[DESCRIPTION]

[Title of Invention] METHOD FOR MANUFACTURING TONER [Technical Field]

[0001] The present invention relates to a method for manufacturing a toner to be used for developing electrostatic images in electrophotograpic methods, electrostatic recording methods and the like.

[Background Art]

[0002] In response to recent demands for energy savings in image formation, efforts are being made to reduce toner fixation temperatures. One proposal has been to reduce fixation temperatures still further by using a polyester with a low softening temperature. Because the softening temperature is low, however, the toner particles may fuse together and blocking may occur when the toner is left standing during storage or transportation.

As a means of achieving both blocking resistance and low-temperature fixability, a technique has been proposed using a crystalline resin with a sharp melt property, meaning that its viscosity decreases sharply when its melting temperature is exceeded (Patent Literatures 1 to 3) .

However, a serious problem has been that when a crystalline polyester (which is a crystalline resin) is used alone as a binder resin, the toner charge gradually escapes after triboelectric charging due to the low electric resistance of the crystalline polyester.

A toner has therefore been proposed containing a reduced amount of crystalline polyester, which is mixed together with an amorphous resin that is compatible with the crystalline polyester (Patent Literature 4).

However, the following problems may occur with a toner containing an amorphous resin together with a crystalline polyester as a binder resin when easily compatible resins are combined.

After passing through a step of heating and melting at equal to or above the melting point of the crystalline polyester or a step of using an organic solvent to dissolve the crystalline polyester during toner manufacture, the amorphous resin and crystalline polyester are present in the toner in a compatibilized state. This induces plasticization of the amorphous resin (in other words, lowering of the glass transition temperature) , as a result of which, although sharp melt properties are good, the charging performance and heat- resistant storability are inadequate and have sometimes been worse.

In the case of a toner in which the crystalline polyester is mixed with an incompatible amorphous resin, the following problems may occur because the resins are incompatible.

Even after passing through a step of heating and melting at equal to or above the melting point of the crystalline polyester or a step of using an organic solvent to dissolve the crystalline polyester during toner manufacture, the amorphous resin and crystalline polyester still phase separate, spontaneously forming a matrix-domain structure corresponding to the compatibility of the resins. As a result, plasticization of the amorphous resin (in other words, lowering of the glass transition temperature) is not induced, and while the charging performance and heat heat-resistant storability are good, low-temperature fixability has been inadequate due to the poor compatibility.

When combining compatible resins, therefore, a method has been proposed for phase separating a compatibilized crystalline polyester and amorphous resin by means of an annealing step of promoting crystallization by heat treating the toner at a temperature at equal to or below the melting point and near the melting point of the crystalline polyester to thereby induce phase separation by crystallizing the crystalline polyester (Patent Literature 5) .

As a method for suppressing compatibilization during toner manufacture, moreover, a method has been proposed of dissolving a crystalline polyester in a solvent, cooling to recrystallize, and then mechanically pulverizing the crystalline polyester and dispersing it in a solvent. Toner components including an amorphous resin are then dissolved or dispersed in the solvent, and a toner is obtained via a granulating step (Patent Literature 6) .

[Citation List]

[Patent Literature]

[0003]

[PTL 1] Japanese Examined Patent Publication No. S56- 13943

[PTL 2] Japanese Examined Patent Publication No. S62- 39428

[PTL 3] Japanese Patent Application Publication No. H4-120554

[PTL 4] Japanese Patent Application Publication No. 2003-50478

[PTL 5] Japanese Patent Application Publication No. 2006-65077

[PTL 6] Japanese. Patent Application Publication No. 2012-63534

[Summary of Invention]

[Technical Problem]

[0004] When the process includes an annealing step of heat treatment at a temperature at equal to or below the melting point and near the melting point of the crystalline polyester as in Patent Literature 5, this promotes crystallization of the crystalline polyester, inducing phase separation between it and the amorphous resin. However, the annealing step must be performed for a long time or under high-temperature conditions in order to adequately phase separate the crystalline polyester by heat treatment once it has been already compatibilized and melted into the amorphous resin.

In this case, because the domains of the crystalline polyester grow large at the same time that the phase-separation structure is forming during crystallization, the crystalline polyester domains (which are low-resistance components) are likely to be exposed on the surface of the toner, which can detract from charging performance.

With a toner manufacturing method involving mechanical pulverization following recrystallization of a crystalline polyester as in Patent Literature 6, it is possible to achieve both low-temperature fixability and storability because the crystalline polyester and amorphous resin are thoroughly phase separated. However, it is difficult to control the domain size of the crystalline polyester, and coarse domains in excess of 0.5 μιη occur. Moreover, because the crystalline polyester is dispersed in a solvent and droplets are then granulated into a toner size, it is difficult to produce uniform domains of the crystalline polyester in the toner. As a result, the crystalline polyester domains (which are low-resistance components) are likely to be exposed on the surface of the toner, which may detract from charging performance. That is, when crystalline resins and amorphous resins are compatibilized together in conventional manufacturing methods, it has been difficult to adequately phase separate the crystalline resin and the amorphous resin in the toner while also dispersing the crystalline resin uniformly in the form of minute domains. As a result, it has been difficult to achieve low- temperature fixability, storability and charging performance all at a high level.

[Solution to Problem]

[0005] The inventors in this case discovered as a result of exhaustive research that the following two points are critical for achieving adequate phase separation of a crystalline resin and an amorphous resin in a toner while thoroughly dispersing the crystalline resin in the form of minute domains when a crystalline resin and an amorphous resin are compatibilized together.

First, it is important to first compatibilize the crystalline resin and the amorphous resin and uniformly ix the crystalline resin and the amorphous resin together in the toner or in the resin component of the toner.

Second, it is important to form a phase-separated structure of the crystalline resin and the amorphous resin by a mechanism other than crystal growth of the crystalline resin due to conventional heat treatment.

Specifically, it was discovered that it is important to include the following steps in the toner manufacturing process.

(1) A compatibilization step of heating to equal to or above the melting point of the crystalline resin, or melting with an organic solvent, to thereby compatibilize the crystalline resin and the amorphous resin in the toner or the resin component of the toner and obtain a compatibilized blend.

(2) A step of adding a good solvent for the amorphous resin and a poor solvent for the crystalline resin to the compatibilized blend after the compatibilization step to thereby precipitate the crystalline resin.

With these steps, the crystalline resin is thoroughly phase separated from the amorphous resin and forms uniformly dispersed minute domains in the toner or the resin component of the toner.

[0006] The reasons why the crystalline resin is thoroughly phase separated from the amorphous resin and forms uniformly dispersed minute domains in the toner or the resin component of the toner in this method are not entirely clear, but may be as follows.

The mechanism of this invention differs from the mechanism of phase separation involving crystal growth of the crystalline resin caused by conventional heat treatment. In this invention, phase separation and crystal growth of the crystalline resin are not induced at the same time, and instead the different solubilities of the amorphous resin and the crystalline resin in organic solvents are exploited.

That is, a solvent that is a good solvent for the amorphous resin and a poor solvent for the crystalline resin is added to thereby precipitate only the crystalline resin compatibilized with the amorphous resin, inducing phase separation. It is believed that it is thus possible to induce adequate phase separation in the toner or the resin component of the toner before the domains of the crystalline resin grow too large.

That is, the toner manufacturing method of this invention includes a step of compatibilizing a crystalline resin and an amorphous resin that is compatible with the crystalline resin in order to uniformly disperse the crystalline resin in the toner or the resin component of the toner. In order to form minute domains of the crystalline resin, moreover, it includes a solvent treatment step that induces adequate phase separation of the compatibilized crystalline resin in the toner or the resin component of the toner before the domains of the crystalline resin grow too large.

[0007] That is, this invention relates to a method for manufacturing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin, comprising a compatibilization step of compatibilizing the crystalline resin and the amorphous resin to obtain a compatibilized blend, and a solvent treatment step of treating the compatibilized blend with an organic solvent, wherein the organic solvent is a good solvent for the amorphous resin and a poor solvent for the crystalline resin.

[Advantageous Effects of Invention]

[0008] The present invention can provide a method for manufacturing a toner having both low-temperature fixability and storability, as well as good charging performance.

Further features of the present invention will become apparent from the following description of exemplary embodiments.

[Description of Embodiments]

[0009] The toner manufacturing method of the present invention (hereunder sometimes called the method of this invention) is a method for manufacturing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin, comprising a compatibilization step of compatibilizing the crystalline resin and the amorphous resin to obtain a compatibilized blend, and a solvent treatment step of treating the compatibilized blend with an organic solvent, wherein the organic solvent is a good solvent for the amorphous resin and a poor solvent for the crystalline resin.

The compatibilization step and the solvent treatment step using a specific organic solvent in the method of this invention are explained first.

[0010] Compatibility

The compatibility between the crystalline resin and the amorphous resin necessary for achieving low- temperature fixability of the toner in this invention is explained.

As discussed above, when manufacturing a toner by mixing a crystalline resin with an amorphous resin that is hardly compatible with the crystalline resin, a matrix-domain structure corresponding to the compatibility of the resins is formed spontaneously because the resins are hardly compatible with each other. As a result, plasticization of the amorphous resin is not induced, and low-temperature fixability has been inadequate. By contrast, this invention is a method for manufacturing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin, whereby a high level of low-temperature taxability is achieved because the crystalline resin, which is blended uniformly in the resin component of the toner, can rapidly induce plasticization of the toner as a whole.

[0011] Compatibilization step

The compatibilization step in this invention is a step of compatibilizing a crystalline resin and an amorphous resin compatible with the crystalline resin (hereunder sometimes simply called an amorphous resin) to obtain a compatibilized blend.

Specific examples include a step of heating the crystalline resin and the amorphous resin to equal to or above a melting point of the crystalline resin to thereby compatibilize the crystalline resin and the amorphous resin and obtain a compatibilized blend; and a step of dissolving the crystalline resin and the amorphous resin in an organic solvent capable of dissolving the crystalline resin and the amorphous resin, to thereby compatibilize the crystalline resin and the amorphous resin and obtain a compatibilized blend. Once the crystalline resin and the amorphous resin have been compatibilized, they can also be cooled or the organic solvent can be removed to obtain a compatibilized blend. The heating temperature in the compatibilization step may be any temperature at equal to or above the melting point of the crystalline resin, or preferably a temperature 5°C or more higher than the melting point of the crystalline resin, or more preferably a temperature 10°C or more higher than the melting point of the crystalline resin.

The upper limit of the heating temperature in the compatibilization step is determined afte.r considering the effects on costs and the like, and is not particularly limited, but is preferably a temperature about 140°C higher than the melting point of the crystalline resin.

In the compatibilization step, by either (1) melting the crystalline resin by heating the crystalline resin and the amorphous resin to equal to or above the melting point of the crystalline resin, or (2) dissolving the crystalline resin and the amorphous resin in an organic solvent capable of dissolving the crystalline resin and the amorphous resin, the crystalline resin is compatibilized and made to form a compatibilized blend with the co-existing, high- affinity amorphous resin, and becomes uniformly blended in the resin component of the toner.

As a result, a high level of low-temperature fixability is achieved when the toner is fixed because the crystalline resin uniformly blended in the resin component of the toner can induce plasticization of the toner as a whole.

[0012] The compatibility between the crystalline resin and the amorphous resin may ^' be considered as follows. The compatibilized blend obtained by compatibilizing the crystalline resin and the amorphous resin in the compatibilization step preferably satisfies the following formula (Formula 1):

0.00 < {Wt/(Wr x Z/100) } < 0.50 (Formula 1).

Wt : An amount of heat of fusion (J/g) derived from the crystalline resin during second temperature rise in measurement of the compatibilized blend by differential scanning calorimeter (DSC)

Wr: An amount of heat of fusion (J/g) during second temperature rise in measurement of the crystalline resin by differential scanning calorimeter (DSC)

Z: A content ratio (mass%) of the crystalline resin in the compatibilized blend

[0013] The measurement methods using the differential scanning calorimeter (DSC) are as follows.

0.01 to 0.02 g of a "compatibilized blend (solid) obtained by compatibilizing a crystalline resin and an amorphous resin", or of a "crystalline resin", is accurately weighed into an aluminum pan, the temperature is risen from 0°C to 200°C at a ramp rate of 10°C/min, and a DSC curve for the first temperature rise is obtained.

Next, the temperature is lowered to -100°C from 200°C at a rate of 10°C/min, and then risen again from - 100°C to 200°C at a ramp rate of 10°C/min, and the DSC curve for the second temperature rise is obtained.

In the DSC curve for the second temperature rise, the amount of heat of fusion (J/g) is determined from the area surrounded by the melting endothermic peak and a straight line extending the baseline of the low- temperature side to the high-temperature side.

[0014] The crystalline resin and the amorphous resin are compatibilized in the compatibilized blend obtained in the compatibilization step. Thus, the crystalline resin in the compatibilized blend is not as thoroughly crystallized as it was before compatibilization, and the amount of heat of fusion (J/g) as determined from the melting endothermic peak of the crystalline resin is lower as a result.

In Formula 1 above, the denominator is the product of "the amount of the heat of fusion (Wr) of crystals observed in the crystalline resin by itself" and "the content ratio (Z) of the crystalline resin in the compatibilized blend", and signifies the amount of heat of fusion when the crystalline resin contained in the compatibilized blend is crystallized in the same way as the crystalline resin by itself. Therefore, in the compatibilized blend obtained in the compatibilization step, the greater the degree of compatibilization between the crystalline resin and the amorphous resin, or in other words the greater the compatibility between the crystalline resin and the amorphous resin, the more Wt will be smaller than (Wr x Z/100) .

As {Wt/( r x Z/100)} exceeds 0.50, the degree of compatibilization between the crystalline resin and the amorphous resin in the compatibilization step will tend to decline, and the uniform dispersibility of the crystalline resin in the resulting toner will also tend to be less. Because of the lower compatibility between the crystalline resin and the amorphous resin, moreover, plasticization of the amorphous resin will not be sufficiently induced, and low-temperature fixability will tend to be less.

{ t/(Wr x Z/100)} is more preferably at least 0.00 and not more than 0.40, or still more preferably at least 0.00 and not more than 0.30. A smaller value means that compatibilization is easier, and uniform dispersibility of the crystalline resin in the toner can be increased.

[0015] The compatibilized blend may contain an added release agent or the like as necessary, and the melting endothermic peak of this release agent or the like may be observed. The melting endothermic peak of this release agent or the like can be distinguished from the melting endothermic peak derived from the crystalline resin using the differential scanning calorimeter, by first measuring the release agent or the like by itself and then comparing the resulting melting endothermic peak with the melting endothermic peak derived from the crystalline resin. The release agent or the like by itself can be obtained from the compatibilized blend by Soxhlet extraction using a hexane solvent, but the original added release agent itself may also be used.

With this compatibilization step, it is possible to uniformly disperse the crystalline resin in the toner, and achieve a high level of low-temperature fixability .

However, when the crystalline resin in a compatibilized state is crystallized by heat treatment of the crystalline resin, the domains of the crystalline resin grow larger at the same time that a phase separation structure is forming during crystallization. As a result, the crystalline resin domains (which are low-resistance components) are likely to be exposed on the surface of the toner, detracting from charging performance as discussed above.

Therefore, we discovered as a result of exhaustive research that by performing a solvent treatment step using a specific organic solvent, it was possible to precipitate the crystalline resin and achieve adequate phase separation of the crystalline resin and the amorphous resin in the toner, and also to form very fine, uniformly dispersed domains of the crystalline resin in the toner.

[0016] Solvent treatment step

The solvent treatment step in this invention is a step of treating the compatibilized blend with an organic solvent, with the organic solvent being a good solvent for the amorphous resin and a poor solvent for the crystalline resin.

