recycled PPC paper 100, manufactured by Oji Paper Co., Ltd.) at a rate of 0.8 mg / cm². 2 They were spread evenly to achieve this result. This paper is fixed using a pressure roller at a fixing speed (peripheral speed of the heating roller) of 213 mm / sec and a fixing pressure (pressure of the pressure roller) of 10 kg / cm². 2 The minimum fixing temperature was measured under the specified conditions. Low-temperature fixing performance was evaluated based on the following evaluation criteria. [Evaluation Criteria] ◎: Minimum fixing temperature is 130℃ or lower ○: The minimum fixing temperature is greater than 130°C and 135°C or less. △: The minimum fixing temperature is greater than 135°C and 140°C or lower. ×: The minimum fixing temperature is greater than 140°C.

[0278] <Heat-resistant storage stability> 10g of toner was filled into a 50mL glass container, stored at 50°C for 8 hours, then sieved through a 42-mesh sieve for 2 minutes. The mass of toner remaining on the sieve was measured, and the toner retention rate was calculated as the ratio of the remaining toner to the mass of toner placed on the sieve [(mass of toner remaining on the sieve / mass of toner placed on the sieve) × 100]. The heat-resistant storage performance was then evaluated based on the following evaluation criteria. [Evaluation Criteria] ◎: Survival rate less than 5% ○: Survival rate is 5% or more but less than 15% △: Survival rate is 15% or more but less than 30% ×: Survival rate of 30% or more

[0279] <Cleaning properties> Using the aforementioned image forming apparatus, 50,000 charts (A4 size, landscape orientation) were printed at a rate of 3 prints per job, under laboratory conditions of 21°C, 65% RH, and an image area ratio of 5%. Subsequently, in a laboratory environment of 32°C and 54%RH, 100 evaluation images were printed on A4 size landscape paper, each containing three 43mm wide vertical stripe patterns (relative to the direction of paper travel). The resulting images were visually observed, and the cleaning performance was evaluated based on the following evaluation criteria. [Evaluation Criteria] ◎: No toner that has been filtered out due to poor cleaning can be visually confirmed on the printed paper or on the photoreceptor, and no streaky toner residue can be seen even when the photoreceptor is observed longitudinally under a microscope. ○: Due to poor cleaning, toner that has been smeared through cannot be visually confirmed on either the printed paper or the photoconductor. ×: Due to poor cleaning, toner that has been smeared through can be visually confirmed on both the printed paper and the photoconductor.

[0280] <Transferability> An evaluation machine was used, a modified Fuji Xerox DocuColor 8000 Digital Press, tuned to a line speed of 162 mm / sec and a transfer time of 40 msec. For each developer, the toner adhesion amount was 0.6 mg / cm² on an A4 size sheet. 2 A running test was conducted, outputting the solid pattern as a test image. The primary transfer efficiency in the initial and 100K output of the test image was determined using formula (3) below, and the secondary transfer efficiency in the secondary transfer was determined using formula (4) below. The average of the primary and secondary transfer efficiencies was calculated, and the transferability was evaluated based on the evaluation criteria below. Primary transfer efficiency (%) = (Amount of toner transferred onto the intermediate transfer medium / Amount of toner developed onto the electrophotographic photoreceptor) × 100 ... Equation (3) Secondary transfer efficiency (%) = (Amount of toner transferred onto the intermediate transfer material - Amount of toner remaining on the intermediate transfer material / Amount of toner transferred onto the intermediate transfer material) × 100 ... Equation (4) [Evaluation Criteria] ◎: 90% or more ○: 85% or more and less than 90% △: 80% or more but less than 85% ×: Less than 80%

[0281] [Table 1]

[0282] [Table 2]

[0283] [Table 3]

[0284] The toners of Examples 1 to 8 of the present invention exhibited excellent performance in low-temperature fixing, heat-resistant storage, cleaning, and transferability. In contrast, the toners of Comparative Examples 1 to 7 were unable to achieve a balance between low-temperature fixing, heat-resistant storage, cleaning, and transferability.

