JP2010077319A - Crystalline polyester resin dispersion, method for producing crystalline polyester resin, toner for electrostatic image development, electrostatic image developer, toner cartridge, process cartridge, and image formation apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crystalline polyester resin dispersion that is controlled from coagulation, and the crystalline polyester resin in the dispersion is protected from particle size change and from precipitation from the dispersion, also to provide an easy method for producing the crystalline polyester resin dispersion. <P>SOLUTION: The crystalline polyester resin dispersion is a dispersion of a crystalline polyester resin in an aqueous medium, and a titration curve, whose horizontal axis represents variation of pH measured by titration of the crystalline polyester resin dispersion by sodium hydroxide and the vertical axis represents a value obtained by differentiating the pH by the amount of sodium hydroxide used for the titration, has two peaks, and the crystalline polyester resin dispersion is prepared by dissolving a crystalline polyester resin in a solvent, and by performing the phase inversion emulsification, then by removing solvent after cooling down to -5°C, i.e. recrystallization temperature of the crystalline polyester resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a crystalline polyester resin dispersion, a method for producing a crystalline polyester resin dispersion, a toner for developing an electrostatic charge image, an electrostatic charge image developer, a toner cartridge, a process cartridge, and an image forming apparatus.

  Dispersions using crystalline polyester resins are used for various purposes such as paper coating and hot melt adhesives, but crystalline polyester resin dispersions can be used in various ways to increase storage stability. It is disclosed. Here, the storage stability is generally evaluated by leaving the dispersion under a certain temperature and checking the stability of the particle size. However, in reality, day and night, indoors and outdoors, seasons, inside and outside the vehicle during transportation. There are various temperature fluctuation factors, and there is a demand for a dispersion having a stable particle size against temperature changes.

  For example, a crystalline polyester resin having a melting point of 80 ° C. or higher and an ionic group concentration of 5 mgKOH / g or more and 30 mgKOH / g or less is dispersed, and the crystalline polyester resin has a particle diameter of 30 nm or more and 250 nm or less. A polyester resin aqueous dispersion is disclosed (for example, see Patent Document 1). It is disclosed that the aqueous dispersion of polyester resin is excellent in storage stability and coating property, and an emulsion having a narrow particle size distribution can be obtained.

  In addition, (a) a step of dispersing a resin having an acid group in a basic aqueous medium at a temperature lower than the softening point of the resin; and (b) a dispersion obtained in the step (a). A step of neutralizing at a temperature above the glass transition temperature of the resin and below the softening point; And a step of emulsifying the resin in an aqueous medium by adding an aqueous solution at a temperature of 5 ° C. (see, for example, Patent Document 2).

  On the other hand, many methods for producing toner using a crystalline polyester resin dispersion have been disclosed. For example, a step of neutralizing a binder resin containing a crystalline polyester resin and a colorant and containing a crystalline polyester resin having an acid group (neutralization step) in a molten state, and (emulsification step) A step of bringing the conjugated binder resin into contact with an aqueous medium in a molten state to prepare a dispersion having an average particle size of 0.02 μm or more and 2 μm or less of the dispersed particles mainly composed of the binder resin; Agglomeration step) a step of aggregating the dispersed particles in the dispersion prepared in the emulsification step to form agglomerated particles having at least a binder resin and a colorant as constituent components; and (unification step) the agglomerated particles A method for producing an electrophotographic toner comprising: adding the colorant in at least one of a neutralizing step, an emulsifying step, and an aggregating step. Are disclosed (for example, And Patent Document 3).

Further, the toner includes a crystalline polyester resin and a release agent, and there is a structure in which the crystalline resin polyester resin is in contact with the release agent on the cross section of the ruthenium-dyed toner, and the cross-sectional area of the structure Is 40, 100 ≦ A / (A + B + C) ≦ 70, 10 ≦ 100 × B / (A + B + C, where A is the cross-sectional area of the release agent alone and B is the cross-sectional area of the crystalline resin polyester resin alone. ) ≦ 30, 20 ≦ 100 × C / (A + B + C) ≦ 30 is disclosed (for example, see Patent Document 4).
JP 2007-277497 A JP 2007-106906 A JP 2006-18227 A JP 2008-33057 A

An object of the present invention is to provide a crystalline polyester resin dispersion in which agglomeration of the crystalline polyester resin is suppressed and change in the particle size of the crystalline polyester resin and precipitation in the dispersion are prevented, and the crystalline polyester resin dispersion It is in providing the manufacturing method of the crystalline polyester resin dispersion liquid which can be manufactured easily.
In addition, the viscosity (particularly thixotropic property) at the time of toner production is reduced and productivity is improved, and a uniform coating layer is formed by improving agitation and mixing properties, thereby improving the strength against mechanical stress. Toner for electrostatic charge image development and electrostatic charge image developer, toner cartridge that facilitates supply of electrostatic charge image development toner and enhances the maintenance of the above characteristics, easy handling of electrostatic charge image developer, various It is an object of the present invention to provide a process cartridge capable of enhancing the adaptability to an image forming apparatus having the above structure, and an image forming apparatus having improved strength against mechanical stress.

The above-mentioned subject is achieved by the following present invention.
That is, the invention according to claim 1
The crystalline polyester resin is dispersed in an aqueous medium,
When the titration curve was drawn with the horizontal axis representing the change in pH when titrated with sodium hydroxide and the vertical axis representing the value obtained by differentiating the pH by the amount of sodium hydroxide added dropwise, the titration curve was pH 2 It is a crystalline polyester resin dispersion characterized by having peaks in the region of 0.5 or more and pH 4.5 or less and the region of pH 5.0 or more and pH 7.0 or less.

The invention according to claim 2
The peak in the region of pH 2.5 or more and pH 4.5 or less is peak (1), the peak in the region of pH 5.0 or more and pH 7.0 or less is peak (2), the height P1 of peak (1), 2. The crystalline polyester resin dispersion according to claim 1, wherein the height P2 of 2) satisfies the relationship of the following formula (I).
Formula (I) 1.0 <P1 / P2 <5.0

The invention according to claim 3
3. The crystal according to claim 1, wherein the crystalline polyester resin has a volume average particle diameter D50v of 100 nm to 300 nm and a particle size distribution index GSDv of 1.0 to 1.3. It is a dispersible polyester resin dispersion.

The invention according to claim 4
A step of preparing a solution by stirring and dissolving a crystalline polyester resin and a solvent in a temperature range of −15 ° C. or higher and + 15 ° C. or lower of the melting point of the crystalline polyester resin and lower than the boiling point of the solvent. When,
Adding a neutralizing agent to the solution;
A step of mixing and stirring the solution to which the neutralizing agent is added and an aqueous medium to prepare an emulsion;
Cooling the emulsion to a recrystallization temperature of the crystalline polyester resin to -5 ° C or lower;
And a step of removing the solvent from the emulsion after cooling. The method for producing a crystalline polyester resin dispersion, comprising:

The invention according to claim 5
An electrostatic charge image developing toner prepared by using the crystalline polyester resin dispersion according to any one of claims 1 to 3.

The invention according to claim 6
An electrostatic image developer comprising at least a toner, wherein the toner is the electrostatic image developing toner according to claim 5.

The invention according to claim 7 provides:
A toner cartridge comprising at least toner, wherein the toner is the electrostatic image developing toner according to claim 5.

The invention according to claim 8 provides:
A process cartridge comprising at least a developer holder and containing the electrostatic image developer according to claim 6.

The invention according to claim 9 is:
An image carrier, development means for developing the electrostatic image formed on the image carrier as a toner image with the electrostatic image developer according to claim 6, and a toner image formed on the image carrier. An image forming apparatus comprising: transfer means for transferring onto a recording medium; and fixing means for fixing a toner image transferred onto the recording medium.

  According to the first aspect of the present invention, the aggregation of the crystalline polyester resin is suppressed as compared to the case where the peak in the titration curve is one, and the change in the particle size of the crystalline polyester resin and the precipitation in the dispersion liquid are suppressed. Is prevented.

  According to the invention of claim 2, the aggregation of the crystalline polyester resin is suppressed compared to the case where the relational expression (I) between the peak (1) and the peak (2) is not satisfied, and the particle size of the crystalline polyester resin is reduced. Changes and sedimentation in the dispersion are prevented.

  According to the invention of claim 3, the aggregation of the crystalline polyester resin is suppressed and the change in the particle size of the crystalline polyester resin is suppressed as compared with the case where the volume average particle diameter D50v and the particle size distribution index GSDv of the crystalline polyester resin are not taken into consideration. And settling in the dispersion is prevented.

  According to the invention of claim 4, a crystalline polyester resin dispersion liquid in which aggregation of the crystalline polyester resin is suppressed and a change in the particle size of the crystalline polyester resin and sedimentation in the dispersion liquid is prevented is easily produced. can do.

  According to the invention of claim 5, compared to the case where the crystalline polyester resin dispersion to be used does not have the above-described configuration, the viscosity at the time of toner production is reduced and the productivity is improved, and the strength of the toner against mechanical stress is increased. improves.

  According to the sixth aspect of the present invention, the toner is more resistant to mechanical stress than the case without this configuration.

  According to the seventh aspect of the present invention, it is possible to facilitate the supply of the electrostatic image developing toner whose strength against mechanical stress is improved and to improve the maintainability of the above characteristics as compared with the case where this configuration is not provided. it can.

  According to the eighth aspect of the present invention, compared to the case without this configuration, the toner can easily handle the electrostatic image developer whose strength against mechanical stress is improved, and can be applied to image forming apparatuses having various configurations. Can increase the sex.

  According to the ninth aspect of the present invention, the strength of the toner against mechanical stress is improved as compared with the case where this configuration is not provided.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<First embodiment: Crystalline polyester resin dispersion>
In the crystalline polyester resin dispersion according to the first embodiment, the crystalline polyester resin is dispersed in an aqueous medium (hereinafter simply referred to as “aqueous medium”), and the pH of the crystalline polyester resin dispersion when titrated with sodium hydroxide is measured. When a titration curve is drawn with the horizontal axis representing the change and the vertical axis representing the value obtained by differentiating the pH with the amount of sodium hydroxide added, the titration curve has a pH range of 2.5 to 4.5. It has a peak in each region of pH 5.0 or more and pH 7.0 or less.

Conventionally, in the crystalline polyester resin dispersion liquid, there has been a problem that the particle diameter change of the crystalline polyester resin occurs due to the aggregation of the crystalline polyester resin, or sedimentation occurs in the dispersion liquid. In particular, when left in an environment where the temperature changes, the particle size change of the crystalline polyester resin and the precipitation in the dispersion of the crystalline polyester resin occurred remarkably. In addition, even when pressure was applied to the crystalline polyester resin dispersion by pumping or the like, the phenomenon that the particle size of the crystalline polyester resin changed was significant.
With regard to this problem, the present inventors presumed that the cause was a lack of repulsive force due to carboxylic acid, and studied a method for increasing the repulsive force due to carboxylic acid. Specifically, the change in pH when the crystalline polyester resin dispersion is titrated with a sodium hydroxide aqueous solution is plotted on the horizontal axis, and the value obtained by differentiating the pH by the amount of sodium hydroxide dropped is plotted on the vertical axis. The relationship between the measured titration curve and the storage stability of the crystalline polyester resin dispersion was examined in detail.
As a result, the crystalline polyester resin dispersion having titration curves each having a peak in the region of pH 2.5 or more and pH 4.5 or less and the region of pH 5.0 or more and pH 7.0 or less is stored in an environment where the temperature changes. Crystalline polyester resin when particle size change of crystalline polyester resin is suppressed and stored (left) in an environment where temperature changes even when stressed by a pump or the like. It was found that sedimentation in the dispersion liquid was suppressed and the storage stability was excellent.

The reason is not clear, but it is presumed as follows.
In the titration curve, the crystalline polyester resin dispersion having peaks in the region of pH 2.5 or more and pH 4.5 or less and in the region of pH 5.0 or more and pH 7.0 or less is present on the particle surface of the crystalline polyester resin. It is presumed that the density of the carboxylic acid is dense. Compared to the case of having one peak, the crystalline polyester resin dispersion having two peaks changes its dissociation state when another carboxylic acid is present, and the second peak appears. That is, since the carboxylic acid is dense on the particle surface of the crystalline polyester resin, the repulsive force between the particles is increased, and it is presumed that the storage stability is excellent as described above.
On the other hand, from the viewpoint of settling in the crystalline polyester resin dispersion, the particle size of the crystalline polyester resin is preferably small. However, when the particle size is small, the distance between the particles in the dispersion is reduced. There is also a drawback that self-aggregation is likely to occur. However, in the crystalline polyester resin dispersion having two peaks as described above, it is assumed that the self-aggregation hardly occurs even if the particle size is small because the repulsive force between the particles is strong.

  Conventionally, when a toner is produced using a crystalline polyester resin dispersion, there has been a problem that the viscosity of the system tends to increase when the crystalline polyester resin dispersion is aggregated in a medium. If the viscosity of the system is high, the stirrability deteriorates, resulting in problems such as generation of coarse powders and fine powders. In addition, in order to reduce the viscosity of the system, it is necessary to lower the solid content concentration, and productivity is reduced. There was a problem of lowering.

However, when an electrostatic charge developing toner is produced by a method such as an aggregation coalescence method using the crystalline polyester resin dispersion according to the first embodiment, the viscosity of the system in the aggregation step can be reduced. As a result, it has been found that the dispersibility after stirring is improved and coarse powder and fine powder are reduced, and the solid content concentration during aggregation is increased, and as a result, toner productivity is improved.
The reason why the viscosity of the system during agglomeration can be lowered is not clear, but is presumed as follows. Since the carboxylic acid is densely present on the particle surface of the crystalline polyester resin, the hydrophilicity of the particle surface is strong and good wettability with water is obtained. Accordingly, it is presumed that even if the crystalline polyester resin is present as particles in the aqueous medium, it is difficult to become a resistance point.

  Hereinafter, the crystalline polyester resin dispersion according to the first embodiment will be described in more detail.