This is a step of adding a specific organic solvent that is a good solvent for the amorphous resin and a poor solvent for the crystalline resin to the compatibilized blend obtained in the compatibilization step, to thereby precipitate the crystalline resin compatibilized with the amorphous resin, and obtain a solvent-treated product in which separation of a crystalline phase has been induced.

With this solvent treatment step, the crystalline resin and the amorphous resin are thoroughly phase separated, and the crystalline resin becomes uniformly dispersed as minute domains. The reasons for this are not clear, but may be as follows.

The solvent treatment step of this invention operates by a different mechanism from phase separation involving crystal growth of the crystalline resin caused by conventional heat treatment. This is because instead of inducing phase separation and crystal growth of the crystalline resin simultaneously by heat treatment, it exploits the different solubilities of the amorphous resin and the crystalline resin in an organic solvent.

That is, in the solvent treatment step a solvent that is a good solvent for the amorphous resin and a poor solvent for the crystalline resin is added, causing only the crystalline resin compatibilized with the amorphous resin to crystallize and precipitate while the amorphous resin is in a solubilized state, and thereby achieving phase separation of the crystalline resin. As a result, adeguate phase separation can be achieved without causing the domains of the crystalline resin to grow larger in the toner or the resin component of the toner.

[0017] In the solvent treatment step, the crystalline resin and the amorphous resin are phase separated as discussed above.

Thus, the solvent-treated product obtained in the solvent . treatment step preferably satisfies the following Formula 2:

1.00 > {(Wta - Wt0)/(Wr0 x Z/100)} > 0 (Formula 2). Wta: An amount of heat of fusion (J/g) derived from the crystalline resin during first temperature rise in measurement of the solvent-treated product by differential scanning calorimeter (DSC) WtO: An amount of heat of fusion (J/g) derived from the crystalline resin during first temperature rise in measurement of compatibilized blend by differential scanning calorimeter (DSC)

WrO: An amount of heat of fusion (J/g) during first temperature rise in measurement of the crystalline resin by differential scanning calorimeter (DSC)

Z: A content ratio (massl) of the crystalline resin in compatibilized blend.

[0018] The measurement methods using the differential scanning calorimeter (DSC) are as follows.

0.01 to 0.02 g of a "compatibilized blend (solid)", a "solvent-treated product (solid)" or a "crystalline resin" is accurately weighed into an aluminum pan, the temperature is risen from 0°C to 200°C at a ramp rate of 10°C/min, and a DSC curve for the first temperature rise is obtained.

In the resulting DSC curve, the amount of heat of fusion (J/g) is determined from the area surrounded by the melting endothermic peak and a straight line extending the baseline of the low-temperature side to the high-temperature side.

[0019] The numerator of Formula 2 above is the amount of heat of fusion (J/g) derived from the crystalline resin crystallized in the solvent treatment step, while the denominator is the product of "the amount of heat of fusion (WrO) of crystals observed in the crystalline resin by itself" and "the content ratio (Z) of the crystalline resin in the compatibilized blend", and signifies the amount of heat of fusion (J/g) when the crystalline resin contained in the compatibilized blend is crystallized in the same way as the crystalline resin by itself.

In the solvent-treated product obtained in the solvent treatment step, the crystalline resin and the amorphous resin are phase separated, and in the compatibilized blend obtained in the compatibilization step, the crystalline resin compatibilized with the amorphous resin is crystallized. Thus, { ( ta - t0)/(Wr0 x Z/100)} is greater than 0.

By calculating the value of {(Wta - Wt0)/(Wr0 x Z/100)}, it is possible to determine the amount of crystalline resin crystallized and precipitated in the solvent treatment step, or in other words the degree of phase separation of the crystalline resin and the amorphous resin.

In this invention, 0.80 > {(Wta - Wt0)/(Wr0 x Z/100)} > 0.05 is more desirable, and 0.50 > {(Wta - Wt0)/(Wr0 x Z/100)} > 0.10 is still more desirable in order to further improve the charging performance.

The value of {(Wta - Wt0)/(Wr0 x Z/100)} can be controlled for example by adjusting the added amount of the organic solvent in the solvent treatment step. [0020] The solvent-treated product may contain an added release agent or the like as necessary, and the melting endothermic peak of this release agent or the like may be observed. The melting endothermic peak of this release agent or the like can be distinguished from the melting endothermic peak derived from the crystalline resin using differential scanning calorimeter, by first measuring the release agent or the like by itself and then comparing the resulting melting endothermic peak with the melting endothermic peak derived from the crystalline resin. The release agent or the like by itself can be obtained from the compatibilized blend by Soxhlet extraction using a hexane solvent, but the original added release agent itself may also be used.

[0021] Organic solvent

In this invention, the organic solvent used in the solvent treatment step may be any that is a good solvent for the amorphous resin and a poor solvent for the crystalline resin, without any particular limitations.

When the organic solvent is a good solvent for both the amorphous resin and the crystalline resin, it is difficult to precipitate the crystalline resin compatibilized with the amorphous resin in the eompatibilization step. On the other hand, when it is a poor solvent for both the amorphous resin and the crystalline resin, the solvent will not be able to penetrate the amorphous resin, and will thus not be able to penetrate the crystalline resin compatibilized with the amorphous resin and induce precipitation of the crystalline resin.

In this invention, a poor solvent is a solvent in which a resin has a solubility of less than 10 g/L at the treatment temperature used in the solvent treatment step. A good solvent is a solvent in which a resin has a solubility of 100 g/L or more at the treatment temperature used in the solvent treatment step.

That is, in this invention a good solvent for the amorphous resin is a solvent in which the amorphous resin has a solubility of 100 g/L or more at the treatment temperature used in the solvent treatment step, and a poor solvent for the crystalline resin is a solvent in which the crystalline resin has a solubility of less than 10 g/L at the treatment temperature used in the solvent treatment step.

The greater the difference between the solubility of the amorphous resin and the solubility of the crystalline resin in the organic solvent the better. When the crystalline resin and the amorphous resin are in a compatibilized state as discussed above, the solubility of the crystalline resin at the treatment temperature used in the solvent treatment step is preferably 5 g/L or less for purposes of precipitating the crystalline resin.

[0022] In this invention, the solubilities of the amorphous resin and the crystalline resin in the organic solvent are calculated by the following method.

A specific mass quantity (1 to 200 g) of the amorphous resin or crystalline resin is added to 1 L of the organic solvent, and agitated for 12 hours at the treatment temperature (25°C for example) of the solvent treatment step, and the solubility is evaluated based on the presence or absence of precipitates or turbidity.

Considering a case in which the organic solvent is added to an aqueous medium containing the compatibilized blend, phase separation of an oil phase may occur in the aqueous medium if the organic solvent has poor water solubility. If the compatibilized blend or the like becomes incorporated into this oil phase, a coarse powder is likely to be produced. Thus, the organic solvent is preferably a hydrophilic solvent. In this invention, a hydrophilic solvent is preferably one having a solubility of 50 g/L or more in water at the treatment temperature used in the solvent treatment step .

[0023] In this invention, specific examples of the organic solvent include, but are not limited to, ethyl acetate, methyl acetate, methyl ethyl ketone and isopropanol. When treating the compatibilized blend with the organic solvent, treatment is preferably performed with thorough agitation so as not to produce coarse particles. Moreover, treatment with the organic solvent is preferably accomplished by dissolving or suspending the organic solvent in an aqueous medium containing a surfactant or the like, and then adding this to a dispersion of the compatibilized blend dispersed in an aqueous medium containing a surfactant or the like.

In this invention, the added amount of the organic solvent in the solvent treatment step cannot be generally specified because it depends on the type of crystalline resin and amorphous resin and the type of organic solvent used. Adding more solvent relative to the resin serves to promote plasticization of the amorphous resin, so that the solvent treatment step can progress rapidly. However, if too much is added the crystalline resin is more likely to dissolve in the organic solvent, and less likely to precipitate. Phase separation of the aforementioned oil phase also becomes more likely, and coarse powder is more likely to occur as a result.

Thus, the added amount of the organic solvent in the solvent treatment step is preferably at least 1 and not more than 500 mass parts, or more preferably at least 5 and not more than 250 mass parts, or still more preferably at least 5 and not more than 150 mass parts per 100 mass parts of the compatibilized blend. When using an organic solvent with poor solubility in water, the added amount of the organic solvent relative to the compatibilized blend can be increased by using ion exchange water or the like to dilute the concentration of the compatibilized blend in an agueous dispersion.

[0024] The temperature for treatment with the organic solvent in the solvent treatment step may be any that causes the crystalline resin contained in the compatibilized blend to have a solubility within the aforementioned range.

At higher treatment temperatures, crystallization of the crystalline resin is induced rapidly as the viscosity of the amorphous resin decreases, but the crystalline resin is more likely to dissolve as it is when more solvent is added, and is thus less likely to precipitate .

In this invention, the temperature for treatment with the organic solvent is preferably a temperature at least 20°C below the melting point of the crystalline resin, or more preferably at least 30°C below the melting point of the crystalline resin, or still more preferably at least 40°C below the melting point of the crystalline resin.

The time of treatment with the organic solvent in the solvent treatment step cannot be generally specified because it depends on the treatment temperature and the added amount of the organic solvent, but generally at least 30 minutes and not more than 10 hours is preferred.

Once the desired crystal phase has separated, the organic solvent can be removed by cooling and pressure reduction to obtain a solvent-treated product. In order to prevent dissolution of the crystalline resin and re-compatibilization of the crystalline resin and the amorphous resin, removal of the organic solvent is preferably performed at a temperature at least 30°C below the melting point of the crystalline resin, or more preferably at least 40°C below the melting point of the crystalline resin, or still more preferably at least 50°C below the melting point of the crystalline resin. A still lower temperature is preferred.

This solvent treatment step may also be performed multiple times in order to form a specific phase- separation structure.

[0025] Structural observation of toner cross-section With the solvent treatment step, the crystalline resin is adequately phase-separated from the amorphous resin, and the crystalline resin is dispersed uniformly as minute domains. This dispersed state can be confirmed by structural observation of a toner cross- section using a transmission electron microscope (TEM) . First, the toner to be observed is dispersed thoroughly in a cold-curing epoxy resin, and then cured for 1 day or more in atmosphere at 40°C to obtain a cured product of enveloped toner.

Next, an ulfrathin film section is cut out of the cured product with a microtome having diamond teeth, and the resulting thin film section is stained with ruthenium tetroxide or osmium tetroxide.

Next, a photograph is taken with a transmission electron microscope (TEM) at a magnification (about lOOOOx) at which a cross-section of one particle of toner appears in the field.

When stained with ruthenium tetroxide or osmium tetroxide, components with different degrees of crystallinity in the toner appear with contrast. It is thus possible to identify domains of the crystalline resin contained in the toner by transmission electron microscopy.

Of the resulting images of toner cross-sections, photographs are taken of 20 toner particle cross- sections having a major axis from 0.9 to 1.2 times the volume-average particle diameter of the toner, and the phase-separation structures of the amorphous resin and crystalline resin and the size and degree of dispersion of the domains formed by the crystalline resin can be measured and analyzed by using an image analysis system (Nireco Corporation, Luzex AP) to analyze the photographed images.

Because in a toner obtained by the method of this invention the crystalline resin is made to precipitate and form domains in the toner by addition of a poor solvent following a compatibilization step, minute needle crystals are formed uniformly in the toner. The major axis of the needle crystals formed by the crystalline resin in the toner is preferably 0.5 um or less, and the smaller the size, the greater the number of boundaries with the amorphous resin, and the greater the plasticization effect in the fixation step. Thus, the major axis of the needle crystals is preferably 0.3 μπϊ or less. If the major axis of the needle crystals exceeds 0.5 μπι, they are likely to be exposed on the toner surface.

[0026] Granulating step

The method of this invention may include a granulating step whereby, particles with a volume- average particle diameter of from 3 μιη to 10 μιτι are obtained. The granulating step is not particularly limited as long as particles with a volume-average particle diameter of from 3 μπι to 10 μια are obtained, and may be performed before the compatibilization step and the solvent treatment step, between the compatibilization step and the solvent treatment step, or after the compatibilization step and the solvent treatment step. The following three embodiments are desirable examples.

[0027] The method for measuring the volume-average particle diameter of the particles (aggregate particles, toner particles, etc.) is as follows.

Using a Coulter Multisizer III (Beckman Coulter, Inc. ) as the measurement unit, measurement is performed in accordance with the operating manual.

The electrolyte solution may be a roughly 1% aqueous sodium chloride solution using primary sodium chloride, but ISOTON-II (Coulter Scientific Japan, Co. Ltd.) may also be used.

The specific measurement methods are as follows.

0.1 to 5 mL of a surfactant (alkyl benzene sulfonate) is added as a dispersing agent to 100 to 150 mL of the electrolyte solution. 2 to 20 mg of a measurement sample (toner particles etc.) is added to the electrolyte solution containing the added dispersing agent.

The electrolyte solution with the sample suspended therein is dispersed for 1 to 3 minutes with an ultrasonic disperser. Using a 100 μπι aperture tube mounted as an aperture on the measurement unit, the volumes of particles with a particle diameter of 2.00 μπι or more are measured in the resulting dispersed solution, and the volume distribution of the particles is calculated. The volume-average particle diameter of the particles (with the median value of each channel given as the typical value for each channel) is determined.

Thirteen channels are used: 2.00 μπι to less than 2.52 μπι; 2.52 μιη to less than 3.17 μτη; 3.17 μπι to less than 4.00 μπι; 4.00 μπι to less than 5.04 μπι; 5.04 μπι to less than 6.35 μm; 6.35 to less than 8.00 μπι; 8.00 μπι to less than 10.08 μπι; 10.08 μm to less than 12.70 μιη; 12.70 μαη to less than 16.00 μπι; 16.00 μπι to less than 20.20 μπι; 20.20 μm to less than 25.40 μπι; 25.40 μπι to less than 32.00 μπι; and 32.00 μm to less than 40.30 μπι.

[0028] (i) Granulating step - Compatibilization step. - Solvent treatment step

That is, the method of this invention is a method for manufacturing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin, comprising

a granulating step of obtaining a particle containing the crystalline resin and the amorphous resin and having a volume-average particle diameter of from 3 μιη to 10 μιτι,

a compatibilization step of compatibilizing the crystalline resin and the amorphous resin in the particle to obtain a compatxbilized blend, and

a solvent treatment step of treating the compatibilized blend in the particle with an organic solvent, wherein the organic solvent is a good solvent for the amorphous resin and a poor solvent for the crystalline resin.

[0029] (ii) Compatibilization step - Granulating step - Solvent treatment step

That is, the method of this invention is a method for manufacturing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin, comprising

a compatibilization step of compatibilizing a crystalline resin and an amorphous resin to obtain a compatibilized blend,

a granulating step of obtaining a particle containing the compatibilized blend and having a volume-average particle diameter of from 3 um to 10 μπι, and

a solvent treatment step of treating the compatibilized blend in the particle with an organic solvent, wherein the organic solvent is a good solvent for the amorphous resin and a poor solvent for the crystalline resin.

[0030] (iii) Compatibilization step - Solvent treatment step - Granulating step

That is, the method of this invention is a method for manufacturing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin, comprising a compatibilization step of compatibilizing a crystalline resin and an amorphous resin to obtain a compatibilized blend,

a solvent treatment step of treating the compatibilized blend with an organic solvent to obtain a solvent-treated product, and

a granulating step of obtaining a particle containing the solvent-treated product and having a volume-average particle diameter of from 3 μπι to 10 μπι, wherein the organic solvent is a good solvent for the amorphous resin and a poor solvent for the crystalline resin .

[0031] When the organic solvent is added in the granulating step, coarse particles may occur as the amorphous resin plasticizes, or it may be difficult to control the particle diameter.

Therefore, when the solvent treatment step is performed before the granulating step, the organic solvent should be thoroughly removed so that there is no residual organic solvent.