[0285] Examples of the present invention are as follows: <1> Toner matrix particles containing a binder resin, A toner having resin fine particles on the surface of the toner matrix particles, The glass transition temperature of the toner during the first heating cycle, as determined by differential scanning calorimetry (DSC), is between 20°C and 50°C. The glass transition temperature of the tetrahydrofuran (THF)-insoluble component of the toner during the first DSC heating cycle is between -40°C and 10°C. The average circularity of the aforementioned toner is 0.970 or more and 0.985 or less. The toner is characterized in that the standard deviation of the average circularity is 0.020 or less. <2> The standard deviation of the mean circularity is 0.014 or less, <1> This is the toner described in [the document]. <3> The glass transition temperature (Tg) of the toner during the first heating cycle, as determined by differential scanning calorimetry (DSC), is between 40°C and 50°C. The glass transition temperature of the THF-insoluble component of the toner during the first heating step by DSC is between -40°C and 5°C. The glass transition temperature (Tg) of the THF-soluble component of the toner during the second heating by DSC is 20°C or higher and 65°C or lower. <1> from <2> It is the toner described in one of the following lists. <4> The content of the resin fine particles is 0.2% by mass or more and 5% by mass or less relative to the toner, <1> from <3> It is the toner described in one of the following lists. <5> The aforementioned binder resin is a polyester resin. The polyester resin contains a trivalent or tetravalent aliphatic polyhydric alcohol component having 3 to 10 carbon atoms, <1> from <4> It is the toner described in one of the following lists. <6> The aforementioned polyester resin contains a diol component, The diol component has a main chain portion with 3 to 9 carbon atoms and an alkyl group in the side chain, <5> This is the toner described in [the document]. <7> The polyester resin has at least one of urethane bonds and urea bonds. <5> from <6> It is the toner described in one of the following lists. <8> The aforementioned <1> from <7> This toner storage unit is characterized by storing the toner described in any of the following. <9> The aforementioned <8> This is an image forming apparatus characterized by having the toner storage unit described above. <10> The aforementioned <1> from <7> An image forming apparatus having a toner as described in any of the following: Electrostatic latent image carrier, An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, A developing means comprising a toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image, This is an image forming apparatus characterized by having [a certain feature].

[0286] The aforementioned <1> from <7> Toner as described in any of the above <8> The toner storage unit described above, and the <9> from <10> According to the image forming apparatus described in any of the above, the aforementioned problems of the conventional method can be solved and the objective of the present invention can be achieved. [Explanation of Symbols]

[0287] 10 Photoconductor drum 40 Developer 58 Corona Charger 80 Transfer Rollers 90 Cleaning device 110 Process Cartridges 210 Paper feed section 211 Paper feed cassette 212 Paper feed roller 220 Conveying section 221 Laura 222 Timing Roller 223 Paper output roller 224 Paper Output Tray 230 Image creation section 233 Exposure Unit 240 Transfer section 241 Drive roller 242 Driven roller 243 Intermediate transfer belt 244 Primary Transfer Roller 245 Secondary opposing roller 246 Secondary Transfer Roller 250 Fuser 251 Fixing belt 252 Pressure roller [Prior art documents] [Patent Documents]

[0288] [Patent Document 1] Japanese Patent Publication No. 2002-372806

Claims

1. Toner matrix particles containing a binder resin, A toner having resin fine particles on the surface of the toner matrix particles, The glass transition temperature of the toner during the first heating cycle, as determined by differential scanning calorimetry (DSC), was 42°C. The glass transition temperature of the tetrahydrofuran (THF)-insoluble component of the toner during the first DSC heating cycle is -37°C. The average circularity of the aforementioned toner is 0.970 or more and 0.985 or less. A toner characterized in that the standard deviation of the average circularity is 0.020 or less.

2. The toner according to claim 1, wherein the standard deviation of the mean circularity is 0.014 or less.

3. The toner according to any one of claims 1 to 2, wherein the glass transition temperature (Tg) of the THF-soluble component of the toner during the second heating by DSC is 20°C or higher and 65°C or lower.

4. The toner according to any one of claims 1 to 3, wherein the content of the resin fine particles is 0.2% by mass or more and 5% by mass or less relative to the toner.

5. The aforementioned binder resin is a polyester resin. The toner according to any one of claims 1 to 4, wherein the polyester resin contains a trivalent or tetravalent aliphatic polyhydric alcohol component having 3 to 10 carbon atoms.

6. The polyester resin contains a diol component, The toner according to claim 5, wherein the diol component has a main chain portion with 3 to 9 carbon atoms and an alkyl group in the side chain.

7. The toner according to any one of claims 5 to 6, wherein the polyester resin has at least one of urethane bonds and urea bonds.

8. A toner storage unit characterized by storing the toner described in any one of claims 1 to 7.

9. An image forming apparatus characterized by having the toner storage unit described in claim 8.

10. An image forming apparatus having the toner according to any one of claims 1 to 7, Electrostatic latent image carrier, An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, A developing means comprising a toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image, An image forming apparatus characterized by having the following features.

Images