(Titration curve)
As described above, the crystalline polyester resin dispersion according to the first embodiment has a value obtained by differentiating the pH change when titrated with sodium hydroxide, with the amount of sodium hydroxide dropped from the pH, on the horizontal axis. When the titration curve is drawn on the vertical axis, it is essential that the titration curve has peaks in the region of pH 2.5 or more and pH 4.5 or less and in the region of pH 5.0 or more and pH 7.0 or less, respectively. To do.

  Here, the titration curve of the crystalline polyester resin dispersion is measured as follows. All titration operations are performed in an environment of room temperature 22 ° C. ± 1 ° C. This is because if the temperature changes, the titer also changes. Therefore, the crystalline polyester resin dispersion, ion-exchanged water, 0.3M nitric acid, 0.3M sodium hydroxide aqueous solution, and 20% by mass Dowfax2A1 aqueous solution (anionic surfactant) to be used had a room temperature of 22 ° C. ± 1 ° C. in advance. Let stand for 48 hours or more in the environment to keep the temperature stable.

  First, ion-exchanged water having a conductivity of 1.5 μS / cm or less is added to the crystalline polyester resin dispersion to adjust the solid content concentration to 10% by mass. Add 5 wt% of surfactant (the active ingredient of Dowfax2A1 is calculated as 46 wt%) and mix.

  200 g of the obtained dispersion is collected in a 500 ml beaker and stirred using a magnetic stirrer. Next, while setting a pH meter in a beaker and recording the pH of the dispersion, the pH is lowered to 2.5 using 0.3 M nitric acid, and after stirring for 10 minutes, the pH is higher than 2.5. If so, the pH is lowered again to 2.5. Five minutes after the pH adjustment again, 0.25 ml of 0.3M sodium hydroxide aqueous solution is dropped, and the pH after dropping is recorded. The pH value is taken as a reading value 15 seconds after dropping the aqueous sodium hydroxide solution. Furthermore, 0.3M sodium hydroxide aqueous solution is dripped continuously 0.25 ml at a time, The pH at that time is recorded, and the data of pH change with respect to 0.3M sodium hydroxide aqueous solution dripping amount are obtained. From this data, a value [ΔpH / 0.25 [ml]] obtained by dividing the amount of change in pH after the 0.3M sodium hydroxide aqueous solution is dropped by the amount of the 0.3M sodium hydroxide aqueous solution dropped is calculated. The calculated ΔpH / 0.25 [ml] value is plotted on a graph with respect to the pH before dropping the 0.3 M aqueous sodium hydroxide solution to create a titration curve.

  Here, M of 0.3 M is a symbol of Moller, and the 0.3 M sodium hydroxide aqueous solution refers to an aqueous solution in which 0.3 mol of sodium hydroxide is dissolved in 1 liter of water.

  In the created titration curve, the peak in the region from pH 2.5 to pH 4.5 is peak (1), the peak in the region from pH 5.0 to pH 7.0 is peak (2), and peak (1) and peak ( 2) the position (pH) and the height of peak (1) (value of ΔpH / 0.1 [ml]) P1 and the height of peak (2) (value of ΔpH / 0.1 [ml]) P2. read.

It is preferable that the relationship between P1 and P2 satisfies the following formula (I).
Formula (I) 1.0 <P1 / P2 <5.0

If P1 / P2 <5.0, P2 does not become too small, that is, it is presumed that the carboxylic acid on the particle surface is kept in a good dense state, and the aggregation of the crystalline polyester resin is more effectively suppressed. Thus, the change in the particle size of the crystalline polyester resin and sedimentation in the dispersion are prevented. On the other hand, when P1 / P2 <1.0, P2 does not become too large, that is, it is presumed that the carboxylic acid on the particle surface is not too dense. Thereby, the phenomenon that the crystalline polyester resin tends to be stabilized and becomes thermally unstable and the particle size changes is suitably suppressed.
The numerical range of P1 / P2 is more preferably 1.3 or more and 4.0 or less, and particularly preferably 1.5 or more and 3.0 or less.

  Here, the definition of the “peak” will be described. The peak refers to the maximum value (the point at which the state changes from increasing to decreasing) appearing in the titration curve drawn by the above method. However, from the viewpoint of excluding the maximum value that may appear due to measurement error, etc., the peak is defined as the “peak” in this specification by performing three measurements and measuring the maximum value that appears in all three measurements. To do. In each measurement, the pH value at which the peak appears may be slightly shifted, but if the pH value is within ± 0.15, the peak appears at the same pH. If the same sample is repeatedly measured, the concentration of the neutralizing agent changes and the peak position and intensity change greatly. Therefore, three measurements are performed using a newly prepared sample. Thus, the maximum peak appearing in the region of pH 2.5 or more and pH 4.5 or less that appeared in three measurements is peak P1, and the maximum peak that appears in the region of pH 5.0 or more and pH 7.0 or less is peaked. It is defined as P2.

  The peak in the titration curve is not particularly limited, but can be adjusted, for example, by controlling the cooling operation in the “cooling step” in the manufacturing method according to the second embodiment described later. Moreover, the relationship of P1 / P2 can be adjusted by controlling the cooling rate in the cooling step. Details will be described later.

(Volume average particle diameter D50v, particle size distribution index GSDv)
In the crystalline polyester resin dispersion according to the first embodiment, the volume average particle diameter D50v of the crystalline polyester resin in the dispersion is preferably from 100 nm to 300 nm. When D50v is 100 nm or more, self-aggregation of particles is suitably suppressed. Moreover, sedimentation of the particle | grains in a dispersion liquid is suppressed suitably because D50v is 300 nm or less. In addition, More preferably, they are 120 nm or more and 250 nm or less, Especially preferably, they are 140 nm or more and 200 nm or less.

  The particle size distribution index GSDv of the crystalline polyester resin in the dispersion is preferably 1.0 or more and 1.3 or less. When the particle size distribution is not too wide, generation of coarse powder and fine powder is suppressed, and sedimentation of particles in the dispersion and self-aggregation of the particles are preferably suppressed.

  By using a crystalline polyester resin dispersion that satisfies the range of the volume average particle diameter D50v and the particle size distribution index GSDv, for example, when the temperature is continuously changed from 5 ° C. to 40 ° C. every 24 hours. In addition, storage stability is improved.

Here, a method for measuring the volume average particle diameter D50v and the particle size distribution index GSDv of the crystalline polyester resin in the dispersion will be described.
The volume average particle size D50v and the particle size distribution index GSDv are measured using a laser diffraction particle size distribution measuring device (LS13 320: manufactured by Beckman Coulter, Inc.). As a measuring method, the crystalline polyester resin dispersion is adjusted with ion-exchanged water so that the solid content becomes 1% by mass, and this is put into a cell until an appropriate concentration (displayed concentration value 40 to 45) is obtained. Wait 10 seconds and measure when the concentration in the cell is stable.
For the divided particle size range (channel), a cumulative distribution is drawn from the small diameter side with respect to the divided particle size range (channel). The particle diameter to be defined is defined as a volume average particle diameter D50v, and the particle diameter that is 84% cumulative in volume is defined as a volume average particle diameter D84v. The volume average particle diameter is the D50v. Also, using these, the volume average particle size distribution index (GSDv) is calculated from (D84v / D16v) ^1/2 .

(Crystalline polyester resin)
As described above, the crystalline polyester resin dispersion according to the first embodiment is obtained by dispersing the crystalline polyester resin in an aqueous medium. Hereinafter, the crystalline polyester resin used in the crystalline polyester resin dispersion according to the first embodiment will be described.

  The crystalline polyester resin is synthesized from a divalent acid (dicarboxylic acid) component and a divalent alcohol (diol) component, and “crystalline polyester resin” refers to differential scanning calorimetry (DSC). In FIG. 4, it is not a step-like change in endothermic amount, but has a clear endothermic peak. In the case of a polymer obtained by copolymerizing other components with respect to the main chain of the crystalline polyester resin, when the other components are 50% by mass or less, this copolymer is also called a crystalline polyester resin.

In the crystalline polyester resin, examples of the acid for becoming an acid-derived constituent component include various dicarboxylic acids, but the dicarboxylic acid as the acid-derived constituent component is not limited to one type, and two or more types of dicarboxylic acids may be used. Dicarboxylic acid-derived components may be included. Further, the dicarboxylic acid may contain a sulfonic acid group in order to improve the emulsifiability in the emulsion aggregation method.
The “acid-derived constituent component” refers to a constituent portion that was an acid component before the synthesis of the polyester resin, and the “alcohol-derived constituent component” below is an alcohol component before the synthesis of the polyester resin. Refers to the constituent parts.

The dicarboxylic acid is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear carboxylic acid. Examples of the linear carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10- Decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, Or lower alkyl esters and acid anhydrides thereof.
Among them, those having 6 to 10 carbon atoms are preferable. In order to increase the crystallinity, these linear dicarboxylic acids are preferably used in an amount of 95 mol% or more, more preferably 98 mol% or more of the acid component.

  As the acid-derived constituent component, in addition to the aliphatic dicarboxylic acid-derived constituent component, a constituent component such as a dicarboxylic acid-derived constituent component having a sulfonic acid group can be included. Further, when the toner particles are prepared by emulsifying or suspending the entire resin in water, if the sulfonic acid group is present, it can be emulsified or suspended without using a surfactant as described later.

  Examples of the dicarboxylic acid having a sulfone group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, sodium 5-sulfoisophthalate is preferable from the viewpoint of productivity. The content of the dicarboxylic acid having a sulfonic acid group is preferably 2.0 constituent mol% or less, and more preferably 1.0 constituent mol% or less. The above “constitutive mol%” refers to a percentage when each constituent component (acid-derived constituent component, alcohol-derived constituent component) in the polyester resin is 1 unit (mol).

  In the crystalline polyester resin, an aliphatic dialcohol is desirable as an alcohol to be a constituent component derived from alcohol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, 1,12-undecanediol, Examples include 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol. Among them, those having 2 to 10 carbon atoms are preferable. In order to enhance crystallinity, these linear dialcohols are preferably used in an amount of 95 mol% or more, more preferably 98 mol% or more of the alcohol constituent.

  Examples of other divalent dialcohols include, for example, bisphenol A, hydrogenated bisphenol A, ethylene oxide or (and) propylene oxide adducts of bisphenol A, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, Examples include propylene glycol, dipropylene glycol, 1,3-butanediol, and neopentyl glycol. These may be used individually by 1 type and may use 2 or more types together.

  If necessary, monovalent acids such as acetic acid and benzoic acid, monovalent alcohols such as cyclohexanol and benzyl alcohol, benzenetricarboxylic acid, and naphthalenetricarboxylic acid for the purpose of adjusting the acid value and hydroxyl value. Trivalent alcohols such as acids and the like, anhydrides thereof, lower alkyl esters thereof, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like can also be used.

  Other monomers are not particularly limited. For example, a conventionally known divalent or carboxylic acid which is a monomer component described in Polymer Data Handbook: Basic Edition (edited by Polymer Society: Bafukan) There are divalent alcohols. Specific examples of these monomer components include divalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and cyclohexanedicarboxylic acid. And dibasic acids such as these, anhydrides thereof, and lower alkyl esters thereof. These may be used individually by 1 type and may use 2 or more types together.

Crystalline polyester resins can be combined in any combination from the monomer components described above, for example, polycondensation (chemical doujin), polymer experimental studies (polycondensation and polyaddition: Kyoritsu Publishing) and polyester resin handbook (Nikkan Kogyo Shimbun) Etc.) can be synthesized by using a conventionally known method, and a transesterification method, a direct polycondensation method or the like can be used alone or in combination.
Specifically, the polymerization can be carried out at a polymerization temperature of 140 ° C. or higher and 270 ° C. or lower. The reaction system is reduced in pressure as necessary, and the reaction is carried out while removing water and alcohol generated during the condensation. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizing solvent and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. In the case where a monomer having poor compatibility exists in the copolymerization reaction, it is preferable that the monomer having poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polycondensed together with the main component. The molar ratio (acid component / alcohol component) at the time of reacting the acid component and the alcohol component varies depending on the reaction conditions and the like, and thus cannot be generally stated. 1 to 1 / 0.9. In the case of a transesterification reaction, an excessive amount of a monomer that can be distilled off under vacuum, such as ethylene glycol, propylene glycol, neopentyl glycol, and cyclohexanedimethanol, may be used.

Catalysts that can be used in the production of crystalline polyester resins include titanium acetate, titanium propionate, titanium hexanoate, titanium octanoate and other aliphatic monocarboxylic acid titanium, titanium oxalate, titanium succinate, titanium maleate, Aliphatic titanium dicarboxylates such as titanium adipate and titanium sebacate, titanium aliphatic tricarboxylates such as titanium hexanetricarboxylate and isooctanetricarboxylic acid, titanium aliphatic polycarboxylates such as titanium octanetetracarboxylate and titanium decanetetracarboxylate , Titanium monocarboxylic acid such as titanium benzoate, titanium phthalate, titanium terephthalate, titanium isophthalate, titanium naphthalene dicarboxylate, titanium biphenyl dicarboxylate, anthracene Aromatic dicarboxylic acid titanium such as titanium oxide; Aromatic tricarboxylic acid titanium such as titanium trimellitic acid and titanium naphthalenetricarboxylate; Aromatic tetracarboxylic acid titanium such as benzenetetracarboxylic acid titanium and naphthalenetetracarboxylic acid titanium; Titanium aromatic carboxylates, titanium titanates of aliphatic titanium carboxylates and titanium aromatic carboxylates and alkali metal salts thereof, titanium halides such as dichlorotitanium, trichlorotitanium, tetrachlorotitanium, tetrabromotitanium, Tetraalkoxy titanium such as tetrabutoxy titanium (titanium tetrabutoxide), tetraoctoxy titanium, tetrastearyloxy titanium, titanium acetylacetonate, titanium diisopropoxide bisacetylacetonate, Tan triethanolaminate, titanium-containing catalysts, such as.
However, the titanium-containing catalyst is mainly used as a catalyst, and other catalysts may be mixed and used. As other catalysts, those according to the amorphous polyester resin can be used.