When the solvent treatment step is performed after the granulating step, it may be by a dry process or a wet process. In a dry process, the particle obtained in the granulating step are circulated and exposed to an air flow containing a gas of the organic solvent.

In a wet process, the particle obtained in the granulating step is first dispersed by a known method in an aqueous medium containing a surfactant, and the organic solvent is then added.

A wet process is preferred because there is less change in particle size due to addition of the organic solvent.

When the compatibilization step and solvent treatment step are performed before the granulating step as in (iii) above, treatment in the granulating step is preferably performed below the melting point of the crystalline resin so that the crystalline resin and the amorphous resin do not re-compatibilize .

Thus, the solvent treatment step is preferably performed after the granulating step, and more preferably the organic solvent is added with the particle obtained in the granulating step dispersed in an aqueous medium containing a surfactant.

[0032] The compatibilization step, solvent treatment step and granulating step may be accomplished by known toner manufacturing methods such as the suspension polymerization, kneading pulverization, emulsion aggregation and dissolution suspension methods and the like, and are not restricted to any particular method.

Applications of the compatibilization step, solvent treatment step and granulating step using the suspension polymerization, kneading pulverization and emulsion aggregation methods are given here as specific examples, but they are not limited to these. Suspension polymerization method

In the suspension polymerization method, a polymerizable monomer for constituting the amorphous resin is dissolved or dispersed uniformly together with the crystalline resin and other materials such as a colorant, a release agent and the like as necessary to obtain a polymerizable monomer composition. Next, this polymerizable monomer composition is dispersed with a suitable agitator in an aqueous medium containing a dispersion stabilizer as necessary. The polymerizable monomer is then polymerized to obtain particles of the desired particle size (granulating step) . A toner can then be obtained by filtering, washing and drying the resulting particles by known methods. Next, silica, alumina, titania, calcium carbonate and other inorganic fine particles and vinyl resin, polyester resin, silicone resin and other resin fine particles may be added by applying shear force in a dry state. These inorganic fine particles and resin fine particles function as external additives such as flowability aids, cleaning aids.

In the suspension polymerization method, the compatibilization step and solvent treatment step can then be performed after the granulating step.

Kneading pulverization method

In the kneading pulverization method, the constituent resin materials of the toner are thoroughly mixed together with a release agent, colorant and other additives added as necessary, and melt kneaded with a heat roller, kneader or other known thermal kneading machine (kneading step). They are then mechanically pulverized to the desired toner particle size (pulverization step) , and classified to obtain the desired particle size distribution (classification step) , producing the toner.

The toner obtained by kneading pulverization has a distorted shape, with an average circularity of normally less than 0.955. Therefore, a step of heat spheroidizing the toner obtained by kneading pulverization by a known method such as a water dispersion heating method (dispersing and heating the toner in water) or heat treatment method (heating the toner in a hot air flow) may be included as necessary.

[0033] In this kneading pulverization method, the granulating step corresponds to the pulverization step and classification step whereby resin particles with a volume-average particle diameter of from 3 μπι to 10 μπι are obtained.

The granulating step may be performed after the compatibilization step and the solvent treatment step, or between the compatibilization step and the solvent treatment step, or after the compatibilization step and the solvent treatment step. Examples of the various cases are given below. (1) When the granulating step is performed after the compatibilization step and the solvent treatment step, the compatibilization step is a kneading step of heating a resin composition containing the crystalline resin and the amorphous resin to equal to or above the melting point of the crystalline resin, and melting and kneading the resin composition.

In the kneading step, the crystalline resin and the amorphous resin present in the resin component of the toner are compatibilized by heating them to equal to or above the melting point of the crystalline resin to obtain a compatibilized blend.

Next, this compatibilized blend is subjected to a further solvent treatment step by treating it with an organic solvent.

In this solvent treatment step, the compatibilized blend obtained in the compatibilization step can be kneaded again after addition of the organic solvent.

(2) When the granulating step is performed between the compatibilization step and the solvent treatment step, resin particles that have passed through the compatibilization step as well as the pulverization and classification steps (granulating step) may be circulated and exposed to an air flow containing a gas of the organic solvent in the solvent treatment step (dry method) . Alternatively, the resin particles may be dispersed by a known method in an aqueous medium containing a surfactant, and the organic solvent may then be added to the resulting dispersion, and agitated (wet method) .

(3) When the granulating step is performed before the compatibilization step and the solvent treatment step, the compatibilization step is a step of heat spheroidizing a toner obtained via a kneading step, pulverization step and classification step by heating it to equal to or above the melting point of the crystalline resin by a known method, such as water dispersion heating by dispersing and heating the toner in water or heat treatment by heating the toner in a hot air flow.

In this heat spheroidizing step, heating to equal to or above the melting point of the crystalline resin serves to compatibilize the crystalline resin and the amorphous resin in the resin constituting the toner _/ producing a compatibilized blend.

Next, in the solvent treatment step, for example the compatibilized blend obtained by the compatibilization step can be dispersed by known methods in an aqueous medium containing a surfactant to obtain a dispersion, to which the organic solvent is then added and agitated.

[0034] Each step in the kneading pulverization method is explained below.

Kneading step Melt kneading of the constituent materials of the toner can be accomplished using a known thermal kneading machine such as a heating roller and a kneader. In this kneading step, the constituent materials of the toner are preferably mixed thoroughly in advance with a mixer.

The mixer may be a HENSCHEL MIXER (Mitsui Mining Co., Ltd.), a super mixer (KAWATA MFG Co., Ltd.), a Ribocone (OKAWARA MFG. CO., LTD.), a Nauta Mixer, Turbulizer or Cyclomix (Hosokawa Micron) , a spiral pin mixer (Pacific Machinery & Engineering Co., Ltd), or a Loedige mixer (MATSUBO Corporation) .

The thermal kneading machine may be a KRC kneader (KURIMOTO, LTD.), a Buss Ko-Kneader (Buss Corp.), a TEM extruder (TOSHIBA MACHINE CO., LTD), a TEX biaxial kneader (Japan Steel Works, LTD.), a PCM kneader (Ikegai) , a triple roll mill, mixing roll mill or kneader (INOUE MFG., INC.), a Kneadex (Mitsui Mining Co., Ltd.), an MS pressure kneader or kneader-ruder (Moriyama) , or a Banbury Mixer (KOBE STEEL, LTD.).

Pulverization step

The pulverization step is a step of first cooling the kneaded product obtained in the kneading step until it is hard enough to pulverize, and mechanically pulverizing the kneaded product to the particle size of the toner with a known pulverizing machine such as a target plate jet mill, fluidized-bed jet mill, rotary mechanical mill and the like. From the standpoint of pulverizing efficiency, it is desirable to use a fluidized-bed jet mill as the pulverizing machine.

The pulverizing machine may be a counter jet mill, micron jet or Inomizer (Hosokawa Micron), an IDS mill or PJM jet pulverizer (Nippon Pneumatic Mfg. Co., Ltd.), a Cross Jet Mill (KURIMOTO, LTD.), an Ulmax (NISSO ENGINEERING CO., LTD), an SK Jet-O-Mill (SEISHIN ENTERPRISE Co., Ltd.), a Kryptron (Kawasaki Heavy Industries, Ltd.), a Turbo Mill (FREUND TURBO), or a Super Rotor (Nisshin Engineering Inc.) or the like.

Classification Step

The classification step is a step of classifying the finely pulverized product obtained in the pulverization step to obtain a toner having a desired particle size distribution.

A known device such as an air classifier, inertial classifier or sieve classifier may be used as the classifier for classification. Specific examples include the Classiel, Micron Classifier and Spedic Classifier (SEISHIN ENTERPRISE Co., Ltd.), the Turbo Classifier (Nisshin Engineering Inc.), the Micron Separator and Turboplex (ATP) , the TSP Separator (Hosokawa Micron), the Elbow Jet (Nittetsu Mining Co., Ltd.), the Dispersion Separator (Nippon Pneumatic Mfg. Co., Ltd.) and the YM Microcut (Yasukawa Shoji). Silica, alumina, titania, calcium carbonate and other inorganic fine particles and vinyl resin, polyester resin, silicone resin and other resin fine particles may be added as necessary to a toner prepared via these steps by applying shear force in a dry state. These inorganic fine particles and resin fine particles function as external additives such as flowability aids and cleaning aids.

[0035] ^' Emulsion aggregation method

The emulsion aggregation method is a method for preparing a toner by first preparing an aqueous dispersion of fine particles consisting of the constituent materials of the toner that are sufficiently small relative to the target particle size, aggregating those fine particles in an aqueous medium until the particle size of the toner is achieved, and then heating to fuse the resin.

That is, in the emulsion aggregation method, a toner is manufactured via a ^' dispersion step of preparing a dispersion of fine particles consisting of the constituent materials of the toner, an aggregation step of aggregating fine particles consisting of the constituent materials of the toner and controlling the particle size until the particle size of the toner is achieved, a fusion step of fusing the resin contained in the resulting aggregate particles, and a subsequent cooling step. In the emulsion aggregation method, the aforementioned granulating step is the aggregation step, which yields resin particles with a volume-average particle diameter of from 3 μπι to 10 μπι.

The granulating step (aggregation step) may be performed either after the compatibilization step and solvent treatment step, or between the compatibilization step and the solvent treatment step, or before the compatibilization step and the solvent treatment step. Examples of these various cases are given below.

(1) When the granulating step (aggregation step) is performed either after the compatibilization step and solvent treatment step or between the compatibilization step and the solvent treatment step

The compatibilization step is a step of dissolving the crystalline resin and the amorphous resin in an organic solvent capable of dissolving the crystalline resin and the amorphous resin, and mixing them using a dispersant in a known agitator, emulsifier, disperser or other mixing device to obtain a compatibilized blend (composite fine particles) in which the crystalline resin and the amorphous resin are compatibilized together (this step doubles as an emulsification step) .

Dissolving the crystalline resin and the amorphous resin in an organic solvent capable of dissolving the crystalline resin and the amorphous resin induces compatibilization of the crystalline resin and the amorphous resin, and then uniformly disperses the crystalline resin in the resulting composite fine particles .

In the solvent treatment step, the organic solvent, which a good solvent for the amorphous resin and a poor solvent for the crystalline resin, is added and agitated in a dispersion obtained by dispersing the compatibilized blend (composite fine particles) by known methods in an aqueous medium containing a surfactant.

When the granulating step (aggregation step) is performed after the compatibilization step and the solvent treatment step, the granulating step (aggregation step) and fusion step may be performed, below the melting point of the crystalline resin so that the crystalline resin and the amorphous resin are not re-compatibilized in the subsequent steps.

The specific organic solvent added in the solvent treatment step should be thoroughly removed because coarse particles are likely to occur in the subsequent granulating step (aggregation step) and fusion step if there is residual organic solvent in an aqueous dispersion containing the composite fine particles.

(2) When the granulating step (aggregation step) is performed before the compatibilization step and the solvent treatment step The compatibilization step is a fusion step of heating and fusing aggregate particles with the toner particle diameter obtained by aggregating fine particles of the crystalline resin with fine particles of the amorphous resin, at equal to or above the melting point of the crystalline resin. Heating to equal to or above the melting point of the crystalline resin in the fusion step produces a compatibilized blend in which the crystalline resin and the amorphous resin in the aggregate particles are compatibilized together.

An aqueous dispersion containing the compatibilized blend is then added to the organic solvent and agitated in the subsequent solvent treatment step.

[0036] The various steps of the emulsion aggregation method are explained further below.

Dispersion step

An aqueous dispersion of fine particles of the amorphous resin and crystalline resin may be prepared by known methods, but the techniques are not particularly limited. Examples of known methods include emulsion polymerization, self-emulsification, phase inversion emulsification in which a resin is emulsified by adding an aqueous medium to a solution of the resin dissolved in an organic solvent, and forced emulsification in which a resin is forcibly emulsified by high-temperature treatment in an aqueous medium, without an organic solvent.

Specifically, the amorphous resin and crystalline resin are dissolved in an organic solvent that dissolves both, and a surfactant or basic compound is added. Next, this is agitated with a homogenizer or the like as an aqueous medium is gradually added to thereby precipitate resin fine particles. Subsequently, the solvent is removed by heating or pressure reduction to prepare an aqueous dispersion of resin fine particles. The organic solvent used to dissolve the resin may be any capable of dissolving the resin, but an organic solvent such as tetrahydrofuran that forms a homogenous phase with water is preferred for suppressing the occurrence of coarse powder.

The surfactant used during this emulsification is not particularly limited, but examples include sulfuric acid ester salts, sulfonic acid salts, carboxylic acid salts, phosphate esters, soaps and other anionic surfactants; amine salts, quaternary ammonium salts and other cationic surfactants; and polyethylene glycols, alkyl phenol ethylene oxide adducts, polyvalent alcohols and other nonionic surfactants and the like. One kind of surfactant may be used alone, or two or more may be combined.

Examples of the basic compound used during this emulsification include sodium hydroxide, potassium hydroxide and other inorganic bases; and ammonia, triethylamine, trimethylamine, dimethylamino ethanol, diethylamino ethanol and other organic bases. One kind of base may be used alone, or two or more may be combined .

The 50% particle diameter on a volume basis (d50) of the fine particles of the amorphous resin is preferably from 0.05 to 1.0 μιτι, or more preferably from 0.05 to 0.4 μπι.

Keeping the 50% particle diameter on a volume basis (d50) within this range makes it easy to obtain toner particles with a volume-average particle diameter of from 3 μπι to 10 μτη, suitable for toner particles.

The 50% particle diameter on a volume basis (d50) of the fine particles of the crystalline resin is preferably from 0.05 to 0.5 μπι or more preferably from 0.05 to 0.3 μπι from the standpoint of controlling the occurrence of coarse particles in the aggregation step.

The 50% particle diameter on a volume basis (d50) can be measured using a dynamic light scattering particle size distribution analyzer (Nanotrac UPA- EX150: NIKKISO CO., LTD.) .

[0037] An aqueous dispersion of colorant fine particles is used as necessary, and can be prepared by the known methods described below, but preparation is not limited to these methods. This is prepared by mixing a colorant, an aqueous medium and a dispersing agent in a known agitator, emulsifier, disperser or other mixer. Known dispersing agents such as surfactants and polymeric dispersing agents may be used as the dispersing agent in this case.

Both surfactants and polymeric dispersing agents can be removed in the subsequent washing step, but a surfactant is preferred from the standpoint of washing efficiency.

Examples of surfactants include sulfuric acid ester salts, sulfonic acid salts, phosphate esters, soaps and other anionic surfactants; amine salts, quaternary ammonium salts and other cationic surfactants; and polyethylene glycols, alkyl phenol ethylene oxide adducts, polyvalent alcohols and other nonionic surfactants.

Of these, a nonionic surfactant or anionic surfactant is preferred. A combination of a nonionic surfactant and an anionic surfactant may also be used. One kind of surfactant may be used, or a combination of two or more may be used. The concentration of the surfactant in the aqueous medium may be from 0.5 to 5 mass%.

The content of the colorant fine particles in the aqueous dispersion is not particularly limited, but is preferably from 1 to 30 mass% of colorant fine particles relative to the total mass of the aqueous dispersion.

Regarding the dispersed particle size of the colorant fine particles in the aqueous dispersion, a 50% particle diameter on a volume basis (d50) of 0.5 μτ or less is preferred from the standpoint of dispersib.ility of the colorant in the final toner. For similar reasons, the 90% particle diameter on a volume basis (d90) is preferably 2 μπι or less. The dispersed particle size of colorant fine particles dispersed in an aqueous medium is measured with a dynamic light scattering particle size distribution analyzer (Nanotrac UPA-EX150: NIKKISO CO., LTD.).

Examples of the known agitator, emulsifier, disperser or other mixer used for dispersing the colorant in the aqueous medium include ultrasonic homogenizers , jet mills, pressure homogenizers, colloid mills, ball mills, sand mills and paint shakers. These may be used alone or in combination.

[0038] An aqueous dispersion of release agent fine particles is used as necessary, and may be prepared by the known methods described below, but the methods are not limited to these.

An aqueous dispersion of release agent fine particles can be prepared by adding a release agent to an aqueous medium containing a surfactant, and heating to equal to or above the melting point of the release agent while dispersing it in particle form with a homogenizer capable of applying strong shear force (for example, M Technique Co., Ltd. Clearmix - otion) or a pressure discharge disperser (for example, a Gaulin Co. Gaulin Homogenizer), and then cooling to below the melting point.

Regarding the dispersed particle size of the release agent fine particles in the aqueous dispersion, the 50% particle diameter on a volume basis (d50) is preferably from 0.03 to 1.0 |im, or more preferably from 0.1 to 0.5 jam. Preferably no coarse particles of 1 μπι or more are present.

When the dispersed particle size of the release agent fine particles is within this range, the release agent has good elution during fixing, the hot offset temperature can be raised, and filming on the photosensitive member can be repressed. The dispersed particle size of the release agent fine particles in the aqueous medium can be measured with a dynamic light scattering particle size distribution analyzer (Nanotrac UPA-EX150: NIKKISO CO., LTD.).

[0039] Aggregation step

In the aggregation step, an aqueous dispersion of the amorphous resin fine particles and an aqueous dispersion of the crystalline resin fine particles are mixed together with an aqueous dispersion of release agent fine particles and an aqueous dispersion of colorant fine particles as necessary, to prepare a liquid mixture. Next, the fine particles contained in the resulting liquid mixture are aggregated to form aggregate particles of the desired particle diameter. An aggregating agent is added and mixed, and appropriate heat and/or mechanical force is applied as necessary during this process to form aggregate particles by aggregating the resin fine particles, colorant fine particles and release agent fine particles.

An aggregating agent containing bivalent or higher metal ions is preferably used as the aggregating agent. An aggregating agent containing bivalent or higher metal ions has strong aggregating force, and a small added amount can ionically neutralize the acidic polar groups of the resin fine particles and the ionic surfactant contained in the aqueous dispersions of resin fine particles, aqueous dispersion of colorant fine particles and aqueous dispersion of release agent fine particles. As a result, the resin fine particles, colorant fine particles and release agent fine particles are aggregated by the effects of salting-out and ion cross-linkage.

Examples of aggregating agents containing bivalent or higher metal ions include bivalent and higher metals salts and polymers of metal salts. Specific examples include, but are not limited to, calcium chloride, calcium nitrate, magnesium chloride, magnesium sulfate, zinc chloride and other bivalent inorganic metal salts, iron chloride (III), iron sulfate (III), aluminum sulfate, aluminum chloride and other trivalent metal salts, and polyaluminum chloride, polyaluminum hydroxide, calcium polysulfide and other inorganic metal salt polymers. One kind may be used alone, or two or more may be combined.

The aggregating agent may be added either as a dry powder or as an aqueous solution dissolved in an aqueous medium, but for purposes of achieving uniform aggregation, an aqueous solution is preferred.

The aggregating agent is preferably added and mixed at a temperature no greater than the glass transition temperature of the resin contained in the liquid mixture. Uniform aggregation is promoted by mixing under these temperature conditions . The aggregating agent may be mixed into the liquid mixture using a homogenizer, mixer or other known mixing apparatus .

As discussed above, the average particle diameter of the aggregate particles formed in the aggregation step is preferably controlled to a volume-average particle diameter of from 3 μπι to 10 μπι. The particle diameter of the aggregate particles can be easily controlled by appropriately adjusting the temperature, the solids concentration, the concentration of the aggregating agent and the agitation conditions.

Toner particles having a core-shell structure can be manufactured by including a shell attachment step of further adding resin fine particles for forming a shell phase to the liquid dispersion of aggregate particles obtained in the aggregation step, and attaching the resin fine particles to the surface of the aggregate particles, after which the aggregate particles with the resin fine particles attached to the surface are fused in the subsequent fusion step (discussed below). The resin fine particles added here for forming a shell phase may be resin particles having the same structure as a resin contained in the aggregate particles, or resin particles having a different structure.

[0040] Fusion step

In the fusion step, an aggregation terminator is added under the same agitation used in the aggregation step to a liquid dispersion containing the aggregate particles obtained in the aggregation step. Examples of the aggregation terminator include a basic compound that stabilizes the aggregate particles by shifting the equilibrium of the acidic polar groups in the resin fine particles towards dissociation; and a chelating agent that stabilizes the aggregate particles by partially dissociating the ion crosslinkages between the acidic polar groups of the resin fine particles and the metal ions of the aggregating agent, forming coordinate bonds with the metal ions. Of these, chelating agents are preferred for their stronger aggregation terminating effects.

Once the dispersion state of the aggregate particles in the liquid dispersion has been stabilized by the action of the aggregation terminator, the dispersion is heated to equal to or above the glass transition temperature of the amorphous resin to fuse the aggregate particles.

When the compatibilization step is performed at the same time as the fusion step, heating is performed to equal to or above the melting point of the crystalline resin to fuse the aggregate particles.

Moreover, when the fusion step is performed after the compatibilization step and the solvent treatment step as discussed above, heating can be performed below the melting point of the crystalline resin so that the crystalline resin and the amorphous resin do not re- compatibilize .

The chelating agent may be a known water-soluble chelating agent, without any particular limitations. Specific examples include tartaric acid, citric acid, gluconic acid and other oxycarboxylic acids and sodium salts of these; and iminodiacetic acid (IDA), nitrilotriacetic acid (NTA) , ethylenediamine tetraacetic acid (EDTA) and sodium salts of these. By coordinating the metal ions of the aggregating agent present in the liquid dispersion of aggregate particles, the chelating agent changes the environment in the liquid dispersion from a statically unstable, aggregation-prone state to a statically stable state resistant to further aggregation. It is thus possible to prevent further aggregation of the aggregate particles in the dispersion, stabilizing the aggregate particles.

In order to be effective even when a smal-1 amount is added and produce toner particles with a sharp particle size distribution, the chelating agent is preferably an organic metal salt having a trivalent or higher carboxylic acid.

From the standpoint of achieving both washing efficiency and stabilization from an aggregated state, the added amount of the chelating agent is preferably from 1 to 30 mass parts or more preferably from 2.5 to 15 mass parts per 100 mass parts of the resin particles.

Toner particles can be obtained by washing, filtering and drying the resin particles prepared via this fusion step. After this, silica, alumina, titania, calcium carbonate and other inorganic fine particles and vinyl resin, polyester resin, silicone resin and other resin fine particles may be added by application of shear force in a dry state, as necessary. These inorganic fine particles and resin fine particles function as external additives such as flowability aids and cleaning aides.

[0041] Next, the constituent materials of this invention are explained.

Crystalline resin

The crystalline resin of the present invention is not particularly limited as long as it has crystallinity and is compatible with the amorphous resin, and may be selected appropriately according to the object.

The crystalline resin exhibits a melting endothermic peak in differential scanning calorimetric measurement using a differential scanning calorimeter (DSC) .

Examples of the crystalline resin include crystalline polyester resin, crystalline polyurethane resin, crystalline polyurea resin, crystalline polyamide resin, crystalline polyether resin, crystalline vinyl resin and modified crystalline resin. One of these alone or a combination of two or more may be used.

Of these, a crystalline polyester resin is preferred from the standpoint of melting point and mechanical strength. The structure of this crystalline polyester resin is not particularly limited, but examples include structures obtained by condensation polymerization of at least one kind of dicarboxylic acid component with at least one kind of diol component. The following are specific examples of the diol, and a C ₄ ~2o linear aliphatic diol is preferred from the standpoint of melting point and ester group concentration: ethylene glycol, 1 , 3-propanediol , 1,4- butanediol, 1 , 5-pentanediol , 1 , 6-hexanediol , 1,7- heptanediol, 1, 8-octanediol, 1 , 9-nonanediol , 1,10- decanediol, 1, 11-undecanediol, 1, 12-dodecanediol, 1,13- tridecanediol, 1, 14-tetradecanediol, 1,18- octadecanediol, 1 , 20-icosanediol , 2-methyl-l , 3- propanediol, cyclohexanediol , cyclohexanedimethanol and other diols. These may be used alone, or two or more may be combined.

A trivalent or higher alcohol may also be used, and examples include glycerine, pentaerythritol, hexamethylol melamine and hexaethylol melamine. These may be used alone, or two or more may be combined.

The following are specific examples of the dicarboxylic acid, and a Ci~2o linear aliphatic dicarboxylic acid is preferred from the standpoint of melting point and ester group concentration as discussed below: oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1 , 9-nonanedicarboxylic acid, 1,10- decanedicarboxylic acid, 1 , 11-undecanedicarboxylic acid, 1, 12-dodecanedicarboxylic acid, 1, 13- tridecanedicarboxylic acid, 1,14- tetradecanedicarboxylic acid, 1, 16- hexadecanedicarboxylic acid, 1, 18- octadecanedicarboxylic acid; 1,1- cyclopentenedicarboxylic acid, 1,4- cyclohexanedicarboxylic acid, 1,3- cyclohexanedicarboxylic acid, 1,3- adamantanedicarboxylic acid and other alicyclic dicarboxylic acids; and phthalic acid, isophthalic acid, terephthalic acid, p-phenylenediacetic acid, m- phenylenediacetic acid, p-phenylenedipropionic acid, m- phenylenedipropionic acid, naphthalene-1 , 4-dicarboxylic acid, naphthalene-1 , 5-dicarboxylic acid and other aromatic dicarboxylic acids. These may be used alone, or two or more may be combined.

A trivalent or higher polyvalent carboxylic acid may also be used, and examples include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid and other trivalent and higher polyvalent carboxylic acids. These may be used alone, or two or more may be combined.

[0042] As discussed above, in general crystalline resins are known to have low volume resistance in comparison with conventional amorphous resins. The inventors believe that the reasons for this are as follows .

Crystalline resins in general form crystal structures exhibiting regular arrangements of molecular chains, and from a macro perspective, appear to maintain a state of restricted molecular movement at temperatures below the melting point. However, crystalline resins are not composed entirely of crystalline structures on a micro scale, and instead form amorphous structural parts in addition to crystalline structural parts having crystalline structures exhibiting regular arrangements of molecular chains.

In the case of a crystalline polyester resin having a melting point range normally used for toner, because the glass transition temperature (Tg) of the crystalline polyester resin is much lower than room temperature, it is thought that the amorphous structural parts cause molecular movement on a micro scale even at room temperature. It is thought that in such environments with high molecular mobility of the resin, charge acceptance is possible via ester bonds that are polar groups and the like, and that the volume resistance of the resin is reduced as a result.

Consequently, a crystalline polyester resin with a low ester group concentration is preferred because it may allow volume resistance to be increased by limiting the concentration of ester groups that are polar groups to a low level.

The value of the ester group concentration is determined primarily by the type of diol component and dicarboxylic acid component, and a low value can be designed by selecting those with large numbers of carbon atoms. However, keeping the ester group concentration low may detract from compatibility with the amorphous resin (discussed below) , or raise the melting point of the resulting crystalline polyester resin.

[0043] The weight-average molecular weight ( w) of the crystalline resin as measured by gel permeation chromatography (GPC) is preferably from 5000 to 50000, or more preferably from 5000 to 20000.

The strength and low-temperature fixability of the resin in the toner can be further improved by keeping the weight-average molecular weight (Mw) of the crystalline resin within this range.

The weight-average molecular weight (Mw) of the crystalline resin can be easily controlled by controlling various known manufacturing conditions for the crystalline resin.

Moreover, the weight-average molecular weight (Mw) of the crystalline resin can be measured as follows by gel permeation chromatography (GPC) . Special grade 2 , 6-di-t-butyl-4-methylphenol (BHT). is added to a concentration of 0.10 mass% to o- dichlorobenzene for gel chromatography, and dissolved at room temperature. The crystalline resin and the o- dichlorobenzene with the added BHT are placed in a sample bottle, and heated on a hot plate set to 150°C to dissolve the crystalline resin.

Once the crystalline resin has dissolved, this is placed in a pre-heated filter unit, and set on the apparatus. The sample that passes through the filter unit is used as the GPC sample.

The sample solution is adjusted to a concentration of about 0.15 mass%.

Measurement is performed under the following conditions using the sample solution.

Apparatus: HLC-8121GPC/HT (TOSOH CORPORATION)

Detector: High-temperature RI

Column: TSKgel GMHHR-H HT, series of 2

(TOSOH CORPORATION)

Temperature: 135.0°C

Solvent: o-dichlorobenzene for gel chromatography (0.10 mass% BHT added)

Flow rate: 1.0 ml/min.

Injected amount: 0.4 ml

A molecular weight calibration curve prepared using standard polystyrene resins (TOSOH CORPORATION, trademark TSK™ standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-1.0, F-4, F-2, F-l, A-5000, A-2500, A-1000, A-500) is used for calculating the molecular weight of the crystalline resin.

[0044] In this invention, the melting point of the crystalline resin is preferably from 50°C to 100°C from the standpoint of low-temperature fixability and storability. Low-temperature fixability is improved with a melting point of 100°C or less, and further improved with a melting point of 90°C or less. Conversely, the storability tends to be poorer when the melting point is less than 50°C.

[0045] The melting point of the crystalline resin can be measured with a differential scanning calorimeter (DSC) .

Specifically, from 0.01 to 0.02 g of sample is accurately weighed into an aluminum pan, the temperature is raised from 0°C to 200°C at a ramp rate of 10°C/min, and a DSC curve is obtained.

The peak temperature of the melting endothermic peak is given as the melting point based on the resulting DSC curve.

The melting point of the crystalline resin in the toner can also be measured by the same method. In this case, a melting point attributable to the release agent in the toner may also be observed. The melting point of the release agent is distinguished from the melting point of the crystalline resin by extracting the release agent from the toner by Soxhlet extraction using a hexane solvent, performing differential scanning calorimetric measurement on the release agent alone by the same methods, and comparing this melting point with the melting point of the toner.

[0046] In this invention, the toner preferably contains from 10 massl to 40 massl of crystalline resin. Better low-temperature fixability is obtained when the toner contains at least 10 mass% of crystalline resin. That is, both low-temperature fixability and charging performance can be obtained at a high level when the toner contains from 10 mass% to 40 mass% of crystalline resin .

[0047] Amorphous resin

In this invention, the amorphous resin is not particularly limited as long as it is compatible with the crystalline resin, and a known resin normally used in toners can be selected appropriately.

Specific examples include the following polymers or resins: single polymers of styrene or substituted styrene such as polystyrene, poly-p-chlorstyrene, polyvinyltoluene; styrene-p-chlorstyrene copolymer, styrene-vinyltoluene copolymer, styrene- vinylnaphthaline copolymer, styrene-acrylate ester copolymer, styrene-methacrylate ester copolymer, styrene-methyl -chloroacrylate copolymer, styrene- acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene- acrylonitrile-indene copolymer and other styrene copolymers; and polyvinyl chloride, phenolic resin, modified phenolic resin, modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum resins and the like.

Of these, a polyester resin is preferred because it is highly compatible with crystalline polyesters, which are crystalline resins having preferred structures, and because it is strong even at low molecular weights.

A resin obtained by condensation polymerization of an alcohol monomer and a carboxylic acid monomer is used as the polyester resin.