  The catalyst is preferably added in the range of 0.02 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the monomer component during the polymerization. However, when the catalyst is used as a mixture, the content of the titanium-containing catalyst is preferably 70% by mass or more, more preferably a titanium-containing catalyst.

  The melting point of the crystalline polyester resin is desirably in the range of 50 ° C. or higher and 120 ° C. or lower, and more preferably in the range of 60 or higher and 110 ° C. or lower.

The differential thermal analysis for determining the melting point is performed by differential scanning calorimetry based on ASTM D3418-8. This measurement was performed as follows.
That is, first, a toner to be measured is set in a differential scanning calorimeter (DSC-50) manufactured by Shimadzu Corporation equipped with an automatic tangential processing system, liquid nitrogen is set as a cooling medium, and a temperature rising rate of 10 ° C./min. To 20 ° C to 150 ° C (first heating process) to obtain the relationship between temperature (° C) and calorie (mW), and then cooled to 0 ° C at a temperature drop rate of -10 ° C / min. The sample was heated again to 150 ° C. at a rate of temperature increase of 10 ° C./min (second temperature increase process), and data was collected. In addition, it hold | maintained for 5 minutes each at 0 degreeC and 150 degreeC. The endothermic peak temperature in the second temperature raising process was regarded as the melting point. The crystalline resin may show a plurality of melting peaks, but the maximum peak was regarded as the melting point.

  The molecular weight of the crystalline polyester resin is preferably in the range of 5000 to 100,000 in weight average molecular weight (Mw), more preferably 10,000 or more, as determined by GPC method using tetrahydrofuran (THF) soluble content. The number average molecular weight (Mn) is preferably in the range of 2000 to 30000, more preferably in the range of 5000 to 15000. The molecular weight distribution Mw / Mn is desirably in the range of 1.5 to 20, more preferably in the range of 2 to 5. When measuring the molecular weight, the crystalline resin is poorly soluble in THF, so it is preferable to dissolve by heating in a 70 ° C. hot water bath.

  The crystalline polyester resin preferably has an acid value in the range of 4 mgKOH / g to 20 mgKOH / g, and more preferably in the range of 6 mgKOH / g to 15 mgKOH / g. The hydroxyl value is preferably in the range of 3 mgKOH / g to 30 mgKOH / g, and more preferably in the range of 5 mgKOH / g to 15 mgKOH / g.

(Aqueous medium)
Next, the aqueous medium used for the crystalline polyester resin dispersion according to the first embodiment will be described.
As the aqueous medium, for example, water such as distilled water or ion exchange water is used.

, Alcohols, acetate esters, ketones, and mixtures thereof. Although these may be used individually by 1 type or may use 2 or more types together, it is necessary for the ratio of water to be 50 mass% or more. Although a surfactant may be included, it is better not to use the surfactant as much as possible because the surfactant may deteriorate the toner characteristics.

The surfactant contained in the aqueous medium is not particularly limited. For example, anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; amine salt type Examples include cationic surfactants such as quaternary ammonium salt type; nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, anionic surfactants and cationic surfactants are preferable.
Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like. Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.

  The crystalline polyester resin dispersion according to the first embodiment is not particularly limited, but depends on the method for producing a crystalline polyester resin dispersion according to the second embodiment below using a method called a phase inversion emulsification method. Simple and reliable production.

<Second Embodiment: Method for Producing Crystalline Polyester Resin Dispersion>
In the phase inversion emulsification method, the crystalline polyester resin is dissolved in a solvent, a neutralizing agent is added and, if necessary, a dispersion stabilizer is added, and an aqueous solvent is added dropwise with stirring. After obtaining the emulsified particles, the solvent in the resin dispersion is removed to obtain an emulsified liquid.

  In the method for producing a crystalline polyester resin dispersion according to the second embodiment, the crystalline polyester resin and the solvent are in a temperature range of −15 ° C. to + 15 ° C. of the melting point of the crystalline polyester resin and the solvent. A step of preparing a solution by stirring and dissolving at a temperature below the boiling point (solution preparation step), a step of adding a neutralizing agent to the solution (neutralizing agent adding step), and the neutralizing agent A step of mixing and stirring the added solution and an aqueous medium to prepare an emulsion (emulsion solution preparation step), and a step of cooling the emulsion to a recrystallization temperature of the crystalline polyester resin to -5 ° C ( A cooling step) and a step of removing the solvent from the cooled emulsion (solvent removing step).

Hereinafter, the manufacturing method of the crystalline polyester resin dispersion according to the second embodiment will be described in detail with an example.
(1) Solution Preparation Step In the phase inversion emulsification method, first, a crystalline polyester resin and a solvent are put into a reaction vessel equipped with a condenser, a stirrer, and a thermometer, and the melting point of the crystalline polyester resin is −15 ° C. The resin is dissolved by heating and stirring at a temperature range of the melting point of + 15 ° C. and below the boiling point of the solvent used.

  The heating temperature is more preferably a temperature range from the melting point of the crystalline polyester resin −10 ° C. to the melting point of the resin + 10 ° C. and less than the boiling point of the solvent used.

  Examples of the solvent for dissolving the crystalline polyester resin include formic acid esters, acetic acid esters, butyric acid esters, ketones, ethers, benzenes, and halogenated carbons. Specifically, esters such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl such as formic acid, acetic acid, butyric acid, acetone, MEK, MPK, MIPK, MBK, MIBK Such as methyl ketones, ethers such as diethyl ether and diisopropyl ether, heterocyclic substituents such as toluene, xylene and benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene , Halogenated carbons such as chloroform, monochlorobenzene, dichloroethylidene and the like can be used alone or in combination of two or more. Of these, acetates, methyl ketones and ethers which are low-boiling solvents are usually preferably used. In particular, alcohols such as acetone, methyl ethyl ketone, acetic acid, ethyl acetate, butyl acetate, toluene and isopropyl alcohol are preferred, and methyl ethyl ketone is most preferred. It is desirable to use a solvent having a relatively high volatility so that the solvent does not remain in the resin particles. The amount of these solvents to be used is 20% by mass or more and 200% by mass or less, and more preferably 40% by mass or more and 150% by mass or less with respect to the resin amount.

(2) Neutralizing agent addition step Next, a neutralizing agent is added and mixed well. The total amount of the neutralizing agent and the mixing time are preferably 5 minutes or more and 300 minutes or less. If it is too short, it cannot be mixed sufficiently, and if it is too long, productivity deteriorates.
The temperature inside the container when adding the neutralizing agent may be the same as the melting temperature of the resin, but when a volatile substance such as ammonia is used as the neutralizing agent, the viewpoint of suppressing the added neutralizing agent from volatilizing. Therefore, the temperature is preferably from the melting point of the crystalline polyester resin to -15 ° C to the melting point of the resin to -5 ° C and lower than the boiling point of the solvent used.

  The neutralizing agent to be used is preferably a basic aqueous solution, and examples thereof include organic salts such as aqueous ammonia, diethylamine, triethylamine, and isopropylamine, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Ammonia water is particularly preferable.

(3) Emulsion Solution Preparation Step Next, the emulsion is phase-shifted by applying a stirring shear while adding an aqueous medium to obtain an O / W type emulsion (emulsion) of the crystalline polyester resin.

(4) Cooling Step After obtaining an O / W type emulsion (emulsion) of the crystalline polyester resin, the crystalline polyester resin is cooled to a recrystallization temperature of −5 ° C. or lower. It should be noted that by controlling the cooling operation in this cooling step, whether or not there are peaks in the above-described titration curve (in the region of pH 2.5 to pH 4.5 and in the region of pH 5.0 to pH 7.0, respectively). Is adjusted. Further, by adjusting the cooling rate, the height P1 of the peak (1) and the height P2 of the peak (2) in the titration curve are controlled. That is, when the cooling rate is increased, the value of P1 / P2 increases, and when the cooling rate is decreased, P1 / P2 decreases. The range of the cooling rate is preferably from 0.1 ° C./min to 5 ° C./min, more preferably from 0.2 ° C./min to 2 ° C./min, and more preferably from 0.3 ° C./min to 1. 0 ° C./min or less is particularly preferable.

  Moreover, the cooling attainment temperature in the cooling step is preferably 0 ° C. or higher and the recrystallization temperature of the crystalline polyester resin is −10 ° C. or lower, preferably 0 ° C. or higher and the recrystallization temperature of the crystalline polyester resin −15 ° C. or lower. It is particularly preferred that

Here, the recrystallization temperature of the crystalline polyester resin is measured as follows.
In the differential scanning calorimetry for determining the melting point, the toner to be measured is set in a differential scanning calorimeter (DSC-50) manufactured by Shimadzu Corporation equipped with an automatic tangential processing system, and liquid nitrogen is set as a cooling medium. Heating from 20 ° C. to 150 ° C. at a rate of temperature increase of 10 ° C./min (first temperature increase process), the relationship between temperature (° C.) and calorie (mW) was determined, and then −10 ° C./min The exothermic peak temperature of the temperature drop spectrum when cooled to 0 ° C. at the temperature drop rate is defined as the recrystallization temperature of the crystalline polyester resin. There may be a plurality of exothermic peaks, but the maximum peak was regarded as the recrystallization temperature.

(5) Solvent removal step The thus-cooled O / W type emulsion (emulsion) is subjected to a heating operation, and further subjected to a decompression operation as necessary to remove the solvent, whereby a crystalline polyester resin dispersion is obtained. can get. The temperature as the heating operation is preferably a temperature of the melting point of the crystalline polyester resin of −50 ° C. or higher and lower than the melting point of the resin, more preferably a melting point of −25 ° C. or higher and a melting point of −5 ° C. or lower. . The higher the temperature, the better the solvent removal efficiency. However, if the temperature is higher than the melting point of the crystalline resin, the crystalline resin may be fused to the apparatus.
The pressure as the depressurization operation is preferably 50 kPa to 1 kPa, and particularly preferably 20 kPa to 5 kPa. The pressure here refers to a state of constant control. As the pressure is lowered, the solvent removal efficiency is improved. However, if the pressure is lowered too much, bumping of the solvent occurs. Therefore, it is preferable to increase the pressure when the remaining amount of the solvent is large and gradually decrease the pressure when the remaining amount of the solvent decreases.

  The crystalline polyester resin used in the second embodiment has a self-water dispersibility containing a functional group that can be anionic by neutralization, and a part or all of the functional group that can be hydrophilic is neutralized with a base. In addition, since a stable aqueous dispersion can be formed under the action of an aqueous medium, it can also be called an emulsion or an emulsion.

  Further, in the crystalline polyester resin dispersion produced by the second embodiment, the content of the crystalline polyester resin is not particularly limited, but is generally adjusted to 5% by mass or more and 50% by mass or less. It is preferable to adjust to 10% by mass or more and 30% by mass or less.

<Third embodiment: toner for developing electrostatic image>
The crystalline polyester resin dispersion according to the first embodiment can be particularly suitably used for production of an electrostatic image developing toner. Hereinafter, the electrostatic image developing toner prepared using the crystalline polyester resin dispersion according to the first embodiment will be described.

The electrostatic image developing toner according to the third embodiment (hereinafter sometimes simply referred to as “toner”) includes a binder resin, a colorant, a release agent, and the like, and at least as the binder resin. The crystalline polyester resin added by the crystalline polyester resin dispersion according to the first embodiment is contained.
Hereinafter, each component of the toner according to the third embodiment will be described.

(Binder resin: crystalline polyester resin)
The content of the crystalline polyester resin in the binder resin is not particularly limited, but is preferably in the range of 2% by mass to 20% by mass, and more preferably in the range of 2% by mass to 14% by mass.

In addition to the crystalline polyester resin, other resins can be used in combination with the binder resin as the crystalline resin. However, the main component of the crystalline resin is the crystalline polyester resin.
Other resins include amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (meth) in a binder resin component in a range of less than 3% by mass. ) Nonyl acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, (meth) Long chain alkyls such as oleyl acrylate and behenyl (meth) acrylate, vinyl resins using one or more of (meth) acrylic esters of alkenyl, or olefins such as ethylene, propylene, butadiene and isoprene , May be used in combination.

(Binder resin: Amorphous polyester resin)
In the toner according to the third embodiment, an amorphous polyester resin can be used in combination with the crystalline polyester resin as a binder resin. The amorphous polyester resin means a polyester resin that does not show an endothermic peak corresponding to a crystalline melting point in addition to a stepwise endothermic point corresponding to a glass transition in differential scanning calorimetry (DSC).

  A known polyester resin can be used as the amorphous polyester resin. The amorphous polyester resin is synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component. In addition, as said amorphous polyester resin, a commercial item may be used and what was synthesize | combined may be used. The amorphous polyester resin may be one kind of amorphous polyester resin, but may be a mixture of two or more kinds of polyester resins.

  The polyvalent carboxylic acid and polyhydric alcohol used for the amorphous polyester resin are not particularly limited, and are, for example, monomer components described in “Polymer Data Handbook: Basics” (Edition of Polymer Society, Bafukan) There are conventionally known divalent or trivalent or higher carboxylic acids and divalent or trivalent or higher alcohols.

Specific examples of these polymerizable monomer components include divalent carboxylic acids such as succinic acid, alkyl succinic acid, alkenyl succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacin. Dibasic acids such as acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, mesaconic acid, and their anhydrides, These lower alkyl esters, aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and the like can be mentioned. Of these compounds, terephthalic acid is preferably contained in an amount of 30 mol% or more of the acid component.
Examples of the trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polyhydric alcohol include divalent alcohols such as hydrogenated bisphenol A, bisphenol derivatives such as ethylene oxide and propylene oxide adducts of bisphenol A; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like. Cyclic aliphatic alcohols; linear diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol; 1,2-propanediol, Branched diols such as 1,3-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol; and the like, and bisphenol A ethylene oxide and propylene oxide adducts. Used to apply.

Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like. The amount of the trivalent or higher crosslinkable monomer used is 10 of the total monomer amount. It is desirable that it is less than mol%. These may be used individually by 1 type and may use 2 or more types together.
If necessary, monovalent acids such as acetic acid and benzoic acid, and monovalent alcohols such as cyclohexanol and benzyl alcohol can also be used for the purpose of adjusting the acid value and hydroxyl value.
Among these, monomers having a long-chain alkyl side chain (4 or more carbon atoms in the side chain) such as 1,2-hexanediol, alkyl succinic acid and alkenyl succinic acid, and anhydrides thereof are 2 mol% or more and 30 mol. % Of the monomer component is preferably included. Among them, it is preferable to contain alkyl succinic acid and alkenyl succinic acid having high hydrophobicity and their anhydrides.

  Examples of the alkyl succinic acid and alkenyl succinic acid and their anhydrides include, for example, n-butyl succinic acid, n-butenyl succinic acid, isobutyl succinic acid, isobutenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, Examples thereof include n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, and anhydrides and lower alkyl esters thereof.

  The alkyl succinic acid, alkenyl succinic acid and their anhydrides preferably have more alkyl groups and alkenyl groups than the constituent monomers used in the crystalline polyester resin. Of the above, n-dodecenyl succinic acid and its anhydride are most preferred.

Amorphous polyester resins can be used in any combination of the above monomer components, for example, polycondensation (chemical doujin), polymer experimental studies (polycondensation and polyaddition: Kyoritsu Publishing), and polyester resin handbook (Nikkan Kogyo Shimbun). And the like, and the transesterification method and the direct polycondensation method can be used alone or in combination.
Specifically, the polymerization can be carried out at a polymerization temperature of 140 ° C. or higher and 270 ° C. or lower. The reaction system is reduced in pressure as necessary, and the reaction is carried out while removing water and alcohol generated during the condensation. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizing solvent and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. In the case where a monomer having poor compatibility exists in the copolymerization reaction, it is preferable that the monomer having poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polycondensed together with the main component. The molar ratio (acid component / alcohol component) at the time of reacting the acid component and the alcohol component varies depending on the reaction conditions and the like, and thus cannot be generally stated. 1 to 1 / 0.9. In the case of a transesterification reaction, an excessive amount of a monomer that can be distilled off under vacuum, such as ethylene glycol, propylene glycol, neopentyl glycol, and cyclohexanedimethanol, may be used.

  Catalysts that can be used in the production of the amorphous polyester resin are tin-containing catalysts such as tin, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, and diphenyltin oxide. However, the tin-containing catalyst is mainly used as the catalyst, and other catalysts may be mixed and used.

  The tin-containing catalyst includes an organic tin-containing catalyst and an inorganic tin-containing catalyst. An organotin-containing catalyst is a compound having a Sn—C bond, and an inorganic tin-containing catalyst is a compound having no Sn—C bond. The tin-containing catalyst includes a di-type, a tri-type, and a tetra-type, and the di-type is preferably used, and an inorganic tin-containing catalyst is preferable.

  Examples of inorganic tin-containing catalysts include branched and unbranched types such as unbranched alkyltin tins such as tin diacetate, dihexanoate tin, dioctanoate tin and tin distearate, tin dineopentylate and tin di (2-ethylhexyl) ate. Examples include tin carboxylates such as tin alkylcarboxylate and tin oxalate, dialkoxytin such as dioctyloxytin and distearoxytin, tin halides such as tin chloride and tin bromide, tin oxide and tin sulfate. In particular, tin dioctanoate, tin distearate and tin oxide are preferred.

  Examples of the other catalysts include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metal compounds such as zinc, manganese, antimony, titanium, zirconium, and germanium; phosphorous acid compounds; phosphoric acid Compounds; and amine compounds; specifically, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride , Manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, zirconium tet Butoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, ethyl triphenylphosphonium bromide, Examples include compounds such as triethylamine and triphenylamine.

  The catalyst is preferably added in the range of 0.02 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the monomer component during the polymerization. However, when the catalyst is used as a mixture, the content of the tin-containing catalyst is preferably 70% by mass or more, and more preferably a tin-containing catalyst.

  As the molecular weight of the amorphous polyester resin, those having a weight average molecular weight (Mw) in the range of 12000 or more and 150,000 or less can be suitably used. Particularly, the Mw is in the range of 14000 or more and 40000 or less, and the number average molecular weight Mn is 4000 or more. The range of 20000 or less is more suitable, the Mw is preferably in the range of 16000 or more and 30000 or less, and the Mn is more preferably in the range of 5000 or more and 12000 or less. Further, Mw / Mn, which is an index of molecular weight distribution, is preferably in the range of 2 to 10.

Two types of amorphous polyester resins having different molecular weights can also be used. At this time, the Mw of one kind of amorphous polyester resin is preferably in the range of 35000 to 70000, and the Mn is preferably in the range of 5000 to 20000. The other amorphous polyester resin preferably has a Mw range of 10,000 to 25,000 and a Mn range of 3000 to 12000.
When two or more amorphous polyester resins are used, it is preferable that at least one of the above-mentioned alkyl succinic acid and alkenyl succinic acid and their anhydrides are included as constituents.

The molecular weight and molecular weight distribution can be measured by a method known per se, but are generally measured by gel permeation chromatography (hereinafter abbreviated as “GPC”).
The molecular weight distribution was measured under the following conditions. Tosoh Corporation HLC-8120GPC, SC-8020 apparatus was used as the GPC apparatus, the column was TSKgei, SuperHM-H (6.0 mm ID × 15 cm × 2), and the chromatographic THF manufactured by Wako Pure Chemical Industries, Ltd. was used as the eluent. (Tetrahydrofuran) was used. As experimental conditions, the sample concentration was 0.5%, and the flow rate was 0.6 ml / min. Sample injection volume 10 μl, measurement temperature 40 ° C., calibration curve is A-500, F-1, F-10, F-80, F-380, A-2500, F-4, F-40, F-128, Made from 10 samples of F-700. The data collection interval in sample analysis was 300 ms.

The amorphous polyester resin preferably has an acid value in the range of 5 mgKOH / g to 25 mgKOH / g, and more preferably in the range of 7 mgKOH / g to 20 mgKOH / g.
The acid value was measured by weighing 2 g of the resin and dissolving it in 160 ml of acetone-toluene, or dissolving it with insufficient heat, and then using this sample with the potentiometric titration method of JIS-K0070-1992. It was measured. The same applies to the following.
The hydroxyl value measured by JIS-K0070 is desirably in the range of 5 mgKOH / g to 40 mgKOH / g.

The glass transition temperature of the amorphous polyester resin is preferably in the range of 30 ° C. or higher and 90 ° C. or lower, and more preferably in the range of 50 ° C. or higher and 70 ° C. or lower.
The glass transition temperature of the amorphous polyester resin was raised from 0 to 150 ° C. at 10 ° C./min using a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001), and 150 Hold at 5 ° C. for 5 minutes, decrease the temperature from 150 ° C. to 0 ° C. using liquid nitrogen at −10 ° C./minute, hold at 0 ° C. for 5 minutes, and again increase the temperature from 0 ° C. to 150 at 10 ° C./minute. It can be defined as the onset temperature analyzed from the obtained endothermic curve during the second temperature increase.

Furthermore, the amorphous polyester resin preferably has a softening point of 80 ° C. or higher and 130 ° C. or lower, and more preferably 90 ° C. or higher and 120 ° C. or lower.
The softening point of the resin is as follows. Using a flow tester (manufactured by Shimadzu Corporation: CFT-500C), sample amount: 1.05 g, preheating: 300 ° C. at 65 ° C., plunger pressure: 0.980665 MPa, die size: diameter 1 mm, Temperature increase rate: Refers to an intermediate temperature between the melting start temperature and the melting end temperature measured under the condition of 1.0 ° C./min.

Further, when Tm is a temperature at which the loss elastic modulus G ″ (measured at a frequency of 1 rad / s and a strain amount of 20% or less) of the amorphous polyester resin is 10000 Pa, Tm is in a range of 80 ° C. or more and 150 ° C. or less. It is desirable to be in
Here, the loss elastic modulus of the resin is measured as follows. The measuring device is a rheometer manufactured by Rheometrics, trade name “RDA II” (RHIOS system ver. 4.3), the measuring plate is a parallel plate having a diameter of 8 mm, the zero point adjustment temperature is 90 ° C., the plate With a gap of 3.5 mm, a heating rate of 1 ° C. per minute, an initial measurement strain of 0.01% and a measurement start temperature of 30 ° C., the strain is adjusted so that the detected torque becomes about 10 gcm as the temperature rises. % And the measurement was terminated when the detected torque was below the lower limit of the guaranteed measurement value.

  The content of the amorphous polyester resin in the binder resin is not particularly limited, but is preferably in the range of 80% by mass to 98% by mass, and more preferably in the range of 86% by mass to 98% by mass.

In addition to the amorphous polyester resin, other resins can be used in combination with the binder resin as the amorphous resin. However, the main component of the amorphous resin is the amorphous polyester resin.
Examples of resins that can be used as other resins include polystyrene, poly (meth) acrylic acid, and esterified products thereof. Specifically, for example, styrenes such as styrene, parachlorostyrene, α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-acrylic acid 2- Esters having a vinyl group such as ethylhexyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; vinyl nitriles such as acrylonitrile and methacrylonitrile; vinyl methyl ether, vinyl Polymers of monomers such as vinyl ethers such as isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; polyolefins such as ethylene, propylene and butadiene; A copolymer obtained by combining the above or a mixture thereof can be mentioned, and further, an epoxy resin, a polyester resin, a polyurethane resin, a polyamide resin, a cellulose resin, a polyether resin, etc., a non-vinyl condensation resin, or these and the above-mentioned Mixtures with vinyl resins and graft polymers obtained when polymerizing vinyl monomers in the presence of these can also be used. Among them, styrene acrylic copolymer resin, particularly styrene butyl acrylate copolymer resin is preferable.

  In the toner according to the third embodiment, the acid value of the amorphous polyester resin and the acid value of the crystalline polyester resin used are both greater than 7 mgKOH / g and less than 20 mgKOH / g. It is desirable to make the value larger than the acid value of the crystalline polyester resin.

The acid values of the amorphous polyester resin and the crystalline polyester resin are determined from the components contained in the toner by the following method.
First, the crystalline resin and the amorphous resin in the toner are separated. First, the toner is left in a constant temperature bath at a temperature of 50 ° C. and a humidity of 55 RH% for 24 hours to cancel the thermal history of the toner. Thereafter, 10 g of toner is dissolved in 100 g of methyl ethyl ketone (MEK) at room temperature (20 ° C. or more and 25 ° C. or less). This is because when the toner contains a crystalline resin and an amorphous resin, almost only the amorphous resin is dissolved in MEK at room temperature. Therefore, the MEK-soluble component contains an amorphous resin including an amorphous polyester resin. Therefore, after the dissolution, centrifugation (centrifuge “H-18”, Kokusan Co., Ltd., 3500 revolutions) is performed. For 20 minutes), an amorphous polyester resin is obtained from the supernatant. The solid content after centrifugation is dissolved again in 100 g of MEK and centrifuged, and the supernatant is discarded. On the other hand, a crystalline polyester resin is obtained from a supernatant obtained by dissolving the solid content after centrifugation in 100 g of MEK under heating at 70 ° C. and separating it by centrifugation.
The acid values of both resins thus obtained are measured by the above method.

(Coloring agent)
Examples of the colorant used in the toner according to the third embodiment include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa Yellow, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Slen yellow, quinoline yellow, permanent yellow NCG and the like can be mentioned. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 185 or the like is preferably used.

  Magenta pigments include Bengala, Cadmium Red, Red Plum, Mercury Sulfide, Watch Young Red, Permanent Red 4R, Resol Red, Brilliantamine 3B, Brilliantamine 6B, Daypon Oil Red, Pyrazolone Red, Rhodamine B Lake, Lake Red C Pigment Red 31, 146, 147, 150, 176, 238, 269, and the like as Rose Bengal, Eoxin Red, Alizarin Lake, and Naphthol pigments. Pigments include quinacridone pigments. Examples include Red 122, 202, and 209. Among these, Pigment Red 185, 238, 269, and 122 are particularly preferable.

  As cyan pigments, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, chalcoil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare Rate, and the like. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 or the like is preferably used.

Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK.
Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.
Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

  Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white. Acridine, xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenyl Various dyes such as methane, diphenylmethane, thiazine, thiazole, and xanthene are also used. These colorants are used alone or in combination.

  Examples of the black pigment used for the black toner include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon and the like, and carbon black is particularly preferably used. Since carbon black has relatively good dispersibility, it does not require any special dispersion, but it is desirable that it be produced by a production method according to the colorant.

  The colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner. The colorant is preferably added in the range of 1% by mass to 15% by mass with respect to the total toner mass. Moreover, carbon black can be used as a black colorant, and iron, ferrite, magnetite, titanium, solid solution of iron and titanium, etc. can also be used. The amount is different, and can be added in an amount of 12 to 80% by mass. When obtaining the toner in the aqueous phase, it is necessary to pay attention to the water phase transferability of the colorant, and it is desirable to modify the surface in advance and perform, for example, a hydrophobic treatment.

(Release agent)
The toner according to the third embodiment preferably contains a release agent. The release agent used is a substance having a main maximum endothermic peak in DSC measured in accordance with ASTM D3418-8 at 60 ° C. or higher and 120 ° C. or lower and a melt viscosity of 1 mPas or higher and 50 mPas or lower at 140 ° C. It is desirable.

The release agent is a DSC curve measured by a differential scanning calorimeter, and the endothermic start temperature is preferably 40 ° C. or higher, and more preferably 50 ° C. or higher. The endothermic start temperature varies depending on the molecular weight distribution constituting the wax and the molecular weight distribution of the low molecular weight and the type and amount of polar groups of the structure.
In general, when the molecular weight is increased, the endothermic start temperature increases with the melting point, but in this manner, the original low melting temperature and low viscosity of the wax (release agent) are lost. Therefore, it is effective to select and remove only those having a low molecular weight from the molecular weight distribution of the wax. Examples of this method include molecular distillation, solvent fractionation, and gas chromatographic fractionation.
The DSC measurement is as described above.