The following alcohol monomers may be used: polyoxypropylene (2.2) -2, 2-bis (4-hydroxyphenyl) ropane, polyoxypropylene (3.3) -2, 2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2, 2-bis (4-hydroxyphenyl ) propane, polyoxypropylene (2,0) -polyoxyethylene (2 , 0) -2, 2-bis (4- hydroxyphenyl) propane, polyoxypropylene (6) -2, 2-bis (4- hydroxyphenyl) propane and other bisphenol A alkylene oxide adducts; ethylene glycol, diethylene glycol, triethylene glycol, 1 , 2-propylene glycol, 1 , 3-propylene glycol, 1 , 4-butanediol , neopentyl glycol, 1,4- butenediol, 1, 5-pentanediol, 1, 6-hexanediol, 1,4- cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, sorbitol, 1, 2, 3, 6-hexanetetrole, 1, -sorbitan, pentaerythritol , dipentaerythritol, tripentaerythritol, 1,2,4- butanetriol, 1, 2, 5-pentanetriol, glycerol, 2- methylpropanetriol, 2-methyl-l, 2, 4-butanetriol, trimethylol ethane, trimethylol propane and 1,3,5- trihydroxymethyl benzene.

The following are examples of carboxylic acid monomers: phthalic acid, isophthalic acid, terephthalic acid and other aromatic dicarboxylic acids or anhydrides thereof; succinic acid, adipic acid, sebacic acid, azelaic acid and other alkyldicarboxylic acids or anhydrides thereof; succinic acid and anhydrides of succinic acid substituted with C6~i8 alkyl or alkenyl groups; and fumaric acid, maleic acid, citraconic acid and other unsaturated dicarboxylic acids or anhydrides thereof .

The following monomers may also be used: polyvalent alcohols including oxyalkylene ethers of Novolac phenolic resin; and trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and anhydrides thereof and other polyvalent carboxylic acids .

Of these, especially preferred is a resin obtained by condensation polymerization of the bisphenol derivative represented by General Formula (1) below as a bivalent alcohol monomer component with a carboxylic acid component consisting of a bivalent or higher carboxylic acid or acid anhydride or lower alkyl ester thereof (for example, fumaric acid, maleic acid, anhydrous maleic acid, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as a carboxylic acid monomer component.

[0048]

[Chem.l]

(wherein R represents an ethylene group or pyropyrene group, each of x and y is an integer of 1 or greater, and the average Of x + y is from 2 to 10)

[0049] The glass transition temperature of the amorphous resin is preferably from 30°C to 80°C. The storability is improved when the glass transition temperature is 30°C or greater. This also improves the charging performance by making it less likely that resistance will be reduced due to molecular movement of the resin in high-temperature, high-humidity environment.

On the other hand, low-temperature fixability is improved when the glass transition temperature is 80°C or less.

A glass transition temperature of at least 40°C is more preferred for improving the storability. Also, a glass transition temperature of 70°C or less is more preferred for improving the low-temperature fixability.

The glass transition temperature (Tg) can be measured using a differential scanning calorimeter (Mettler-Toledo International Inc. DSC822/EK90) .

Specifically, from 0.01 to 0.02 g of sample is accurately weighed into an aluminum pan, and the temperature is raised from 0°C to 200°C at a ramp rate of 10°C/min. Next, the temperature is lowered from 200°C to -100°C at a rate of 10°C/min, and then raised again from -100°C to 200°C at a ramp rate of 10°C/min, and a DSC curve is obtained.

Based on the resulting DSC curve, the glass transition temperature is the temperature at the intersection on the resulting DSC curve a line extending the low-temperature base line to the high- temperature side and a line drawn at the point tangential to the slope of the curve at the portion of the curve where glass transition temperature changes. in steps reaches a maximum. [0050] In this invention, the softening temperature (Tm) of the amorphous resin is preferably from 70°C to 150°C, or more preferably from 80°C to 140°C, or still more preferably from 80°C to 130°C.

With a softening temperature (Tm) within this temperature range, it is possible to achieve both good blocking resistance and offset resistance, with an appropriate degree of penetration of the paper by the melted toner part during fixing at high temperatures, and good surface smoothness.

In this invention, the softening temperature (Tm) of the amorphous resin can be measured with a constant load extrusion-type capillary rheometer (flow characteristics evaluating device, CFT-500D flow tester, Shimadzu Corporation) .

The CFT-500D is a device that exerts a constant load with a piston from above while heating and melting a measurement sample filled in a cylinder and extruding it through capillaries at the bottom of a cylinder, and can then graph a rheogram based on the descent (mm) of the piston and the temperature (°C) during this process.

In this invention, "melting temperature by the 1/2 method" stated in the attached manual of the flow characteristics evaluating device, CFT-500D flow tester is defined as the softening temperature (Tm) .

The melting temperature by the 1/2 method is calculated as follows. 1/2 of the difference between the descent of the piston when outflow is complete (outflow completion point, called Smax) and the descent of the piston at the beginning of outflow (lowest point, Smin) is determined and given as X (X = (Smax - Smin)/2) . The temperature of the rheogram when the descent of the piston reaches the sum of X and Smin is then given as the melting temperature by the 1/2 method.

For the measurement sample, 1.2 g of amorphous resin is compression molded for 60 seconds at 10 MPa in an environment of 25°C with a tablet molding compressor (for example, a standard manual Newton Press NT-100H, NPa SYSTEM CO., LTD.) into a cylinder 8 mm in diameter.

The specific operations for measurement are performed in accordance with the attached manual.

The CFT-500D measurement conditions are as follows.

Test mode: Temperature raising method

Initiation temperature: 60°C

Saturated temperature: 200°C

Measurement interval: 1.0°C

Ramp rate: 4.0°C/min.

Piston cross-section: 1.000 cm ²

Test load (piston load): 5.0 kgf

Pre-heating time: 300 seconds

Die hole diameter: 1.0 mm

Die length: 1.0 mm [0051] The amorphous resin preferably has ionic groups, namely carboxylic acid groups, sulfonic acid groups or amino groups, in the resin skeleton, and more preferably has carboxylic acid groups.

The acid value of the amorphous resin is preferably from 3 to 35 mg KOH/g, or more preferably from 8 to 25 mg KOH/g.

A good charge quantity can be obtained under both high-humidity and low-humidity environments when the acid value of the amorphous resin is within this range. The acid value is the number of milligrams of potassium hydroxide required to neutralize the free fatty acids, resins acids and the like contained in 1 g of sample, and is measured in accordance with JIS-K0070.

[0052] In this invention, the crystalline resin and the amorphous resin are a compatible combination. The following are considered when selecting a compatible combination of crystalline resin and amorphous resin.

(1) Select a crystalline resin and an amorphous resin with the same resin skeleton.

For example, use a crystalline polyester resin as the crystalline resin and an amorphous polyester resin as the amorphous resin, or else a crystalline acrylic resin as the crystalline resin and an amorphous acrylic resin as the amorphous resin.

(2) The absolute value (ASP value) of the difference between the solubility parameter values (SP values) of the crystalline resin and the amorphous resin used is preferably from 0.00 to 1.70, or more preferably from 0.00 to 1.65, or still more preferably from 0.00 to 1.60.

The SP value can be determined using the Fedors formula. The evaporation energies and molar volumes (25°C) for atoms and atom groups according to "Table 3- 9" of "Basic Science of Coating" pp. 54-57, 1986 (Maki

Shoten) were consulted with respect to the Aei and Δνί values .

Formula: 6i = [Ev/V] ^1/2 = [Aei/Avi] ^{1 2}

Ev: Evaporation energy

V: Molar volume

Aei: Evaporation energy of atoms or atom groups of i component

Δνϊ : Molar volume of atoms or atom groups of i component

For example, a crystalline polyester formed from nonanediol and sebacic acid consists of the atom groups (-COO) x 2 + (-CH ₂ ) x 17 as repeating units, and the calculated SP value is determined by the following formula:

5i = [Aei/Avi] ¹⁷² = [{(4300) x 2 + (1180) x 17}/{(18) x 2 + (16.1) x 17}] ^1/2 .

The SP value (δί) is thus 9.63.

In this invention, the ratio of the crystalline resin to the amorphous resin by mass is preferably 5:95 to 50:50, or more preferably 10:90 to 40:60, or still more preferably 15:85 to 30:70.

[0053] Colorant

Examples of the colorant include known organic pigments or dyes, carbon black, magnetic powders and the like.

Examples of cyan colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds and basic dye lake compounds. Specific examples include C.I. pigment blue 1, C.I. pigment blue 7, C.I. pigment blue 15, C.I. pigment blue 15:1, C.I. pigment blue 15:2, C.I. pigment blue 15:3, C.I. pigment blue 15:4, C.I. pigment blue 60, C.I. pigment blue 62 and C.I. pigment blue 66.

Examples of magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and peryline compounds. Specific examples include C.I. pigment red 2, C.I. pigment red 3, C.I. pigment red 5, C.I. pigment red 6, C.I. pigment red 7, C.I. pigment violet 19, C.I. pigment red 23, C.I. pigment red 48:2, C.I. pigment red 48:3, C.I. pigment red 48:4, C.I. pigment red 57:1, C.I. pigment red 81:1, C.I. pigment red 122, C.I. pigment red 144, C.I. pigment red 146, C.I. pigment red 166, C.I. pigment red 169, C.I. pigment red 177, C.I. pigment red 184, C.I. pigment red 185, C.I. pigment red 202, C.I. pigment red 206, C.I. pigment red 220, C.I. pigment red 221 and C.I. pigment red 254.

Examples of yellow colorants include condensed azo compound, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamido compounds. Specific examples include C.I. pigment yellow 12, C.I. pigment yellow 13, C.I. pigment yellow 14, C.I. pigment yellow 15, C.I. pigment yellow 17, C.I. pigment yellow 62, C.I. pigment yellow 74, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 94, C.I. pigment yellow 95, C.I. pigment yellow

97, C.I . pigment yellow 109, C.I. pigment yellow 110,

C.I. pigment yellow in, C.I. pigment yellow 120, C. I. pigment yellow 127, C. I . pigment yellow 128, C. I. pigment yellow 129, C. I . pigment yellow 147, C. I. pigment yellow 151, C. I. pigment yellow 154, C. I. pigment yellow 155, C. I . pigment yellow 168, C. I. pigment yellow 174, C. I. pigment yellow 175, C. I. pigment yellow 176, C. I . pigment yellow 180, C. I. pigment yellow 1 81, C.I . pigment yellow 191 and C. I . pigment yellow 194.

Examples of black colorants include carbon black, magnetic powders, and blacks blended from yellow colorants, magenta colorants and cyan colorants.

These colorants can be used alone, or mixed, or used in a solid solution. The hue angle, chroma, lightness, lightfastness , OHP transparency, and dispersibility in the toner may be considered in selecting the colorant.

The content of the colorant is preferably from 1 to 20 mass parts per 100 mass parts of the resin component of the toner.

[0054] Release agent

Examples of the release agent include polyethylene and other low-molecular-weight polyolefins; silicones having melting points (softening points) under heating; oleic acid amides, erucic acid amides, ricinoleic acid amides, stearic acid amides and other fatty acid amides; stearyl stearate and other ester waxes; carnuba wax, rice wax, candelilla wax, Japan wax, jojoba oil and other plant waxes; beeswax and other animal waxes; montan wax, ozocerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Trppsch wax, ester wax and other mineral and petroleum waxes; and modified forms of these and the like.

The content of the release agent is preferably from 1 to 25 mass parts per 100 mass parts of the resin component of the toner.

[Examples ]

[0055] This invention is explained in more detail below using examples and comparative examples, but the invention is not limited to these embodiments. Unless otherwise specified, parts and percentages in the examples and comparative examples represent mass parts and percentages.

[0056] Manufacture of amorphous resin fine particles 1

Tetrahydrofuran 200 g

(Wako Pure Chemical Industries, Ltd.)

Polyester resin A 120 g

[Composition (molar ratio): polyoxypropylene ( 2.2 ) -2 , 2- bis (4-hydroxyphenyl ) propane : isophthalic

acid : terephthalic acid = 100:50:50, number-average molecular weight (Mn) = 4,600, weight-average molecular weight (Mw) = 16,500, peak molecular weight (Mp) = 10,400, Mw/Mn = 3.6, softening temperature (Tm) = 122°C, glass transition temperature (Tg) = 70°C, acid value = 13 mg KOH/g]

Anionic surfactant (DKS Co. Ltd., Neogen RK)

0.6 g

These ingredients were mixed and then agitated for 12 hours to dissolve the resin.

2.7 g of N, N-dimethylaminoethanol was then added, and the mixture was agitated at 4000 rpm with a T.K. Robomix high speed mixing system (PRIMIX Corporation) .

360 g of ion-exchange water was then added at a rate of 1 g/min to precipitate resin fine particles. The tetrahydrofuran was then removed with an evaporator to obtain amorphous resin fine particles 1 and a liquid dispersion thereof.

The 50% particle diameter on a volume basis (d50) of the amorphous resin fine particles 1 was 0.13 μπι as measured with a dynamic light scattering particle size distribution analyzer (Nanotrac: NIKKISO CO., LTD.).

[0057] Manufacture of amorphous resin fine particles 2

Amorphous resin fine particles 2 and a liquid dispersion thereof were manufactured in the same way as the amorphous resin fine particles 1 except that a polyester B [composition (molar ratio) : polyoxypropylene (2.2) -2, 2-bis (4- hydroxyphenyl) propane: polyoxyethylene (2.0) -2, 2-bis (4- hydroxyphenyl) propane: terephthalic acid = 35:15:50, Mn = 4,500, Mw = 12,300, Mw/Mn = 2.9, Tm = 115°C, Tg = 65°C, acid value = 12 mg KOH/g] was substituted for the polyester resin A. The 50% particle diameter on a volume basis (d50) of the resulting amorphous resin fine particles 2 was 0.12 μπι.

[0058] Manufacture of amorphous resin fine particles 3

Amorphous resin fine particles 3 and a liquid dispersion thereof were manufactured in the same way as the amorphous resin fine particles 1 except that a polyester C [composition (molar ratio) : polyoxypropylene (2.2) -2, 2-bis (4- hydroxyphenyl) propane : polyoxyethylene (2.0) -2, 2-bis (4- hydroxyphenyl) propane: terephthalic acid = 25:25:50, Mn

= 3,500, Mw = 10,300, Mw/Mn = 2.9, Tm = 110°C, Tg = 60°C, acid value = 12 mg KOH/g] was substituted for the polyester resin A. The 50% particle diameter on a volume basis (d50) of the resulting amorphous resin fine particles 3 was 0.12 jam.

[0059] Manufacture of amorphous resin fine particles 4

Amorphous resin fine particles 4 and a liquid dispersion thereof were manufactured in the same way as the amorphous resin fine particles 1 except that a polyester D [composition (molar ratio) : polyoxyethylene (2.0) -2, 2-bis (4- hydroxyphenyl) propane : terephthalic acid = 50:50, Mn = 3,900, Mw = 12,300, Mw/Mn = 3.1, Tm = 109°C, Tg = 58°C, acid value = 12 mg KOH/g] was substituted for the polyester resin A. The 50% particle diameter on a volume basis (d50) of the resulting amorphous resin fine particles 4 was 0.12 μπι.

[0060] Manufacture of amorphous resin fine particles 5

Tetrahydrofuran 200 g

(Wako Pure Chemical Industries, Ltd.)

Styrene acrylic resin A 120 g

[Composition (molar ratio): styrene : butyl acrylate : stearyl acrylate : acrylic acid = 75:10:10:5, number-average molecular weight (Mn) = 15,600, weight- average molecular weight (Mw) = 36,500, peak molecular weight (Mp) = 30,400, Mw/Mn = 2.3, softening temperature (Tm) = 122°C, glass transition temperature (Tg) = 57°C]

Anionic surfactant (DKS Co. Ltd., Neogen RK)

0,6 g

These ingredients were mixed and then agitated for 12 hours to dissolve the resin.

4.0 g of N, N-dimethylaminoethanol was then added, and the mixture was agitated at 4000 rpm with a T.K. Robomix high speed mixing system (PRIMIX Corporation) .