  The melt viscosity of the release agent is measured with an E-type viscometer. For the measurement, an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) equipped with an oil circulation type thermostat is used. For the measurement, a cone plate / cup combination plate having a cone angle of 1.34 degrees is used. A sample is put into the cup, the temperature of the circulation device is set to 140 ° C., an empty measurement cup and cone are set to the measurement device, and the temperature is kept constant while circulating the oil. When the temperature is stabilized, 1 g of the sample is put in the measuring cup, and the cone is left still for 10 minutes. After stabilization, rotate the cone and measure. The rotational speed of the cone is 60 rpm. The measurement is performed three times, and the average value is taken as the melt viscosity η.

  Specific examples of the release agent include, for example, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene, silicones that exhibit a softening point upon heating, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, and the like. Fatty acid amides, plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, ester waxes such as fatty acid esters and montanic acid esters, montan wax, ozokerite , Ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax and other mineral-based and petroleum-based waxes, and modified products thereof.

(Other additives)
If necessary, inorganic or organic particles can be added to the toner according to the third embodiment.
Examples of the inorganic particles include silica, hydrophobized silica, alumina, titanium oxide, calcium carbonate, magnesium carbonate, tricalcium phosphate, colloidal silica, alumina-treated colloidal silica, cationic surface-treated colloidal silica, anion surface-treated colloidal silica, and the like. It can be used alone or in combination, and it is desirable to use colloidal silica. The particle size is preferably 5 nm or more and 50 nm or less. It is also possible to use particles having different particle sizes in combination. The particles can be added directly at the time of toner production, but it is preferable to use particles dispersed in an aqueous medium such as water using an ultrasonic disperser or the like. In the dispersion, the dispersibility can be improved by using an ionic surfactant, a polymer acid, a polymer base, or the like.

  In addition, a known material such as a charge control agent may be added to the toner. The average particle size of the material added at that time is desirably 1 μm or less, and more preferably 0.01 μm or more and 1 μm or less. The average particle diameter can be measured using, for example, a microtrack.

(Toner production method)
Further, the toner according to the third embodiment will be described in detail together with the manufacturing method thereof.
The method for producing the toner is not particularly limited, but is preferably a wet granulation method. Suitable examples of the wet granulation method include known melt suspension methods, emulsion aggregation methods, and dissolution suspension methods. Hereinafter, the emulsion aggregation method will be described as an example.

  The emulsion aggregation method includes a step of forming aggregated particles in a dispersion in which at least resin particles (hereinafter sometimes referred to as “emulsified liquid”) are dispersed to prepare an aggregated particle dispersion (aggregation step), and the aggregation This is a production method including a step of fusing the aggregated particles by heating the particle dispersion (fusion step). Further, before the aggregation step, the aggregated particles are dispersed (dispersion step), or between the aggregation step and the fusion step, a particle dispersion in which the particles are dispersed is added and mixed in the aggregated particle dispersion, and the aggregated particles are mixed. It may be provided with a step (attachment step) in which particles are attached to form attached particles. In the adhesion step, the particle dispersion is added to and mixed with the aggregated particle dispersion prepared in the aggregation step, and the particles are adhered to the aggregated particles to form adhered particles. Corresponds to particles newly added to the aggregated particles as viewed from the aggregated particles, and is sometimes referred to as “additional particles”.

As the additional particles, in addition to the resin particles, release agent particles, colorant particles and the like may be used singly or in combination. There is no restriction | limiting in particular as a method of adding and mixing the said particle dispersion liquid, For example, you may carry out gradually continuously, and may carry out in steps divided into several times. By providing the adhesion step, a pseudo shell structure can be formed.
In the toner, it is desirable to form a core-shell structure by the operation of adding the additional particles. The binder resin that is the main component of the write-once particles is a shell layer resin. If this method is used, the toner shape can be easily controlled by adjusting the temperature, the number of stirring, the pH and the like in the fusing step.

In the emulsion aggregation method, the crystalline polyester resin dispersion according to the first embodiment is used, and it is preferable to use an amorphous polyester resin dispersion together. It is more preferable to include an emulsification step of emulsifying the amorphous polyester resin to form emulsified particles (droplets).
In the emulsification step, the emulsified particles (droplets) of the amorphous polyester resin are prepared by mixing an aqueous medium and a mixed liquid (polymer liquid) containing the amorphous polyester resin and, if necessary, a colorant. It is formed by applying a shearing force to the solution. At that time, the viscosity of the polymer liquid can be lowered to form emulsified particles by heating to a temperature equal to or higher than the glass transition temperature of the amorphous polyester resin. Moreover, a dispersing agent can also be used. Hereinafter, such a dispersion of emulsified particles may be referred to as an “amorphous polyester resin dispersion”.

  Examples of the emulsifier used when forming the emulsified particles include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser. The size of the emulsified particles (droplets) of the polyester resin is preferably 0.005 μm or more and 0.5 μm or less, more preferably 0.01 μm or more and 0.3 μm or less in terms of the average particle size (volume average particle size). The volume average particle size of the resin particles was measured with a Doppler scattering type particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Microtrac UPA9340).

In addition, since the melt viscosity of the resin at the time of emulsification is not reduced to the desired particle size, by raising the temperature using an emulsifier that can pressurize above atmospheric pressure, emulsifying in a state where the resin viscosity is lowered, An amorphous polyester resin dispersion having a desired particle size can be obtained.
In the emulsification step, a method of previously adding a solvent to the resin may be used for the purpose of reducing the viscosity of the resin. The solvent used is not particularly limited as long as it dissolves the polyester resin, but is not limited to ketone solvents such as tetrahydrofuran (THF), methyl acetate, ethyl acetate, and methyl ethyl ketone, and benzene solvents such as benzene, toluene, and xylene. It is preferable to use ester solvents and ketone solvents such as ethyl acetate and methyl ethyl ketone.

  An alcohol solvent such as ethanol or isopropyl alcohol may be added directly to water or resin. Further, salts such as sodium chloride and potassium chloride, ammonia and the like may be added. Of these, ammonia is preferably used.

  Further, a dispersant may be added. Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, and sodium polyacrylate; sodium dodecylbenzenesulfonate, sodium octadecyl sulfate, sodium oleate, sodium laurate, and potassium stearate. Anionic surfactants such as; cationic surfactants such as laurylamine acetate and lauryltrimethylammonium chloride; zwitterionic surfactants such as lauryldimethylamine oxide; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, Surfactants such as nonionic surfactants such as polyoxyethylene alkylamine; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate Um, and inorganic compounds such as barium carbonate. Among these, anionic surfactants are preferably used. As the usage-amount of the said dispersing agent, 0.01 to 20 mass parts is preferable with respect to 100 mass parts of said polyester resins (binder resin). However, since the dispersant often affects the chargeability, if emulsifiability can be ensured by the hydrophilicity of the polyester resin main chain, the acid value of the terminal, the amount of the hydroxyl value, etc., it is better not to add as much as possible. Good.

  In the emulsification step, the amorphous polyester resin is copolymerized with a dicarboxylic acid having a sulfonic acid group (that is, a suitable amount of a dicarboxylic acid-derived constituent component having a sulfonic acid group in the acid-derived constituent component). Included). The addition amount is preferably 10 mol% or less in the acid component, but it is better not to add as much as possible when emulsifiability can be secured by the hydrophilicity of the polyester resin main chain, the acid value of the terminal, the amount of hydroxyl value, etc. .

  Further, a phase inversion emulsification method may be used for forming the emulsified particles. In the phase inversion emulsification method, at least an amorphous polyester resin is dissolved in a solvent, a neutralizing agent or a dispersion stabilizer is added as necessary, and an aqueous medium is dropped with stirring to obtain emulsified particles. After that, the solvent in the resin dispersion is removed to obtain an emulsion. At this time, the order of adding the neutralizing agent and the dispersion stabilizer may be changed.

  Examples of the solvent for dissolving the resin include formic acid esters, acetic acid esters, butyric acid esters, ketones, ethers, benzenes, and halogenated carbons. Specifically, esters such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl such as formic acid, acetic acid, butyric acid, acetone, MEK, MPK, MIPK, MBK, MIBK Such as methyl ketones, ethers such as diethyl ether and diisopropyl ether, heterocyclic substituents such as toluene, xylene and benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene , Halogenated carbons such as chloroform, monochlorobenzene, dichloroethylidene and the like can be used alone or in combination of two or more. Of these, acetic acid esters, methyl ketones and ethers which are low boiling solvents are usually preferably used, and acetone, methyl ethyl ketone, acetic acid, ethyl acetate and butyl acetate are particularly preferred. It is desirable to use a solvent having a relatively high volatility so that the solvent does not remain in the resin particles. The amount of these solvents used is selected from 20% by mass to 200% by mass, and more preferably from 30% by mass to 100% by mass with respect to the resin amount.

  As the aqueous medium, ion-exchanged water is basically used, but a water-soluble solvent may be included so as not to destroy the oil droplets. Examples of water-soluble solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol and other short carbon chain alcohols; ethylene glycol monomethyl ether, ethylene glycol mono Ethylene glycol monoalkyl ethers such as ethyl ether and ethylene glycol monobutyl ether; ethers, diols, THF, acetone and the like can be mentioned, and ethanol and 2-propanol are preferably used. The amount of these water-soluble solvents used is selected from 1% by mass to 60% by mass, and more preferably from 5% by mass to 40% by mass with respect to the resin amount. Further, the water-soluble solvent is not only mixed with the ion-exchanged water to be added, but may be used by adding it to the resin solution.

Moreover, you may add a dispersing agent to an amorphous polyester resin solution and an aqueous component as needed. As the dispersant, a hydrophilic colloid is formed in an aqueous component, and in particular, cellulose derivatives such as hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose; polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyacrylate, Examples thereof include synthetic polymers such as polymethacrylate, and dispersion stabilizers such as gelatin, gum arabic, and agar. Solid fine powders such as silica, titanium oxide, alumina, tricalcium phosphate, calcium carbonate, calcium sulfate, and barium carbonate can also be used. These dispersion stabilizers are usually added so that the concentration in the aqueous component is 0 to 20% by mass, preferably 0 to 10% by mass.
A surfactant is also used as the dispersant. As examples of the surfactant, those according to those used in the colorant dispersion described later can be used. For example, in addition to natural surfactant components such as saponin, cationic surfactants such as alkylamine hydrochlorides / acetates, quaternary ammonium salts, glycerols, fatty acid soaps, sulfates, alkylnaphthalene sulfonates, sulfones Anionic surfactants such as acid salts, phosphoric acid, phosphoric acid esters, sulfosuccinates and the like can be mentioned, and anionic surfactants and nonionic surfactants are preferably used. In order to adjust the pH of the emulsion, a neutralizing agent may be added. As the neutralizing agent, general acids such as nitric acid, hydrochloric acid, sodium hydroxide and ammonia, and alkalis can be used.
As a method for removing the solvent from the emulsion, a method of volatilizing the solvent from the emulsion to 15 ° C. or more and 70 ° C. or less, and a method of combining this with reduced pressure are preferably used. From the viewpoint of particle size distribution and particle size controllability, it is preferable to use a method of emulsifying by a phase inversion emulsification method and then removing the solvent by reducing the pressure under heating. In addition, when used for toner, from the viewpoint of influence on the charging property, a dispersant and a surfactant are not used as much as possible, depending on the hydrophilicity of the polyester resin main chain, the acid value of the terminal, the amount of hydroxyl value, etc. It is preferable to control emulsifiability.

  Examples of the dispersion method of the colorant and the release agent include general dispersion such as a high-pressure homogenizer, a rotary shearing homogenizer, an ultrasonic disperser, a high-pressure impact disperser, a ball mill having a medium, a sand mill, and a dyno mill. The method can be used and is not limited in any way.

If necessary, an aqueous dispersion of these colorants can be prepared using a surfactant, or an organic solvent dispersion of these colorants can be prepared using a dispersant. Hereinafter, the dispersion of the colorant and the release agent may be referred to as “colorant dispersion” or “release agent dispersion”.
The dispersant used for the colorant dispersion or the release agent dispersion is generally a surfactant. Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol Suitable examples include nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together. Moreover, it is preferable that it is the same polarity as the dispersing agent used for other dispersion liquids, such as a mold release agent dispersion liquid.

  Specific examples of the anionic surfactant include fatty acid soaps such as potassium laurate, sodium oleate and sodium castor oil; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonylphenyl ether sulfate; lauryl sulfonate , Dodecyl sulfonate, dodecyl benzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, etc., sodium alkyl naphthalene sulfonate, naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Sulfonates such as lauryl phosphate, isopropyl phosphate, Phosphoric acid esters such as alkenyl phenyl ether phosphates; dialkyl sodium sulfosuccinates of sodium dioctyl sulfosuccinate, sodium lauryl sulfosuccinate 2, polyoxyethylene sulfo sulfosuccinate salts such as succinic acid lauryl disodium and the like. Of these, alkylbenzene sulfonate compounds such as dodecylbenzene sulfonate and its branched products are preferred.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dihydroxyethyl methyl ammonium chloride, oleyl bis polyoxyethylene methyl ammonium chloride, lauroyl aminopropyl dimethyl ethyl ammonium etosulphate, lauroyl aminopropyl dimethyl hydroxyethyl ammonium perchlorate, alkylbenzene dimethyl Ammonium chloride, alkylto Such as quaternary ammonium salts such as ammonium chloride.

  Specific examples of the nonionic surfactant include polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other alkyl ethers; Alkylphenyl ethers such as oxyethylene nonylphenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxy Alkylamines such as ethylene oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as xylethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether, polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearin Alkanolamides such as acid diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate And the like.

  The addition amount of the dispersant used is desirably 2% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less with respect to the colorant or the release agent.

  The aqueous dispersion medium to be used is preferably one having few impurities such as metal ions such as distilled water and ion exchange water. Moreover, alcohol etc. can also be added. Polyvinyl alcohol, cellulose polymer, and the like can be added, but it is better not to use them as much as possible so that they do not remain in the toner.

  The means for preparing the dispersion of the various additives is not particularly limited, and examples thereof include a ball mill, a sand mill, and a dyno mill having a rotary shearing homogenizer and a media, as well as a colorant dispersion and a release agent. Examples of the dispersion apparatus known per se include an apparatus according to the one used for the preparation of the dispersion, and an optimum apparatus can be selected and used.

  In the aggregation step, it is preferable to use an aggregating agent in order to form aggregated particles. Examples of the flocculant used include a surfactant having a polarity opposite to that of the surfactant used in the dispersant, a general inorganic metal compound (inorganic metal salt), or a polymer thereof. The metal element constituting the inorganic metal salt has a divalent or higher charge belonging to the 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, 3B group in the periodic table (long periodic table). There is no limitation as long as it dissolves in the form of ions in the aggregation system of resin particles.

  Specific examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. And inorganic metal salt polymers. Of these, aluminum salts and polymers thereof are particularly preferred. In general, in order to obtain a sharper particle size distribution, even if the valence of the inorganic metal salt is divalent to monovalent, bivalent to trivalent or higher, and even to the same valence, the polymerization type inorganic metal salt weight Combined is more suitable.

  The addition amount of the flocculant varies depending on the type and valence of the flocculant, but is generally in the range of 0.05% by mass to 0.1% by mass. The aggregating agent does not always remain in the toner due to outflow into the aqueous medium or formation of coarse powder during the toner forming process. In particular, when the amount of the solvent in the resin is large in the toner forming step, the solvent and the flocculant interact and easily flow out into the aqueous medium, so it is necessary to adjust the amount according to the amount of the remaining solvent.

  Although due to the addition of the aggregating agent, the toner according to the third embodiment contains at least one metal element selected from aluminum, zinc, and calcium in an element composition ratio of 0.003% by mass to 0%. .05% by mass or less is preferable. Here, the content of the metal element is determined from the total elemental analysis using a fluorescent X-ray apparatus. The sample was 6 g of toner, pressure-molded with a pressure molder with a load of 10 t and a pressurization time of 1 minute. Using a fluorescent X-ray (XRF-1500) manufactured by Shimadzu Corporation, the measurement conditions were a tube voltage of 40 kV, It is obtained from the elemental composition ratio measured at a tube current of 90 mA and a measurement time of 30 minutes.

  In the fusion step, the agglomeration suspension is controlled to have a pH of 5 or more and 10 or less under stirring according to the aggregation step to stop the progress of aggregation, and the glass transition temperature (Tg) or higher of the resin. The aggregated particles are fused and united by heating at a temperature of (or a temperature equal to or higher than the melting point of the crystalline resin). The heating time may be performed to the extent that desired coalescence is achieved, and may be performed for 0.2 hours or more and 10 hours or less. Thereafter, when the temperature is lowered to Tg or less of the resin to solidify the particles, the particle shape and surface properties change depending on the temperature-decreasing rate. It is preferable to lower the temperature to at most Tg of the resin at a rate of at least 0.5 ° C./min, more preferably at a rate of 1.0 ° C./min.

  Further, while heating at a temperature equal to or higher than the Tg of the resin, particles are grown by adding a pH or a flocculant according to the aggregation step, and when the desired particle size is reached, at least 0.5 ° C. according to the case of the fusion step. It is preferable in terms of simplification of the process because the aggregation process and the fusion process can be performed at the same time if the particle growth is stopped simultaneously with the solidification by lowering the temperature to the Tg of the resin at a rate of / min. It may be difficult to make a core-shell structure.

  After completing the fusing step, the particles are washed and dried to obtain toner particles. In addition, it is preferable to perform substitution cleaning with ion-exchanged water, and the degree of cleaning is generally monitored by the conductivity of the filtrate, and it is preferable that the conductivity is finally 25 μS / cm or less. The washing may include a step of neutralizing ions with an acid or an alkali. The treatment with an acid preferably has a pH of 4.0 or less, and the treatment with an alkali preferably has a pH of 8.0 or more. The solid-liquid separation after washing is not particularly limited, but from the viewpoint of productivity, suction filtration, pressure filtration such as a filter press, and the like are preferably used. Further, the drying method is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, etc. are preferably used, and the final toner moisture content is 1% by mass or less. More preferably, drying is performed so that the content is 0.7% by mass or less.

  The toner particles obtained as described above can be externally mixed with inorganic particles and organic particles as fluidity aids, cleaning aids, abrasives, and the like. Examples of the inorganic particles include all particles usually used as external additives on the toner surface, such as silica, alumina, titanium oxide, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide. These inorganic particles preferably have a hydrophobic surface. As organic particles, for example, they are usually used as external additives on the surface of toner such as vinyl resins such as styrene polymers, (meth) acrylic polymers, and ethylene polymers, polyester resins, silicone resins, and fluorine resins. All particles.

  These particles preferably have a primary particle size of 0.01 μm or more and 0.5 μm or less. Further, a lubricant can be added. Examples of the lubricant include fatty acid amides such as ethylene bisstearyl amide and oleic acid amide, and higher alcohols such as fatty acid metal salt unilin such as zinc stearate and calcium stearate. The primary particle size is preferably 0.5 μm or more and 8.0 μm or less.

  Further, at least two or more of the inorganic particles are used, and at least one of the inorganic particles preferably has an average primary particle size of 30 nm to 200 nm, more preferably 30 nm to 180 nm.

Specifically, silica, alumina, and titanium oxide are preferable, and it is particularly preferable to add hydrophobized silica as an essential component. It is particularly preferable to use silica and titanium oxide in combination. It is also preferable to use organic particles having a particle size of 80 nm or more and 500 nm or less in combination. Examples of the hydrophobizing agent for hydrophobizing the external additive include known materials, such as silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconium coupling agents. Examples include silicone oil and polymer coating treatment.
The external additive is adhered or fixed to the toner surface by applying a mechanical impact force with a sample mill or a Henschel mixer.

(Toner characteristics)
The volume average particle size of the toner according to the third embodiment is preferably in the range of 4 μm to 9 μm, more preferably in the range of 4.5 μm to 8.5 μm, and still more preferably in the range of 5 μm to 8 μm. It is.

In addition, the above toner draws a cumulative distribution from the small diameter side to the particle size range (channel) obtained by dividing the particle size distribution measured by the following method from the small diameter side, and the particle size that becomes 16% cumulative is the volume. Volume average particle size distribution calculated from (D84% / D16%) ^1/2 when the particle size of D16% and cumulative 50% is defined as volume D50% and the cumulative particle size of 84% is defined as volume D84%. The index (GSDv) is preferably 1.15 or more and 1.30 or less, and more preferably 1.15 or more and 1.25 or less.

  The volume average particle diameter and the like can be measured using Multisizer II (manufactured by Beckman Coulter, Inc.) with an aperture diameter of 50 μm. At this time, the measurement was performed after the toner was dispersed in an electrolyte aqueous solution (isoton aqueous solution) (concentration: 10% by mass) and dispersed by ultrasonic waves for 30 seconds or more. As for the particle size distribution, the particle size range divided on the basis of the particle size distribution measured using Multisizer II (number of divisions: 1.26 μm to 50.8 μm up to 16 channels, 0.1 on the log scale). Specifically, the channel 1 is divided into 1.26 μm and less than 1.59 μm, the channel 2 is 1.59 μm and less than 2.00 μm, and the channel 3 is 2.00 μm and less than 2.52 μm. The log values of the lower limit value on the left side are (log 1.26 =) 0.1, (log 1.59 =) 0.2, (log 2.00 =) 0.3, ..., 1.6 In other words, the cumulative distribution of the volume and the number is subtracted from the small particle diameter side, and the particle size that becomes 16% cumulative is the volume D16v, the number D16p, and the particle size that becomes 50% cumulative. Volume D50v (body Product average particle diameter), several D50p, and the cumulative particle diameter of 84% was defined as volume D84v and number D84p.

The toner preferably has a spherical shape with a shape factor SF1 in the range of 110 to 145. When the shape is spherical within this range, transfer efficiency and image density are improved, and high-quality image formation can be performed.
The shape factor SF1 is more preferably in the range of 110 to 135.

Here, the shape factor SF1 is obtained by the following formula (II).
SF1 = (ML ² / A) × (π / 4) × 100 Formula (II)
In the above formula (II), ML represents the absolute maximum length of the toner particles, and A represents the projected area of the toner particles.

  The SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and can be calculated as follows, for example. That is, an optical microscope image of toner particles dispersed on the surface of a slide glass is taken into a Luzex image analyzer through a video camera, the maximum length and projected area of 100 particles are obtained, calculated by the above formula (II), and the average value thereof Is obtained.

  Further, the content of titanium in the crystalline resin component in the chloroform-soluble component of the toner by the high frequency inductively coupled plasma emission analysis (ICP-AES) is in the range of 10 ppm or more and 500 ppm or less. It is desirable that the tin content in the amorphous resin component is in the range of 50 ppm to 1500 ppm by high frequency inductively coupled plasma emission spectrometry.

In order to determine the amount of titanium and the amount of tin in the amorphous polyester resin and the crystalline polyester resin from the components contained in the toner, the following method is used.
First, the crystalline resin and the amorphous resin in the toner are separated. First, the toner is allowed to stand for 24 hours in a constant temperature bath at a temperature of 50 ° C. and a humidity of 55 RH%, and the thermal history of the toner is cancelled. Thereafter, 10 g of toner is dissolved in 100 g of methyl ethyl ketone (MEK) at room temperature (20 ° C. or more and 25 ° C. or less). This is because when the toner contains a crystalline resin and an amorphous resin, almost only the amorphous resin is dissolved in MEK at room temperature. Therefore, the MEK-soluble component contains an amorphous resin including an amorphous polyester resin. Therefore, after the dissolution, centrifugation (centrifuge “H-18”, Kokusan Co., Ltd., 2500 revolutions) For 15 minutes), an amorphous polyester resin is obtained from the supernatant. MEK in which the amorphous resin is dissolved is removed by a vacuum dryer to obtain the amorphous resin. The solid content after centrifugation is dissolved again in 100 g of MEK and centrifuged, and the supernatant is discarded. On the other hand, a crystalline polyester resin is obtained from a supernatant obtained by dissolving the solid content after centrifugation in 100 g of MEK under heating at 70 ° C. and separating it by centrifugation. The amount of tin and titanium can be confirmed by the above method for both resins thus obtained.

  The titanium content is more preferably in the range of 30 ppm to 200 ppm. The tin content is more preferably in the range of 100 ppm to 1000 ppm.

  The toner preferably has an absolute charge in the range of 15 μC / g to 70 μC / g, and more preferably in the range of 20 μC / g to 50 μC / g. The charge ratio (HH / LL) between 30 ° C. and 80 RH% under high temperature and high humidity (HH) and 10 ° C. and 20 RH% under low temperature and low humidity (LL) is 0.5 to 1.5. A range is desirable, and a range of 0.7 to 1.2 is more preferable.

  The toner preferably has an insoluble content of tetrahydrofuran (hereinafter referred to as “THF”) of 10% by mass or less in the binder resin component. The THF-insoluble matter can be measured by dissolving the resin in THF at a concentration of 5% by mass in a 60 ° C. hot water bath, filtering through a membrane filter or the like, drying the filter residue, and measuring the mass. .

<Fourth Embodiment: Electrostatic Charge Image Developer>
The electrostatic image developing toner according to the third embodiment is used as it is as a one-component developer or as a two-component developer composed of a carrier.

  The carrier is preferably a carrier coated with a resin, and more preferably a carrier coated with a nitrogen-containing resin. Examples of the nitrogen-containing resin include acrylic resins containing dimethylaminoethyl methacrylate, dimethylacrylamide, acrylonitrile, and the like, amino resins containing urea, urethane, melamine, guanamine, aniline, amide resins, and urethane resins. These copolymer resins may also be used. As the carrier coating resin, two or more of the nitrogen-containing resins may be used in combination. Moreover, you may use combining the said nitrogen containing resin and resin which does not contain nitrogen. The nitrogen-containing resin may be used in the form of particles and dispersed in a resin not containing nitrogen. In particular, urea resin, urethane resin, melamine resin, and amide resin are preferable.

In general, the carrier needs to have an appropriate electrical resistance value, and specifically, an electrical resistance value of 10 ⁹ Ωcm or more and 10 ¹⁴ Ωcm or less is required. For example, when the electrical resistance value is as low as 10 ⁶ Ωcm, such as an iron powder carrier, an insulating resin (volume resistivity is 10 ¹⁴ Ωcm or more) is coated, and the conductive powder is dispersed in the resin coating layer. Is desirable.

  Specific examples of the conductive powder include metals such as gold, silver and copper; carbon black; semiconductive oxides such as titanium oxide and zinc oxide; titanium oxide, zinc oxide, barium sulfate, aluminum borate and potassium titanate. And the like, such as powder coated with tin oxide, carbon black, or metal. Among these, carbon black is preferable.

  Examples of the method for forming the resin coating layer on the surface of the carrier core material include an immersion method in which a powder of the carrier core material is immersed in the solution for forming the coating layer, and a solution for forming the coating layer on the surface of the carrier core material. Spraying method for spraying, fluidized bed method for spraying the solution for forming the coating layer in a state where the carrier core material is floated by flowing air, and a kneader for mixing the carrier core material and the coating layer forming solution in a kneader coater to remove the solvent. Examples of the coater method include a powder coating method in which a coating resin is made into particles and mixed at a temperature equal to or higher than the melting point of the coating resin in a carrier core material and a kneader coater and then cooled to form a coating. The kneader coating method and the powder coating method are particularly preferably used. The average film thickness of the resin coating layer formed by the above method is usually in the range of 0.1 μm to 10 μm, and more preferably 0.2 μm to 5 μm.

The core material used for the carrier (carrier core material) is not particularly limited, and examples thereof include magnetic metals such as iron, steel, nickel, and cobalt, or magnetic oxides such as ferrite and magnetite, glass beads, and the like. In particular, when a magnetic brush method is used, a magnetic carrier is desirable. The average particle diameter of the carrier core material is generally preferably 10 μm or more and 100 μm or less, and more preferably 20 μm or more and 80 μm or less.
The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is in the range of toner: carrier = 1: 100 to 30: 100, more preferably in the range of 3: 100 to 20: 100. desirable.