360 g of ion-exchange water was then added at a rate of 1 g/min to precipitate resin fine particles. This was then dispersed for about an hour with a high- pressure impact disperser (Nanomizer, yoshida kikai co. , ltd.), and the tetrahydrofuran was removed with an evaporator to obtain amorphous resin fine particles 5 and a liquid dispersion thereof.

The 50% particle diameter on a volume basis (d50) of the amorphous resin fine particles 5 was 0.15 μπι as measured with a dynamic light scattering particle size distribution analyzer (Nanotrac: NIKKISO CO., LTD.).

[0061] Manufacture of crystalline resin fine particles 1

Tetrahydrofuran 200 g

(Wako Pure Chemical Industries, Ltd.) Crystalline polyester A 120 g

[Composition (molar ratio): 1 , 9-nonanediol : sebacic acid = 100:100, number-average molecular weight (Mn) = 5,500, weight-average molecular weight (Mw) = 15,500, peak molecular weight (Mp) = 11,400, Mw/Mn = 2.8, melting point = 72°C, acid value = 13 mg KOH/g]

Anionic surfactant (DKS Co. Ltd., Neogen RK)

0.6 g

These ingredients were mixed and then agitated for

3 hours at 50°C to dissolve the resin.

2.7 g of N, N-dimethylaminoethanol was then added, and the mixture was agitated at 4000 rpm with a T.K. Robomix high speed mixing system (PRIMIX Corporation) .

360 g of ion-exchange water was then added at a rate of 1 g/min to precipitate resin fine particles. The tetrahydrofuran was then removed with an evaporator to obtain crystalline resin fine particles 1 and a liquid dispersion thereof.

The 50% particle diameter on a volume basis (d50) of the crystalline resin fine particles 1 was 0.30 μιη as measured with a dynamic light scattering particle size distribution analyzer (Nanotrac: NIKKISO CO., LTD. ) .

[0062] Manufacture of crystalline resin fine particles 2

Crystalline resin fine particles 2 and a liquid dispersion thereof were manufactured in the same way as the crystalline resin fine particles 1 except that a crystalline polyester B [composition (molar ratio) :

I, 6-hexanediol: sebacic acid = 100:100, Mn = 4,400, Mw =

II, 300, Mw/Mn = 2.5, melting point = 68°C, acid value = 12 mg KOH/g] was substituted for the crystalline polyester A. The 50% particle diameter on a volume basis (d50) of the resulting crystalline resin fine particles 2 was 0.20 μπι.

[0063] Manufacture of crystalline resin fine particles 3

Crystalline resin fine particles 3 and a liquid dispersion thereof were manufactured in the same way as the crystalline resin fine particles 1 except that a crystalline polyester C [composition (molar ratio) : 1, 12-dodecanediol : sebacic acid = 100:100, Mn = 3,500, Mw = 10, 300, Mw/Mn = 2.9, melting point = 87°C, acid value = 12 mg KOH/g] was substituted for the crystalline polyester A. The 50% particle diameter on a volume basis (d50) of the resulting crystalline resin fine particles 3 was 0.32 μπι.

[0064] Manufacture of crystalline resin fine particles 4

Toluene 200 g

(Wako Pure Chemical Industries, Ltd.)

Crystalline acrylic resin A 120 g

[Composition (molar ratio): behenyl acrylate: 100, number-average molecular weight (Mn) = 10,500, weight- average molecular weight (Mw) = 32,500, peak molecular weight (Mp) = 27,400, Mw/Mn = 3.2, melting point = 60°C]

Anionic surfactant (DKS Co. Ltd., Neogen RK)

0.6 g

These ingredients were mixed and then agitated for

3 hours at 50°C to dissolve the resin.

The mixture was agitated at 4000 rpm with a T.K. Robomix high speed mixing system (PRI IX Corporation) .

360 g of ion-exchange water was then added at a rate of 10 g/min to precipitate resin fine, particles, which were then dispersed for about an hour with a high-pressure impact disperser (Nanomizer, yoshida kikai co. , ltd.), and the toluene was removed with an evaporator to obtain crystalline resin fine particles 4 and a liquid dispersion thereof.

The 50% particle diameter on a volume basis (d50) of the crystalline resin fine particles 4 was 0.32 μπι as measured with a dynamic light scattering particle size distribution analyzer (Nanotrac: NIKKISO CO., LTD. ) .

[0065] Solubility test of amorphous resin and crystalline resin

The polyester resins A to D, styrene acrylic resin A, crystalline polyesters A to C and crystalline acrylic resin A described above were added in specific mass amounts to 1 L of each the various organic solvents shown in Table 1 and agitated for 12 hours in an environment of 25°C, which is the treatment temperature of the solvent treatment step (described below) , and solubility was evaluated. The evaluation results are shown in Table 1.

Based on the solubility test results for each resin, ethyl acetate, methyl ethyl ketone (MEK) , acetone and methyl acetate, which are good solvents for the amorphous resins but poor solvents for the crystalline resins, were used as the organic solvents added in the solvent treatment step when manufacturing the toners described below.

Evaluation Standard

A: Completely dissolves 100 g of added resin, producing a clear liquid

B: Completely dissolves 10 g of added resin, producing a clear liquid, but produces a nonuniform liquid with some undissolved matter observed when 100 g of resin is added

C: Produces a nonuniform liquid with undissolved matter when 10 g of resin is added

[0066] [Table 1] Ethyl Methyl

Resin MEK Acetone Toluene Ethanol acetate acetate

Polyester resin A A A A A A C

Polyester resin B A A A A A C

Polyester resin C A A A A A C

Polyester resin D A A A A A C

Styrene acrylic resin A A A A A A B

Crystalline polyester A C C C C B C

Crystalline polyester B C C C C B C

Crystalline polyester C C C C C B C

Crystalline acrylic resin A C C C C B C

[0067] Manufacture of colorant fine particles

Colorant 10.0 parts

(cyan pigment, Dainichiseika Pigment Blue 15:3) Anionic surfactant (DKS Co. Ltd., Neogen RK)

1.5 parts

Ion-exchange water 88.5 parts

These ingredients were mixed, dissolved, and dispersed for about an hour with a high-pressure impact disperser (Nanomizer, yoshida kikai co. , ltd.) to disperse the colorant and prepare a liquid dispersion of colorant fine particles.

The 50% particle diameter on a volume basis (d50) of the resulting colorant fine particles was 0.20 UJTI as measured with a dynamic light scattering particle size distribution analyzer (Nanotrac: NIKKISO CO., LTD.).

[0068] Manufacture of release agent fine particles

Release agent 20.0 parts (HNP-51, melting point 78°C, NIPPON SEIRO CO.,

LTD. )

Anionic surfactant (DKS Co. Ltd., Neogen RK)

1.0 part

Ion-exchange water 79.0 parts

These ingredients were placed in a mixer equipped with an agitator, heated to 90°C, and dispersed for 60 minutes by agitating under conditions of rotor speed 19000 rpm, screen speed 19000 rpm in a shear agitation site with an outer rotor diameter of 3 cm and a clearance of 0.3 mm while being circulated to a Clearmix W-Motion (M Technique Co., Ltd.).

This was then cooled to 40°C under cooling conditions of rotor speed 1000 rpm, screen speed 0 rpm, cooling rate 10°C/min to obtain a liquid dispersion of release agent fine particles. The 50% particle diameter on a volume basis (d50) of the release agent fine particles was 0.15 μπι as measured with a dynamic light scattering particle size distribution analyzer (Nanotrac: NIKKISO CO., LTD.).

[0069] Example 1

Granulating step-Aggregation Step

Liquid dispersion of amorphous resin fine particles 1 320 parts

Liquid dispersion of crystalline resin fine particles 1 80 parts

Liquid dispersion of colorant fine particles 50 parts

Liquid dispersion of release agent fine particles

50 parts

Ion-exchange water 400 parts

These materials were placed in a round-bottomed stainless-steel flask and mixed, after which an aqueous solution of 2 parts magnesium sulfate dissolved in 98 parts of ion-exchange water was added, and the mixture was dispersed for 10 minutes at 5000 rpm with a homogenizer (IKA Co. Ultra-Turrax T50) .

This was then heated to 58°C in a heating water bath with a stirring blade with the rotation controlled appropriately to agitate the mixture, and maintained at 58°C for 1 hour to yield aggregate particles with a volume-average particle diameter of about 6.0

Compatibilization step

A solution of 20 mass parts of trisodium citrate dissolved in 380 parts of ion-exchange water was added to a liquid dispersion containing these aggregate particles, which was then heated to 85°C. This was maintained for 2 hours at 85°C to obtain thoroughly fused toner particles with a volume-average particle diameter of about 5.8 μπι and an average circularity of 0.968.

The average circularity was measured and calculated using a Sysmex FPIA-3000 flow particle imaging instrument in accordance with the attached manual.

Solvent treatment step

The aqueous dispersion of toner particles obtained in the compatibilization step was cooled to 25°C with continuing agitation, 15 parts of ethyl acetate were added, and the mixture was kept sealed for 3 hours.

The pressure was then reduced with an evaporator with the temperature maintained at 25°C to remove the ethyl acetate, and following filtration and solid- liquid separation, the filtrate was thoroughly washed with ion-exchange water and dried with a vacuum drier to obtain toner particles 1 with a volume-average particle diameter of 5.4 μηα. The formulation and properties of the resulting toner particles 1 are shown in Table 2.

[0070] Example 2

Toner particles 2 were obtained as in Example 1 except that the liquid dispersion of amorphous resin fine particles 1 was replaced with a liquid dispersion of amorphous resin fine particles 2. The resulting toner particles 2 had a volume-average particle diameter of 5.5 The formulation and properties of the toner particles 2 are show in Table 2.

[0071] Example 3

Toner particles 3 were obtained as in Example 1 except that the liquid dispersion of amorphous resin particles 1 was replaced with a liquid dispersion of amorphous resin particles 3, and the treatment temperature in the aggregation step was changed from 58°C to 53°C. The resulting toner particles 3 had a volume-average particle diameter of 5.8 μπι. The formulation and properties of the toner particles 3 are shown in Table 2.

[0072] Example 4

Toner particles 4 were obtained as in Example 1 except that the heating temperature in the compatibilization step was changed from 85°C to 80°C. The resulting toner particles 4 had a volume-average particle diameter of 5.8 μπι. The formulation and properties of the toner particles 4 are shown in Table 2.

[0073] Example 5

Toner particles 5 were obtained as in Example 1 except that the heating temperature in the compatibilization step was changed from 85°C to 95°C. The resulting toner particles 5 had a volume-average particle diameter of 5.8 μτ . The formulation and properties of the toner particles 5 are shown in Table

2-

[0074] Example 6

Toner particles 6 were obtained as in Example 1 except that the 15 parts of ethyl acetate added in the solvent treatment step were replaced with 3 parts of ethyl acetate. The resulting toner particles 6 had a volume-average particle diameter of 5.9 μπι. The formulation and properties of the toner particles 6 are shown in Table 2.

[0075] Example 7

Toner particles 7 were obtained as in Example 1 except that the 15 parts of ethyl acetate added in the solvent treatment step were replaced with 60 parts of ethyl acetate. The resulting toner particles 7 had a volume-average particle diameter of 5.8 μι. The formulation and properties of the toner particles 7 are shown in Table 2.

[0076] Example 8

Granulating step-Aggregation step

Liquid dispersion of amorphous resin fine particles 1 320 parts

Liquid dispersion of crystalline resin fine particles 1 80 parts

Liquid dispersion of colorant fine particles

50 parts

Liquid dispersion of release agent fine particles

50 parts

Ion-exchange water 400 parts

These materials were placed in a round-bottomed stainless-steel flask and mixed, after which an aqueous solution of 2 parts magnesium sulfate dissolved in 98 parts of ion-exchange water was added, and the mixture was dispersed for 10 minutes at 5000 rpm with a homogenizer (IKA Co. Ultra-Turrax T50) .

This was then heated to 58°C in a heating water bath with a stirring blade with the rotation controlled appropriately to agitate the mixture, and maintained at 58°C for 1 hour to yield aggregate particles with a volume-average particle diameter of about 6.0 μιη.

Compatibilization step

A solution of 20 parts of trisodium citrate dissolved in 380 parts of ion-exchange Water was added to a liquid dispersion containing these aggregate particles, which was then heated to 85°C. This was maintained for 2 hours at 85°C to obtain thoroughly fused toner particles with a volume-average particle diameter of about 5.8 μπι and an average circularity of 0.968.

Solvent treatment step

Cooling water was added to the water bath, the aqueous dispersion of toner particles obtained in the compatibilization step was cooled to 25°C with continuing agitation, 2800 parts of ion-exchange water were added, followed by 200 parts of ethyl acetate, and the mixture was maintained in a sealed condition for 3 hours .

The pressure was then reduced with an evaporator with the temperature maintained at 25°C to remove the ethyl acetate, and following filtration and solid- liquid separation, the filtrate was thoroughly washed with ion-exchange water and dried with a vacuum drier to obtain toner particles 8 with a volume-average particle diameter of 5.4 μτ . The formulation and properties of the resulting toner particles 8 are shown in Table 2.

[0077] Example 9

Toner particles 9 were obtained as in Example 1 except that the liquid dispersion of crystalline resin fine particles 1 was replaced with a liquid dispersion of crystalline resin fine particles 2. The resulting toner particles 9 had a volume-average particle diameter of 5.8 μπι. The formulation and properties of the toner particles 9 are shown in Table 2.

[0078] Example 10

Toner particles 10 were obtained as in Example 1 except that the liquid dispersion of crystalline resin fine particles 1 was replaced with a liquid dispersion of crystalline resin fine particles 3, and the heating temperature in the compatibilization step was changed from 85°C to 90°C. The resulting toner had had a volume-average particle diameter of 5.8 Jim. The formulation and properties of the toner particles 10 are shown in Table 2.

[0079] Example 11

Toner particles 11 were obtained as in Example 1 except that the liquid dispersion of amorphous resin fine particles 1 was replaced with a liquid dispersion of amorphous resin fine particles 5, the liquid dispersion of crystalline resin fine particles 1 was replaced with a liquid dispersion of crystalline resin fine particles 4, and the treatment temperature in the aggregation step was changed from 58°C to 53°C. The resulting toner particles 11 had a volume-average particle diameter of 5.8 μπι. The formulation and properties of the toner particles 11 are shown in Table

2-

[0080] Example 12

Toner particles 12 were obtained as in Example 1 except that the 15 parts of ethyl acetate added in the solvent treatment step were changed to 30 parts of methyl ethyl ketone. The resulting toner particles 12 had a volume-average particle diameter of 5.8 μπι. The formulation and properties of the toner particles 12 are shown in Table 2.

[0081] Example 13

Toner particles 13 were obtained as in Example 1 except that the 15 parts of ethyl acetate added in the solvent treatment step were changed to 50 parts of acetone. The resulting toner particles 13 had a volume-average particle diameter of 5.8 μπι. The formulation and properties of the toner particles 13 are shown in Table 2.

[0082] Example 14 Toner particles 14 were obtained as in Example 1 except that the 15 parts of ethyl acetate added in the solvent treatment step were changed to 30 parts of methyl acetate. The resulting toner particles 14 had a volume-average particle diameter of 5.8 μιη. The formulation and properties of the toner particles 14 are shown in Table 2.

[0083] Example 15

Compatibilization step

Toluene 200 g

(Wako Pure Chemical Industries, Ltd.)