<Fifth Embodiment: Image Forming Apparatus>
Next, an image forming apparatus according to the fifth embodiment using the electrostatic charge image developer according to the fourth embodiment (the electrostatic charge image developing toner according to the third embodiment) will be described.
The image forming apparatus includes an image carrier, a developing unit that develops the electrostatic image formed on the image carrier as a toner image with the electrostatic image developer according to the fourth embodiment, and the image carrier. The image forming apparatus includes a transfer unit that transfers the formed toner image onto a recording medium, and a fixing unit that fixes the toner image transferred onto the recording medium.

In this image forming apparatus, for example, the part including the developing unit may have a cartridge structure (process cartridge) that can be attached to and detached from the image forming apparatus main body. As the process cartridge, a developer holding body is used. A process cartridge that includes at least the electrostatic charge image developer according to the fourth embodiment is preferably used.
Hereinafter, an example of the image forming apparatus according to the fifth embodiment will be described, but the present invention is not limited to this. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

  FIG. 1 is a schematic diagram showing a quadruple tandem full-color image forming apparatus. The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter simply referred to as “units”) 10Y, 10M, 10C, and 10K are juxtaposed at a predetermined distance in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the main body of the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a driving roller 22 and a support roller 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other from the left to the right in the drawing. It is designed to travel in the direction toward 10K. The support roller 24 is urged away from the drive roller 22 by a spring or the like (not shown), and a predetermined tension is applied to the intermediate transfer belt 20 wound around the support roller 24. Further, an intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the driving roller 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K includes yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The four color toners can be supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K described above have the same configuration, here, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction. 10Y will be described as a representative. Note that the second to fourth units are denoted by reference numerals with magenta (M), cyan (C), and black (K) instead of yellow (Y) in the same parts as the first unit 10Y. Description of 10M, 10C, 10K is omitted.

The first unit 10Y has a photoreceptor 1Y that functions as an image holding member. Around the photoreceptor 1Y, an electrostatic charge image is formed by exposing the surface of the photoreceptor 1Y to a predetermined potential with a charging roller 2Y and the charged surface with a laser beam 3Y based on the color-separated image signal. An exposure device 3; a developing device (developing means) 4Y for supplying the charged toner to the electrostatic image and developing the electrostatic image; a primary transfer roller 5Y (primary) for transferring the developed toner image onto the intermediate transfer belt 20; A transfer unit), and a photoconductor cleaning device (cleaning unit) 6Y for removing toner remaining on the surface of the photoconductor 1Y after the primary transfer.
The primary transfer roller 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described. First, prior to the operation, the surface of the photoreceptor 1Y is charged to a potential of about −600V to −800V by the charging roller 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (a resistance equivalent to that of a general resin), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic charge image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y flows. On the other hand, this is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic image formed on the photoreceptor 1Y in this way is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is visualized (developed image) by the developing device 4Y.

  In the developing device 4Y, for example, yellow toner having a volume average particle diameter of 7 μm including at least a yellow colorant, a crystalline resin, and an amorphous resin is accommodated. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged charge on the photoreceptor 1Y, and a developer roll (developer holder). Is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a predetermined primary transfer bias is applied to the primary transfer roller 5Y, and the electrostatic force directed from the photoreceptor 1Y to the primary transfer roller 5Y generates a toner image. The toner image on the photoreceptor 1 </ b> Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time is a (+) polarity opposite to the polarity (−) of the toner, and is controlled to about +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rollers 5M, 5C, and 5K after the second unit 10M is also controlled according to the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner.

  The intermediate transfer belt 20 onto which the four color toner images have been transferred in multiple layers through the first to fourth units is disposed on the image transfer surface side of the intermediate transfer belt 20 and the support roller 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roller (secondary transfer means) 26 is connected to a secondary transfer portion. On the other hand, the recording paper (transfer object) P is fed at a predetermined timing into a gap where the secondary transfer roller 26 and the intermediate transfer belt 20 are pressed against each other via a supply mechanism, and a predetermined secondary transfer bias is supported. Applied to the roller 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, so The toner image is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to the resistance detected by a resistance detection means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

Thereafter, the recording paper P is sent to a fixing device (fixing means) 28, where the toner image is heated, and the color-superposed toner image is melted and fixed on the recording paper P. The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.
The image forming apparatus exemplified above is configured to transfer the toner image onto the recording paper P via the intermediate transfer belt 20, but the present invention is not limited to this configuration, and the toner image is directly transferred from the photoconductor. It may be a structure that is transferred to a recording sheet.

<Sixth Embodiment: Process Cartridge / Seventh Embodiment: Toner Cartridge>
FIG. 2 is a schematic configuration diagram showing a preferred example of a process cartridge according to the sixth embodiment that accommodates the electrostatic charge image developer according to the fourth embodiment. In the process cartridge 200, a charging roller 108, a developing device 111, a photosensitive member cleaning device (cleaning unit) 113, an opening 118 for exposure, and an opening 117 for static elimination exposure are attached to a rail 116 together with the photosensitive member 107. Are combined and integrated with each other.
The process cartridge 200 is detachable from an image forming apparatus main body including a transfer device 112, a fixing device 115, and other components (not shown). It forms a forming apparatus. Reference numeral 300 denotes a recording sheet.

  The process cartridge shown in FIG. 2 includes a charging device 108, a developing device 111, a cleaning device (cleaning means) 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. Can be selectively combined. In the process cartridge of the present invention, in addition to the developing device 111, the photosensitive member 107, the charging device 108, the cleaning device (cleaning means) 113, the opening 118 for exposure, and the opening 117 for static elimination exposure. It comprises at least one selected from the group consisting of.

  Next, a toner cartridge according to a seventh embodiment will be described. The toner cartridge according to the seventh embodiment is detachably attached to the image forming apparatus, and at least the toner cartridge that stores toner to be supplied to the developing unit provided in the image forming apparatus is described above. It is the toner according to the third embodiment. Note that the toner cartridge according to the seventh embodiment only needs to store at least toner. For example, a developer may be stored depending on the mechanism of the image forming apparatus.

  Therefore, in the image forming apparatus having a configuration in which the toner cartridge can be attached and detached, by using the toner cartridge containing the toner, it is possible to maintain storability even in a toner cartridge whose container is miniaturized, It is possible to achieve low-temperature fixing while maintaining high image quality.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which the toner cartridges 8Y, 8M, 8C, and 8K can be attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are respectively the developing devices ( And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge is low, the toner cartridge can be replaced.

EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited by the following Example.
In this example, the crystalline polyester resin dispersion is obtained by the following method. That is, first, the crystalline polyester resin and the solvent are stirred and dissolved at a temperature in the range of −15 ° C. to + 15 ° C. of the melting point of the crystalline polyester resin and less than the boiling point of the solvent to obtain a solution. Prepare and add neutralizing agent to the solution. The emulsified liquid is prepared by mixing and stirring the solution containing the neutralizing agent and the aqueous medium, and after cooling the emulsified liquid to a recrystallization temperature of −5 ° C. or lower of the crystalline polyester resin, A crystalline polyester resin dispersion is prepared by removing the solvent. In this embodiment, the electrostatic image developing toner is prepared using the crystalline polyester resin dispersion prepared as described above. Hereinafter, it demonstrates along the above.

[Example 1]
<Production of crystalline polyester resin dispersion>
(1) Preparation of crystalline polyester resin (C1)-1,10-dodecanedioic acid: 50 mol%
-1,9-nonanediol: 50 mol%
The monomer component was placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube. After the reaction vessel was replaced with dry nitrogen gas, titanium tetrabutoxide ( 0.25 parts by mass of (reagent) was added, and the mixture was stirred and reacted at 170 ° C. for 3 hours under a nitrogen gas stream. Furthermore, the temperature was raised to 210 ° C., the pressure in the reaction vessel was reduced to 3 kPa, and the reaction was stirred for 13 hours under reduced pressure to obtain a crystalline polyester resin (C1). The crystalline polyester resin (C1) had a melting point Tc by DSC of 73.6 ° C., a weight average molecular weight Mw by GPC of 25000, a number average molecular weight Mn of 10500, and an acid value AV of 10.1 mgKOH / g.

(2) Production of crystalline polyester resin dispersion (C1) In a 2 L separable flask equipped with a stirring blade, a condenser, a thermometer, and a water dropping device, 300 parts by mass of the crystalline polyester resin (C1) and methyl ethyl ketone (solvent ) 105 parts by mass and 90 parts by mass of isopropyl alcohol (solvent) were added, heated to 70 ° C. in a hot water bath, maintained at 70 ° C., and the resin was dissolved while stirring and mixing at 100 rpm. Process]. Thereafter, the stirring rotation speed was set to 150 rpm, the hot water bath was set to 66 ° C., and the mixture was left for 30 minutes to stabilize the temperature. Next, 15 parts by mass of 10% by mass aqueous ammonia (reagent) is added in 1 minute [neutralizing agent addition step] After mixing for 10 minutes, 7 parts by mass of ion-exchanged water (aqueous medium) kept at 66 ° C. A total of 900 parts by mass was added dropwise at a rate of parts / min to cause phase inversion to obtain an emulsion [emulsion preparation step].
After completion of the water dripping, while discharging hot water in the hot water bath, 10 ° C. cold water having the same amount as the discharged hot water was added to the hot water bath, and the flask was cooled to 20 ° C. The cooling rate to 20 ° C was 0.9 ° C / min [cooling step].
800 parts by mass of the cooled emulsion and 500 parts by mass of ion-exchanged water were placed in a 2 L eggplant flask and set in an evaporator (Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, the mixture was heated at 60 ° C. for 30 minutes in a hot water bath to stabilize the liquid temperature, and then pressure reduction was started. Depressurization conditions are the capacity limit speed of the pump from 101 kPa to 50 kPa, and the pressure is reduced from 50 kPa to 7 kPa in 172 minutes. The solvent was recovered [solvent removal step]. When the solvent recovery amount reached 850 parts by mass, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a crystalline polyester resin dispersion (C1). The volume average particle diameter D50v of the resin particles in this dispersion was 170 nm, and the particle size distribution index GSDv was 1.17. Ion exchange water was added to the resulting dispersion to adjust the solid content concentration to 30% by mass.

(3) Titration of the dispersion The crystalline polyester resin dispersion (C1) was titrated with sodium hydroxide by the above-mentioned method, and the change in pH was plotted on the horizontal axis with the amount of sodium hydroxide added dropwise. A titration curve was drawn with the differentiated value on the vertical axis. The titration curve is shown in FIG. The calculation results of the height P1 of the peak (1), the height P2 of the peak (2), and P1 / P2 are shown in Table 1 below.

<Manufacture of developer>
(1) Preparation of release agent dispersion / release agent (Nippon Seiki Co., Ltd., trade name: FNP0090, melting point Tw 89.7 ° C.)
: 270 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, active ingredient amount: 60% by mass): 13.5 parts by mass (3.0 parts by mass as the active ingredient relative to the release agent) %)
-Ion-exchanged water: 721.6 parts by mass After mixing the above components and dissolving the release agent at an internal liquid temperature of 120 ° C with a pressure discharge type homogenizer (Gorin homogenizer manufactured by Gorin), the dispersion pressure is 5 MPa. Dispersion treatment was carried out for 120 minutes at 40 MPa for 360 minutes, followed by cooling to obtain a release agent dispersion. The volume average particle diameter D50v of the particles in this dispersion was 230 nm. Thereafter, ion exchange water was added to adjust the solid content concentration to 20.0% by mass to obtain a release agent dispersion.

(2) Preparation of Colorant Dispersion Cyan Pigment (Daiichi Seika Co., Ltd .: ECB-301): 200 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC): 33 parts by mass
(Active ingredient 60% by mass. 10% by mass with respect to the colorant)
-Ion-exchanged water: 750 parts by mass 280 parts by mass of ion-exchanged water and an anionic system in a stainless steel container whose liquid level is about 1/3 of the height of the container when all of the above components are added. After adding 20 parts by mass of a surfactant and sufficiently dissolving the surfactant, all of the cyan pigment was added, and the mixture was stirred using a stirrer until there was no wet pigment, and was sufficiently degassed. . After defoaming, the remaining ion-exchanged water was added, and the mixture was dispersed for 10 minutes at 5000 revolutions using a homogenizer (manufactured by IKA, Ultra Tarrax T50).

  After defoaming, the mixture was dispersed again at 6000 rpm for 10 minutes using a homogenizer, and then defoamed by stirring for one day with a stirrer. Subsequently, the dispersion liquid was dispersed at a pressure of 240 MPa using a high-pressure impact disperser ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). The dispersion was equivalent to 25 passes in terms of the total charge and the processing capacity of the apparatus. The obtained dispersion was allowed to stand for 72 hours to remove precipitates, and ion exchange water was added to adjust the solid content concentration to 15% by mass. The volume average particle diameter D50 of the particles in this colorant dispersion was 115 nm. As the volume average particle diameter D50, an average value of three measured values excluding the maximum value and the minimum value among the five times measured by Microtrack was used.

(3) Preparation of aqueous aluminum sulfate solution ・ Aluminum sulfate powder (Asada Chemical Co., Ltd .: 17% by mass aluminum sulfate)
: 35 parts by mass / ion exchanged water: 1965 parts by mass were charged into a 2 liter container and stirred at 30 ° C. until the precipitate disappeared to prepare an aqueous aluminum sulfate solution.