Polyester resin A 96 g

[Composition (molar ratio): polyoxypropylene ( 2.2 ) -2 , 2- bis ( 4-hydroxyphenyl ) propane : isophthalic

acid: terephthalic acid = 100:50:50, number-average molecular weight (Mn) = 4,600, weight-average molecular weight (Mw) = 16,500, peak molecular weight (Mp) = 10,400, Mw/Mn = 3.6, softening temperature (Tm) = 122°C, glass transition temperature (Tg) = 70°C, acid value = 13 mg KOH/g]

Crystalline polyester A 24 g

[Composition (molar ratio): 1 , 9-nonanediol : sebacic acid = 100:100, number-average molecular weight (Mn) = 5,500, weight-average molecular weight (Mw) = 15,500, peak molecular weight (Mp) = 11,400, Mw/Mn = 2.8, melting point = 78°C, acid value = 13 mg KOH/g]

Anionic surfactant (DKS Co. Ltd., Neogen RK) 1.0 g

These ingredients were mixed, heated to 80°C, and agitated and dissolved for 3 hours. This was then agitated at 4000 rpm with a with a T.K. Robomix high speed mixing system (PRIMIX Corporation). 360 g of ion-exchange water was then added at a rate of 10 g/min to precipitate resin fine particles. This was then dispersed for about one hour with a high-pressure impact disperser (Nanomizer, yoshida kikai co. , ltd.), and the toluene was removed with an evaporator to obtain composite fine particles 1 of amorphous resin and crystalline resin, and, a liquid dispersion thereof

The 50% particle diameter on a volume basis (d50) of the composite fine particles 1 of amorphous resin and crystalline resin was 0.19 μπι as measured with a dynamic light scattering particle size distribution analyzer (Nanotrac: NIKKISO CO., LTD.).

Solvent treatment step

15 parts of ethyl acetate were added at 25°C under constant agitation to an aqueous dispersion of the composite fine particles 1 of amorphous resin and crystalline resin obtained by the compatibilization step, and the mixture was kept sealed for 3 hours.

After this, the pressure was then reduced with an evaporator with the temperature maintained at 25°C to remove the ethyl acetate.

Granulating step-Aggregation step Liquid dispersion of composite fine particles 1 of amorphous resin and crystalline resin 400 parts

Liquid dispersion of colorant fine particles

50 parts

Liquid dispersion of release agent fine particles

50 parts

Ion-exchange water 400 parts

These materials were placed in a round-bottomed stainless-steel flask and mixed, after which a aqueous solution of 2 parts magnesium sulfate dissolved in 98 parts of ion-exchange water was added, and the mixture was dispersed for 10 minutes at 5000 rpm with a homogenizer (IKA Co. Ultra-Turrax T50) .

This was then heated to 58°C in a heating water bath with a stirring blade with the rotation controlled appropriately to agitate the mixture, and maintained at 58°C for 1 hour to yield aggregate particles with a volume-average particle diameter of about 6.0 μιη.

An aqueous solution of 20 parts of trisodium citrate dissolved in 380 parts of ion-exchange water was added to a liquid dispersion containing these aggregate particles, after which an aqueous solution of 10 parts of sodium chloride dissolved in 90 parts of ion-exchange water was added, and the mixture was heated to 68°C. This was maintained for 12 hours at 68°C to obtain thoroughly fused toner particles with a volume-average particle diameter of about 5.8 μπι, an average circularity of 0.945.

Cooling water was added to the water bath, the resulting aqueous dispersion of toner particles was cooled to 25°C with constant agitation, and following filtration and solid-liquid separation, the filtrate was thoroughly washed with ion-exchange water and dried with a vacuum drier to obtain toner particles 15 with a volume-average particle diameter of 5.4 μπι. The formulation and properties of the resulting toner particles 15 are shown in Table 2.

[0084] Example 16

Compatibilization step

Polyester resin A 80 parts

Crystalline polyester A 20 parts

Colorant (cyan pigment, Dainichiseika Pigment

Blue 15:3) 5 parts

Release agent (HNP-51, melting point 78°C, NIPPON

SEIRO CO., LTD.) 5.0 parts

These raw materials were pre-mixed in a HENSCHEL

MIXER, and then kneaded for 2 hours with a biaxial kneading extruder (PCM-30, Ikegai Kogyo) set to 130°C, 200 rpm.

Granulating step-Pulverization step

The resulting kneaded product was cooled and coarsely pulverized with a cutter mill, and the resulting coarsely pulverized product was finely pulverized with a T-250 Turbo Mill (FREUND TURBO) and classified with a multi-grade classifier utilizing the Coanda effect to obtain toner particles with a volume- average particle diameter of 5.8 μπι.

Solvent treatment step

100 parts of the toner particles obtained via the compatibilization step and granulating step above were placed in a round-bottomed stainless-steel flask, and an aqueous solution of 10 parts of anionic surfactant

(DKS Co. Ltd., Neogen RK) dissolved in 890 parts of ion-exchange water was added, and the mixture was exposed to ultrasound for 1 hour with an ultrasonic disperser (Ultrasonic Dispersion System Tetora 150

(Nikkaki Bios Co., Ltd.)) to obtain an aqueous dispersion of toner particles.

The flask was then placed in a water bath maintained at 25°C to adjust the aqueous dispersion of toner particles to 25°C, the aqueous dispersion was agitated with a stirring blade as 15 parts of ethyl acetate were added, and the mixture was kept sealed for 3 hours.

The ethyl acetate was then removed with an evaporator, and following filtration and solid-liquid separation, the filtrate was thoroughly washed with ion-exchange water and dried with a vacuum drier to obtain toner particles 16 with a volume-average particle diameter of 5.8 μπι. The formulation and properties of the toner particles 16 are shown in Table 2.

[0085] Example 17

Granulating step-Suspension polymerization step 18 parts of cyan pigment ( Dainichiseika Pigment Blue 15:3) as a colorant, 180 parts of styrene as a polymerizable monomer and 130 parts of glass beads (dia. 1 mm) were mixed and dispersed for 3 hours in an attritor (NIPPON COKE & ENGINEERING. CO., LTD.), and filtered with a mesh to obtain a colorant-dispersed solution.

Colorant-dispersed solution 132 parts

Styrene 46 parts n-butyl acrylate 17 parts n-stearyl acrylate 17 parts

Release agent (HNP-51, melting point 78°C, NIPPON SEIRO CO., LTD.) 25 parts

Aluminum salicylate compound (Bontron E-88, Orient Chemical Industries Co., Ltd.) 2 parts

Divinyl benzene 0.1 parts

Polyester resin A 10 parts

Crystalline acrylic resin A 10 parts

710 parts of ion-exchange water and 450 parts of an 0.1 mol/L Na ₃ P0 ₄ aqueous solution were then added to a 2-liter 4-necked flask attached to a T.K. Homomixer high speed mixing system (PRIMIX Corporation) , and heated to 60°C with the rotation adjusted to 12000 rpm. 68 parts of 1.0 mol/L CaCl ₂ aqueous solution was added gradually to this, to prepare an aqueous medium containing the fine, poorly water-soluble dispersion stabilizer Ca ₃ (P0 ₄ ) ₂ . The aforementioned composition was then heated to 60°C, and uniformly dissolved and dispersed at 5000 rpm with a T.K. Homomixer high speed mixing system (PRIMIX Corporation) .

10 parts of the polymerization initiator 2,2'- azobis (2, 4-dimethylvaleronitrile) were added to the mixture, which was then added to the aforementioned aqueous medium, and granulated for 15 minutes with the rotation maintained at 12000 rpm. The high-speed agitator was replaced with a propeller agitation blade, and polymerization was continued for 5 hours at a liquid temperature of 60°C, after which the liquid temperature was raised to 80°C and polymerization was continued for 8 hours to obtain toner particles.

Compatibilization step

Upon completion of polymerization, this was temporarily cooled to 30°C, and then ke t in a sealed state at 90°C, which is at equal to or above the melting point of the crystalline acrylic resin A, for 3 hours .

Solvent treatment step

An aqueous dispersion of the toner particles obtained in the compatibilization step was cooled to 25°C with continuing agitation, 40 parts of ethyl acetate were added, and the mixture was kept in a sealed state for 3 hours.

This was kept at 25°C as the pressure was reduced with an evaporator to remove the ethyl acetate, after which dilute hydrochloric acid was added with agitation, followed by 2 hours of agitation at pH 1.5 to dissolve the phosphate and calcium compounds including Ca3(P04) ₂ , after which solid-liquid separation was performed with a filtration device to obtain toner particles. These were added to water and agitated to once again obtain a liquid dispersion, and solid-liquid separation was performed with a filtration device. Re-dispersal of the toner particles in water and solid-liquid separation were repeated until the phosphate and calcium compounds including Ca ₃ (P0 ₄ ) ₂ had been thoroughly removed.

Finally, the solid-liquid separated toner particles were thoroughly dried in a drier to obtain toner particles 17 with a volume-average particle diameter of 7.2 μπι. The formulation and properties of the toner particles 17 are shown in Table 2.

[0086] Comparative Example 1

Granulating step-Aggregation step

Liquid dispersion of amorphous resin fine particles 1 320 parts

Liquid dispersion of crystalline resin fine particles 1 80 parts Liquid dispersion of colorant fine particles

50 parts

Liquid dispersion of release agent fine particles

50 parts

Ion-exchange water 400 parts

These materials were placed in a round-bottomed stainless-steel flask and mixed, after which an aqueous solution of 2 parts magnesium sulfate dissolved in 98 parts of ion-exchange water was added, and the mixture was dispersed for 10 minutes at 5000 rpm with a homogenizer (IKA Co. Ultra-Turrax T50) .

This was then heated to 58°C in a heating water bath with a stirring blade with the rotation controlled appropriately to agitate the mixture, and maintained at 58°C for 1 hour to yield aggregate particles with a volume-average particle diameter of about 6.0 μπι.

Compatibilization step-Fusion step

A solution of 20 parts of trisodium citrate dissolved in 380 parts of ion-exchange water was added to a liquid dispersion containing these aggregate particles, which was then heated to 85°C with continued agitation, and maintained in a sealed condition for 3 hours.

The resulting particles were thoroughly fused toner particles with a volume-average particle diameter of about 5.8 Jim and an average circularity of 0.968. Water was then added to the water bath, the aqueous dispersion of toner particles was cooled to

25°C, and following filtration and solid-liquid separation, the filtrate was washed thoroughly with ion-exchange water, and dried with a vacuum drier to obtain toner particles 18 with a volume-average particle diameter of 5.4 μιτι. The formulation and properties of the resulting toner particles 18 are shown in Table 2.

[0087] Comparative Example 2

Toner particles 19 were obtained as in Comparative Example 1 except that the liquid dispersion of amorphous resin fine particles 1 was replaced with a liquid dispersion of amorphous resin fine particles 4. The resulting toner particles 19 had a volume-average particle diameter of 5.8 μτ . The formulation and properties of the resulting toner particles 19 are shown in Table 2.

[0088] Comparative Example 3

Granulating step-Aggregation step

Liquid dispersion of amorphous resin fine particles 4 320 parts

Liquid dispersion of crystalline resin fine particles 1 80 parts

Liquid dispersion of colorant fine particles

50 parts

Liquid dispersion of release agent fine particles 50 parts

Ion-exchange water 400 parts

These materials were placed in a round-bottomed stainless-steel flask and mixed, after which an aqueous solution of 2 parts magnesium sulfate dissolved in 98 parts of ion-exchange water was added, and the mixture was dispersed for 10 minutes at 5000 rpm with a homogenizer (IKA Co. Ultra-Turrax T50) .

This was then heated to 50°C in a heating water bath with a stirring blade with the rotation controlled appropriately to agitate the mixture, and maintained at 50°C for 1 hour to yield aggregate particles with a volume-average particle diameter of about 6.0 μτη.

Compatibilization step

A solution of 20 parts of trisodium citrate dissolved in 380 parts of ion-exchange water was added to a liquid dispersion containing these aggregate particles, which was then heated to 85°C. This was maintained for 2 hours at 85°C to obtain thoroughly fused toner particles with a volume-average particle diameter of about 5.8 μπι and an average circularity of 0.968.

Solvent treatment step

Cooling water was added to the water bath, the aqueous dispersion of toner particles obtained in the compatibilization step was cooled to 25°C with continuing agitation, 2800 parts of ion-exchange water were added, followed by 200 parts of ethyl acetate, and the mixture was maintained in a sealed condition for 3 hours.

The pressure was then reduced with an evaporator with the temperature maintained at 25°C to remove the ethyl acetate, and following filtration and solid- liquid separation, the filtrate was thoroughly washed with ion-exchange water and dried with a vacuum drier to obtain toner particles 20 with a volume-average particle diameter of 5.4 μπι. The formulation and properties of the resulting toner particles 20 are shown in Table 2.

[0089] Comparative Example 4

Granulating step-Aggregation step

Liquid dispersion of amorphous resin fine particles 1 320 parts

Liquid dispersion of crystalline resin fine particles 1 80 parts

Liquid dispersion of colorant fine particles

50 parts

Liquid dispersion of release agent fine particles

50 parts

Ion-exchange water 400 parts

These materials were placed in a round-bottomed stainless-steel flask and mixed, after which an aqueous solution of 2 parts magnesium sulfate dissolved in 98 parts of ion-exchange water was added, and the mixture was dispersed for 10 minutes at 5000 rpm with a homogenizer (IKA Co. Ultra-Turrax T50) .

This was then heated to 58°C in a heating water bath using a stirring blade with the rotation controlled appropriately to agitate the mixture, and maintained at 58°C for 1 hour to yield aggregate particles with a volume-average particle diameter of about 6.0 urn .

Compatibilization step-Fusion step

A solution of 20 parts of trisodium citrate dissolved in 380 parts of ion-exchange water was added to a liquid dispersion containing these aggregate particles, which was then heated to 85°C with continuing agitation, and maintained in a sealed condition for 2 hours.

The resulting particles were thoroughly fused toner particles with a volume-average particle diameter of about 5.8 μηι and an average circularity of 0.968.

Annealing step by heat treatment

Water was then added to the water bath to cool the aqueous dispersion of toner particles to 25°C, and this was then annealed by heating and then heated again to 50°C and maintained for 12 hours. The aqueous dispersion of toner particles was then cooled to 25°C, and following filtration and solid-liquid separation, the filtrate was washed thoroughly with ion-exchange water, and dried with a vacuum drier to obtain toner particles 21 with a volume-average particle diameter of

5.4 μπι. The formulation and properties of the resulting toner particles 21 are shown in Table 2.

[0090] Comparative Example 5

Granulating step-Aggregation step

Liquid dispersion of amorphous resin fine particles 1 320 parts

Liquid dispersion of crystalline resin fine particles 1 80 parts

Liquid dispersion of colorant fine particles

50 parts

Liquid dispersion of release agent fine particles

50 parts

Ion-exchange water 400 parts

These materials were placed in a round-bottomed stainless-steel flask and mixed, after which an aqueous solution of 2 parts magnesium sulfate dissolved in 98 parts of ion-exchange water was added, and the mixture was dispersed for 10 minutes at 5000 rpm with a homogenizer (IKA Co. Ultra-Turrax T50) .

This was then heated to 58°C in a heating water bath with a stirring blade with the rotation controlled appropriately to agitate the mixture, and maintained at 58°C for 1 hour to yield aggregate particles with a volume-average particle diameter of about 6.0 μιτι.

Compatibilization step-Fusion step A solution of 20 parts of trisodium citrate dissolved in 380 parts of ion-exchange water was added to a liquid dispersion containing these aggregate particles, which was then heated to 85°C with continuing agitation, and maintained in a sealed condition for 2 hours.

The resulting particles were thoroughly fused toner particles with a volume-average particle diameter of about 5.8 um and an average circularity of 0.968.

Solvent treatment step

Cooling water was added to the water bath, the aqueous dispersion of toner particles obtained in the compatibilization step was cooled to 25°C with continuing agitation, 2800 parts of ion-exchange water were added, followed by 200 parts of toluene, and when the mixture was maintained in a sealed condition for 3 hours, coarse particles made up of fused toner particles were observed.

The pressure was then reduced with an evaporator with the temperature maintained at 25°C to remove the toluene, and following filtration and solid-liquid separation, the filtrate was thoroughly washed with ion-exchange water and dried with a vacuum drier, but no toner particles of a size that could be evaluated as discussed below were obtained (toner particles 22) .

[0091] Comparative Example 6

Granulating step-Aggregation step Liquid dispersion of amorphous resin fine particles 1 320 parts

Liquid dispersion of crystalline resin fine particles 1

80 parts

Liquid dispersion of colorant fine particles

50 parts

Liquid dispersion of release agent fine particles

50 parts

Ion-exchange water 400 parts

These materials were placed in a round-bottomed stainless-steel flask and mixed, after which an aqueous solution of 2 parts magnesium sulfate dissolved in 98 parts of ion-exchange water was added, and the mixture was dispersed for 10 minutes at 5000 rpm with a homogenizer (IKA Co. Ultra-Turrax T50) .

This was then heated to 58°C in a heating water bath with a stirring blade with the rotation controlled appropriately to agitate the mixture, and maintained at 58°C for 1 hour to yield aggregate particles with a volume-average particle diameter of about 6.0 μπι.

Compatibilization step-Fusion step

A solution of 20 parts of trisodium citrate dissolved in 380 parts of ion-exchange water was added to a liquid dispersion containing these aggregate particles, which was then heated to 85°C with continuing agitation, and kept sealed for 2 hours. The resulting particles were thoroughly fused toner particles with a volume-average particle diameter of about 5.8 μπι and an average circularity of 0.968.

Solvent treatment step

Cooling water was added to the water bath, the aqueous dispersion of toner particles obtained in the compatibilization step was cooled to 25°C with continuing agitation, 2800 parts of ion-exchange water were added, followed by 200 parts of ethanol, and the mixture was maintained in a sealed condition for 3 hours .

The pressure was then reduced with an evaporator with the temperature maintained at 25°C to remove the ethanol, and following filtration and solid-liquid separation, the filtrate was thoroughly washed with ion-exchange water and dried with a vacuum drier to obtain toner particles 23 with a volume-average particle diameter of 5.4 μπι. The formulation and properties of the resulting toner particles 23 are shown in Table 2.

[0092] Comparative Example 7

Granulating step-Aggregation step

Liquid dispersion of amorphous resin fine particles 1 320 parts

Liquid dispersion of crystalline resin fine particles 1 80 parts

Liquid dispersion of colorant fine particles 50 parts

Liquid dispersion of release agent fine particles

50 parts

Ion-exchange water 400 parts

Ethyl acetate 60 parts

These materials were placed in a round-bottomed stainless-steel flask and mixed, after which an aqueous solution of 2 parts magnesium sulfate dissolved in 98 parts of ion-exchange water was added, and the mixture was dispersed for 10 minutes at 5000 rpm with a homogenizer (IKA Co. Ultra-Turrax T50) .

When this was then heated to 58°C in a heating water bath using a stirring blade with the rotation controlled appropriately to agitate the mixture, coarse particles formed by fusion of toner particles were observed. This was maintained at 58°C for 1 hour to yield aggregate particles with a volume-average particle diameter of about 12.0 μπι.

Compatibilization step-Fusion step

A solution of 20 parts of trisodium citrate dissolved in 380 parts of ion-exchange water was added to a liquid dispersion containing these aggregate particles, which was then heated to 85°C with continuing agitation, and maintained in a sealed condition for 2 hours. The resulting particles were thoroughly fused toner particles with a volume-average particle diameter of about 13.8 μιη and an average circularity of 0.968.

Water was then added to the water bath to cool the aqueous dispersion of toner particles to 25°C, and following filtration and solid-liquid separation, the filtrate was thoroughly washed with ion-exchange water and dried with a vacuum drier, but no toner particles of a size that could be evaluated as discussed below were obtained (toner particles 24).

[0093] Comparative Example 8

Granulating step-Aggregation Step

Liquid dispersion of amorphous resin fine particles 1 320 parts

Liquid dispersion of crystalline resin fine particles 1 80 parts

Liquid dispersion of colorant fine particles

50 parts

Liquid dispersion of release agent fine particles

50 parts

Ion-exchange water 400 parts

These materials, were placed in a round-bottomed stainless-steel flask and mixed, after which an aqueous solution of 2 parts magnesium sulfate dissolved in 98 parts of ion-exchange water was added, and the mixture was dispersed for 10 minutes at 5000 rpm with a homogenizer (IKA Co. Ultra-Turrax T50). This was then heated to 58°C using a heating water bath with a stirring blade with the rotation controlled appropriately to agitate the mixture, and maintained at 58°C for 1 hour to yield aggregate particles with a volume-average particle diameter of about 5.8 μπι.

Compatibilization step-Fusion step

A solution of 20 parts of trisodium citrate dissolved in 380 parts of ion-exchange water was added to a liquid dispersion containing these aggregate particles, 60 parts of ethyl acetate were added under continuing agitation, and the mixture was heated to 85°C and kept sealed for 2 hours.

The resulting particles were thoroughly fused toner particles with a volume-average particle diameter of about 5.8 um and an average circularity of 0.968.

Next, the mixture in a heated state was depressurized with ah evaporator to remove the ethyl acetate, cooling water was added to the water bath, and agitation was continued as the mixture was cooled to 25°C. Following filtration and solid-liquid separation of the resulting liquid dispersion of toner, the filtrate was thoroughly washed with ion-exchange water and dried with a vacuum drier to obtain toner particles 25 with a volume-average particle diameter of 5.4 μιη. The formulation and properties of the resulting toner particles 25 are shown in Table 2.

[0094] Toner evaluation The following evaluations were performed to evaluate the toner properties of the toner particles 1 to 25 above. The results are given in Table 2.

[0095] Evaluation of storability

1.8 parts of silica fine particles that had been hydrophobically treated with silicone oil and had a specific surface area of 200 m ² /g by the BET method were dry mixed with a HENSCHEL MIXER (Mitsui Mining Co., Ltd.) into 100 parts of toner particles, to prepare a toner with an external additive.

This toner was left standing for 3 days in a thermohygrostat and screened for 300 seconds with a shaking width of 1 mm using a 75 μπχ mesh screen, and the amount of toner remaining on the screen was evaluated according to the following standard. The evaluation results are shown in Table 2.

Evaluation Standard

A: Less than 10% of toner remains on screen upon screening after 3 days' still standing in a thermohygrostat at 55°C, 10% RH.

B: 10% or more of toner remains on screen upon screening after 3 days' still standing in a ^' thermohygrostat at 55°C, 10% RH, but less than 10% of toner remains on screen upon screening after 3 days' still standing in a thermohygrostat at 50°C, 10% RH. C: 10% or more of toner remains on screen upon screening after 3 days' still standing in a thermohygrostat at 50°C, 10% RH.

[0096] Evaluation of low-temperature fixability

1.8 parts of silica fine particles that had been hydrophobically treated within silicone oil and had a specific surface area of 200 m ² /g by the BET method were dry mixed with a HENSCHEL MIXER (Mitsui Mining Co., Ltd.) into 100 parts of toner particles, to prepare toner with an external additive.

This toner and a ferrite carrier (average particle diameter 42 μπι) surface coated with silicone resin were mixed to a toner concentration of 8 mass% to prepare a two-component developer.

This two-component developer was loaded into a commercial full-color digital printer (CLCllOO, Canon Inc.), and an unfixed toner image (0.6 mg/cm ² ) was formed on image receiving paper (64 g/m ² ) .

A fixing unit that had been removed from a commercial full color digital copier (imageRUNNER ADVANCE C5051, Canon Inc.) was modified to allow adjustment of the fixation temperature, and used to perform a fixing test with the unfixed image. At normal temperature, normal humidity with the process speed set to 246 mm/second, the condition after the unfixed image was fixed was evaluated visually. The evaluation results are shown in Table 2. Evaluation Standard

A: Fixing possible at temperature range of <120°C

B: Fixing possible at temperatures higher than 120°C and no higher than 125°C

C: Fixing possible at temperatures higher than 125°C and no higher than 130°C

D: Fixing possible at temperatures higher than 130°C and no higher than 140°C

E: Fixing only possible at a temperature range above 140°C

[0097] Evaluation of charging performance

1.8 parts of silica fine particles that had been hydrophobically treated within silicone oil and had a specific surface area of 200 m ² /g by the BET method were dry mixed with a HENSCHEL MIXER (Mitsui Mining Co., Ltd.) into 100 parts of toner particles, to prepare toner with an external additive.

This toner and a ferrite carrier (average particle size 42 μπι) surface coated with silicone resin were mixed to a toner concentration of 8 mass% to prepare a two-component developer.

The charge quantity of the toner here was measured with a Hosokawa Micron E-SPART ANALYZER. The E-SPART ANALYZER is a device that introduces sample particles into a detection part (measurement part) with a simultaneously formed electrical field and sound field, measures the rate of particle movement by the laser doppler method, and measures the particle size and quantity of charge.

Once they enter the measurement part of the device, the sample particles are affected by the sound field and electrical field, deviating horizontally as they fall, and the beat frequency of the horizontal speed is counted. The count value is input interruptively into a computer, and the particle size distribution or charge quantity distribution for each unit particle size is displayed on the computer screen in real time. When the charge quantity of a specific number is measured, the screen stops, and the screen displays the three-dimensional distribution of charge quantities and particle sizes and the charge quantity distribution and average charge quantity (coulombs/weight) and the like for each particle size.

The charge quantity of the toner can be measured by introducing the two-component developer as sample particles into the measurement part of the E-SPART ANALYZER.

Once the triboelectric charge quantity of the initial toner had been measured by this method, the two-component developer was left for one week in a thermohygrostat (temperature 30°C, humidity 80% RH) , and the triboelectric charge- quantity was measured again. The measurement results were entered into the following formula to calculate the triboelectric charge quantity retention rate, which was evaluated by the following standard. The evaluation results are shown in Table 2.

Formula: Toner triboelectric charge retention rate (%) = [triboelectric charge quantity of toner after 1 week] / [triboelectric charge quantity of initial toner] x 100

Evaluation Standard

A: Toner triboelectric charge retention rate is 80% or more

B: Toner triboelectric charge retention rate is at least 60% and less than 80%

C: Toner triboelectric charge retention rate is less than 60%

[0098] [Table 2A]

Amorphous resin Crystalline resin

Organic

Toner

solvent

Toner manufact

or

particles uring Melt heat

method Amorphous SP Crystalline ing SP

treatment A SP

resin value resin point value

(°C)

Emulsion Ethyl Polyester Crystalline

Example 1 1 1 1.14 72 9.63 1.51 aggregation acetate resin A polyester A

Emulsion Ethyl Polyester Crystalline

Example2 2 11.21 72 9.63 1.58 aggregation acetate resin B polyester A

Emulsion Ethyl Polyester Crystalline

Example3 3 1 1.25 72 9.63 1.62 aggregation acetate resin C polyester A

Emulsion Ethyl Polyester Crystalline

Example4 4 11.14 72 9.63 1.51 aggregation acetate resin A polyester A

Emulsion Ethyl Polyester Crystalline

Example5 5 1 1.14 72 9.63 1.51 aggregation acetate resin A polyester A

Emulsion Ethyl Polyester Crystalline

Example6 6 11.14 72 9.63 1.51 aggregation acetate resin A polyester A

Emulsion Ethyl Polyester Crystalline

Example7 7 1 1.14 72 9.63 1.51 aggregation acetate resiri A polyester A

Emulsion Ethyl Polyester Crystalline

Example8 8 11.14 72 9.63 1.51 aggregation acetate resin A polyester A

Emulsion Ethyl Polyester Crystalline

Example9 9 1 1.14 68 9.81 1.33 aggregation acetate resin A polyester B

Emulsion Ethyl Polyester Crystalline

Example 10 10 1 1.14 87 9.49 1.65 aggregation acetate resin A polyester C

Styrene Crystalline

Emulsion Ethyl

Example 1 1 1 1 acrylic 9.97 acrylic 60 8.94 1.03 aggregation acetate

resin A resin A

Emulsion Polyester Crystalline

Example 12 12 MEK 11.14 72 9.63 1.51 aggregation resin A polyester A

Emulsion Polyester Crystalline

Example 13 13 Acetone 11.14 72 9.63 1.51 aggregation resin A polyester A

Emulsion Methyl Polyester Crystalline

Example 14 14 1 1.14 72 9.63 1.51 aggregation acetate resin A polyester A

Emulsion Ethyl Polyester Crystalline

Example 15 15 11.14 72 9.63 1.51 aggregation acetate resin A polyester A

Kneading Ethyl Polyester Crystalline

Example 16 16 1 1.14 72 9.63 1.51 pulverization acetate resin A polyester A

Styrene Crystalline

Suspension Ethyl

Example 7 17 acrylic 9.97 acrylic 60 8.94 1.03 polymerization acetate

resin A resin A

[Table 2B] Amorphous resin Crystalline resin

Organic

Toner

solvent

Toner manufact

or Melt particles uring

heat line ing SP method Amorphous SP Crystal

A S

treatment resin value resin point value

(°C)

Comparative Emulsion Polyester Crystalline

18 - 11.14 72 9.63 1.51 Examplel aggregation resin A polyester A

Comparative Emulsion Polyester Crystalline

19 - 1 1.37 72 9.63 1.74 Example2 aggregation resin D polyester A

Comparative Emulsion Ethyl Polyester Crystalline

20 11.37 72 9.63 1.74 Example3 aggregation acetate resin D polyester A

Comparative Emulsion Heat Polyester Crystalline

21 1 1.14 72 9.63 1.51 Example4 aggregation treatment resin A polyester A

Comparative Emulsion Polyester Crystalline

22 Toluene 11.14 72 9.63 1.51 Example5 aggregation resin A polyester A

Comparative Emulsion Polyester Crystalline

23 Ethanol 11.14 72 9.63 1.51 Example6 aggregation resin A polyester A

Ethyl

acetate

Comparative Emulsion Polyester Crystalline

24 (added in 11.14 72 9.63 1.51 Example 7 aggregation resin A polyester A

granulating

step)

Ethyl

acetate

(added and

Comparative Emulsion Polyester Crystalline

25 removed in 1 1.14 72 9.63 1.51 Example8 aggregation resin A polyester A

compatibi

lization

step)

[Table 2C]

DSC curve

Toner properties in each step

Toner Compatibilization Solvent

particles step treatment step

Low-

Charging

Storability temperature

Wt (Wta-WtO) performance fixability

/ /

(Wr Z/100) (WrO x Z/100)

Example 1 1 0.21 0.31 A A A

Example 2 2 0.35 0.13 A B A

Example3 3 0.45 0.09 A C A

Example4 4 0.31 0.31 A B A

Example5 5 0.21 0.31 A A A

Example6 6 0.21 0.08 A A B

Example 7 7 0.21 0.40 A A A

Example8 8 0.21 0.49 A B A

Example9 9 0.12 0.35 A A A

Example 10 10 0.32 0.18 A B A

Example 1 1 1 1 0.33 0.18 A C A

Example 12 12 0.21 0.35 A A A

Example 13 13 0.21 0.31 A A A

Example 14 14 0.21 0.35 A A A

Example 15 15 0.21 0.31 A A A

Example 1 6 16 0.21 0.45 A A A

Example 1 7 17 0.33 0.18 A C A

Comparative

18 0.21 - C A C Example 1

Comparative

19 0.78 - A E A Example2

Comparative

20 0.78 0.01 A E A Example3

Comparative

21 0.21 - A B C Example4

Comparative

22 Coarse particles formed, could not evaluate

Example5

Comparative

23 0.21 - C A C Example6

Comparative

24 Coarse particles formed, could not evaluate

Example7

Comparative

25 0.21 - C A C Example8

[0099] While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.

[0100] This application claims the benefit of

Japanese Patent Application No. 2014-249317, filed on December 9, 2014, which is hereby incorporated by reference herein in its entirety.