(4) Preparation of Amorphous Polyester Resin Dispersion (A1)-Bisphenol A ethylene oxide 2.2 mol adduct 10 mol%
-Bisphenol A propylene oxide 2.2 mol adduct 40 mol%
・ 22 mol% terephthalic acid
・ Fumaric acid 15 mol%
・ Dodecenyl succinic anhydride 11 mol%
・ Trimellitic anhydride 2 mol%
In a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, among the monomer components, monomer components other than fumaric acid and trimellitic anhydride, and dioctanoic acid tin in a total of 100 parts by mass of the monomer components 0.25 parts by mass with respect to the amount was added. After reacting at 235 ° C. for 6 hours under a nitrogen gas stream, the temperature was lowered to 200 ° C., and the fumaric acid and trimellitic anhydride were added and reacted for 1 hour. Furthermore, it heated up to 220 degreeC in 4 hours, it superposed | polymerized until it became a desired molecular weight under the pressure of 10 kPa, and the pale yellow transparent amorphous polyester resin was obtained. The glass transition point Tg by DSC of this amorphous polyester resin is 59 ° C., the weight average molecular weight Mw by GPC is 23000, the number average molecular weight Mn is 7000, the softening temperature by a flow tester is 106 ° C., and the acid value AV is 11 mgKOH / g. there were.

180 parts by mass of methyl ethyl ketone while maintaining a jacketed 3L reactor (manufactured by Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, thermometer, water dripping device and anchor blade at 40 ° C. in a water circulating thermostatic bath A mixed solvent of 50 parts by mass of isopropyl alcohol and 300 parts by mass of the amorphous polyester resin was added thereto, and the mixture was stirred and dissolved at 150 rpm by a three-one motor to obtain an oil phase. To this stirred oil phase, 15 parts by mass of a 10% by mass aqueous ammonia solution was added dropwise for 1 minute, mixed for 10 minutes, and 900 parts by mass of ion-exchanged water was further added dropwise at a rate of 7 parts by mass per minute. Phase inversion emulsification was performed.
800 parts by mass of the obtained emulsified liquid and 500 parts by mass of ion-exchanged water were placed in a 2 L eggplant flask and set in an evaporator (Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, the mixture was heated at 60 ° C. for 30 minutes in a hot water bath to stabilize the liquid temperature, and then pressure reduction was started. The depressurization condition is the capacity limit speed of the pump from 101 kPa to 60 kPa, depressurizing from 50 kPa to 7 kPa in 250 minutes, maintaining 7 kPa after reaching 7 kPa, and adjusting the degree of vacuum so that the contents do not bump during the process The solvent was recovered [solvent removal step]. When the solvent recovery amount reached 850 parts by mass, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain an amorphous polyester resin dispersion (A1). The volume average particle diameter D50v of the resin particles in this dispersion was 150 nm. Then, it adjusted with ion-exchange water and solid content concentration was 20 mass%.

(5) Preparation of additional amorphous polyester resin dispersion (A1A) 350 parts by mass of the amorphous polyester resin dispersion (A1) was placed in a 500 mL beaker, and a speed at which bubbles were not encased with a magnetic stirrer. While stirring, 3.4 parts by mass of an anionic surfactant (Dowfax 2A1 manufactured by Dow Chemical Company) was added and stirred for 10 minutes, and then the pH was adjusted to 3.8 using 0.3 M nitric acid. After stirring for 30 minutes, the pH was adjusted to 3.8 again to prepare an additional amorphous polyester resin dispersion (A1A).

(6) Toner Production / Crystalline Polyester Resin Dispersion (C1) 57 parts by mass Amorphous Polyester Resin Dispersion (A1) 635 parts by weight Colorant Dispersion 100 parts by weight Release Agent Dispersion 115 parts by weight -Ion-exchanged water 200 parts by mass-Anionic surfactant (Dowfax2A1 manufactured by Dow Chemical Co.) 7.0 parts by mass The above components were put in a 3 L reaction vessel equipped with a thermometer, pH meter, and stirrer, and the temperature was 25 While being dispersed at 5000 rpm with a homogenizer (manufactured by IKA Japan: Ultra Tarax T50) at 125 ° C., 125 parts by mass of the prepared aqueous aluminum sulfate solution was added and dispersed for 6 minutes. After that, a stirrer and a mantle heater are installed in the reaction vessel, and the temperature of the stirrer is adjusted to 0.2 ° C./min until the temperature reaches 40 ° C. The temperature was raised at 0.05 ° C./min, and the particle size was measured with Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter, Inc.) every 10 minutes, and the temperature was reached when the volume average particle size became 5.0 μm. And an additional amorphous polyester resin dispersion (A1A) was added over 5 minutes. After maintaining for 30 minutes after charging, the pH was adjusted to 9.0 using a 4% by mass aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 90 ° C. at a temperature rising rate of 1 ° C./min and held at 90 ° C. When the particle shape and surface property were observed with an optical microscope and a scanning electron microscope (FE-SEM) every 15 minutes, coalescence of the particles was confirmed at 1.0 hour. Cooled to 5 ° C. in 5 minutes.

The cooled slurry was passed through a nylon mesh having an opening of 15 μm to remove coarse powder, and the toner slurry that passed through the mesh was filtered under reduced pressure with an aspirator. The toner remaining on the filter paper is crushed as finely as possible by hand, poured into ion exchange water 10 times the amount of toner at a temperature of 30 ° C., stirred and mixed for 30 minutes, and then filtered again under reduced pressure with an aspirator. The degree was measured. This operation was repeated until the filtrate had a conductivity of 10 μS / cm or less, and the toner was washed. The washed toner was finely crushed with a wet dry granulator (Comil) and then vacuum dried in an oven at 35 ° C. for 36 hours to obtain toner particles.
To 100 parts by mass of the obtained toner particles, 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) are added, Using a sample mill, the mixture was blended at 13000 rpm for 30 seconds. Thereafter, the toner was obtained by sieving with a vibrating sieve having an opening of 45 μm.
The obtained toner had a volume average particle diameter D50v of 6.0 μm and a shape factor of 0.960 (manufactured by Sysmex Corporation, FPIA-3000). When the SEM image of the toner was observed, it had a smooth surface and there were no problems such as protrusion of the release agent and peeling of the surface layer.

(7) Preparation of carrier • Mn—Mg—Sr ferrite particles (average particle size 40 μm): 100 parts by mass • Toluene: 14 parts by mass • Cyclohexyl methacrylate / dimethylaminoethyl methacrylate copolymer (copolymerization mass ratio 99: 1. Weight average molecular weight Mw 80,000): 2.0 parts by mass Carbon black (VXC72: manufactured by Cabot): 0.12 parts by mass The above components excluding ferrite particles and glass beads (φ1 mm, equivalent to toluene) The mixture was stirred at 1200 ppm / 30 min using a company-made sand mill to obtain a resin coating layer forming solution. Further, this resin coating layer forming solution and ferrite particles were put in a vacuum degassing kneader and the pressure was reduced, and toluene was distilled off / dried to form a resin coated carrier.

(8) Preparation of Developer After adding 40 parts by mass of the toner to 500 parts by mass of the carrier and blending with a V-type blender for 20 minutes, the aggregates are removed by a vibrating screen having an aperture of 212 μm, and the developer (A1 )
Further, after adding 100 parts by mass of the toner to 20 parts by mass of the carrier and blending for 20 minutes with a V-type blender, the aggregate is removed by a vibration sieve having an aperture of 212 μm, and a replenishment developer (A1) is obtained. Obtained.

<Evaluation>
(Evaluation of particle size stability of dispersion due to temperature change)
The crystalline polyester resin dispersion (C1) was adjusted to a solid content concentration of 25% by mass using ion-exchanged water, placed in a 500 ml polypropylene container (trade name: Eyeboy), and left in a refrigerator at 5 ° C. for 24 hours. A cycle of leaving in an oven set at 40 ° C. for 24 hours and then leaving again in a refrigerator at 5 ° C. for 24 hours was performed for 30 days. The volume average particle diameter D50v before and after storage for 30 days was measured by the above-described method, and the presence or absence of sedimentation was confirmed.
The change amount of the particle diameter is good when it is within ± 1 nm, Δ is the degree of no practical problem within ± 3 nm, and x is over ± 3 nm. In addition, ○ when there is no sedimentation, △ when sedimentation is very slight (a part of the bottom of the container is hidden), × It was. The results are shown in Table 1 below.

(Evaluation of particle size stability of dispersion by pumping)
The crystalline polyester resin dispersion (C1) was adjusted to a solid concentration of 25% by mass using ion-exchanged water, and a tank with a volume of 3 L and a diaphragm pump (manufactured by ASONE: DP-10BPT) were 3 mm in diameter and long. Using a device connected by a 1.0 m long pipe, circulation operation was performed for 40 minutes at a dispersion liquid amount of 1800 g and a liquid flow rate of 1800 g / min. During operation, sampling was performed every 20 minutes, and the volume average particle diameter D50v was measured by the above-described method.
The test is under conditions of very high stress. The change in particle size at 30 minutes is within ± 3 nm, and the change in particle size at 15 minutes is within ± 3 nm, which is practically acceptable. △, and the case where the amount of change in particle size in the 15th minute exceeds ± 3 nm is taken as x. In addition, ○ when there is no sedimentation, △ when sedimentation is very slight (a part of the bottom of the container is hidden), × It was. The results are shown in Table 1 below.

(Viscosity measurement evaluation in toner aggregation process)
The viscosity in the toner aggregating step is determined by using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) equipped with a water circulation type thermostat after collecting the slurry 15 minutes after the start of the temperature rise in the reaction vessel after the homogenizer dispersion. Measured.
For the measurement, use a cone plate / cup combination plate with a cone angle of 1.34 degrees, set the temperature of the circulation device to 20 ° C, and put 1g of the sample in the measuring cup when the temperature is stable, and shear The value was rotated at a speed of 77 [1 / s] and the value 10 seconds after the start of rotation was read. The measurement was performed three times, and the average value was taken as the viscosity η. The results are shown in Table 1 below.

(Toner durability evaluation)
The obtained developer is set in a developer of DocuCentreColor400 (Fuji Xerox Co., Ltd.), and on the developer developing roll after 30 sheets of A3 paper are output as white paper in an environment of temperature 30 ° C. and humidity 80%. The developer charge amount was measured. Subsequently, the developer charge amount on the developing unit developing roll after 300 sheets of A3 paper were output as white paper was measured. The developer charge amount was measured using a blow-off tribo measuring device (manufactured by Toshiba Chemical Co., Ltd.). From this measurement result, the absolute value ΔQ (μC / g) of the charge amount difference before and after the output of 300 blank sheets was obtained and evaluated according to the following criteria. The evaluation results are shown in Table 1 below.
○: Good ΔQ ≦ 3
Δ: Level of no problem in actual use: ΔQ ≦ 5
×: Level unbearable for actual use: ΔQ> 5

[Example 2]
In Example 1, a crystalline polyester resin dispersion was produced according to Example 1 except that the cooling rate in [Cooling step] in the production of the crystalline polyester resin dispersion (C1) was changed to the speed shown in Table 1 below. Then, titration was performed to produce a developer, which was evaluated. The titration curve by titration of the dispersion is shown in FIG.

Example 3
In Example 1, a crystalline polyester resin dispersion was produced according to Example 1 except that the cooling rate in [Cooling step] in the production of the crystalline polyester resin dispersion (C1) was changed to the speed shown in Table 1 below. Then, titration was performed to produce a developer, which was evaluated. The titration curve by titration of the dispersion is shown in FIG. 5 and the evaluation results are shown in Table 1 below.

Example 4
In Example 1, a crystalline polyester resin dispersion was produced according to Example 1 except that the cooling rate in [Cooling step] in the production of the crystalline polyester resin dispersion (C1) was changed to the speed shown in Table 1 below. Then, titration was performed to produce a developer, which was evaluated. A titration curve by titration of the dispersion is shown in FIG. 6, and each evaluation result is shown in Table 1 below.

Example 5
In Example 1, a crystalline polyester resin dispersion was produced according to Example 1 except that the cooling rate in [Cooling step] in the production of the crystalline polyester resin dispersion (C1) was changed to the speed shown in Table 1 below. Then, titration was performed to produce a developer, which was evaluated. A titration curve by titration of the dispersion is shown in FIG.

Example 6
<Production of crystalline polyester resin dispersion (C2)>
In a 2 L separable flask equipped with a stirring blade, a condenser, a thermometer, and a water dropping device, 300 parts by mass of the crystalline polyester resin (C1), 105 parts by mass of methyl ethyl ketone (solvent), and 90 parts by mass of isopropyl alcohol (solvent) The mixture was heated to 70 ° C. with a hot water bath, maintained at 70 ° C., and the resin was dissolved while stirring and mixing at 100 rpm [solution preparation step]. Thereafter, the stirring speed was set to 150 rpm, the hot water bath was set to 63 ° C., and the mixture was left for 30 minutes to stabilize the temperature. Next, 25 parts by mass of 10% by mass aqueous ammonia (reagent) is added in 1 minute [neutralizing agent addition step] After mixing for 10 minutes, 7 parts by mass of ion-exchanged water (aqueous medium) kept at 66 ° C. A total of 900 parts by mass was added dropwise at a rate of parts / min to cause phase inversion to obtain an emulsion [emulsion preparation step].
After completion of the water dripping, while discharging hot water in the hot water bath, 10 ° C. cold water having the same amount as the discharged hot water was added to the hot water bath, and the flask was cooled to 20 ° C. The cooling rate to 20 ° C was 0.9 ° C / min [cooling step].
Thereafter, a crystalline polyester resin dispersion (C2) was obtained from the obtained crystalline polyester resin (C2) by the method described in the production of the crystalline polyester resin dispersion (C1). The volume average particle diameter D50v of the resin particles in this dispersion was 105 nm, and the particle size distribution index GSDv was 1.22.

  In accordance with Example 1, the crystalline polyester resin dispersion was titrated to produce a developer and evaluated. A titration curve by titration of the dispersion is shown in FIG. 8, and each evaluation result is shown in Table 1 below.

Example 7
<Production of crystalline polyester resin dispersion (C3)>
Into a 2 L separable flask equipped with a stirring blade, a condenser, a thermometer, and a water dropping device, 300 parts by mass of the crystalline polyester resin (C1) and 360 parts by mass of methyl ethyl ketone (solvent) are placed, and up to 70 ° C. in a hot water bath. The mixture was heated and maintained at 70 ° C., and the resin was dissolved while stirring and mixing at 100 rpm [solution preparation step]. Thereafter, the stirring speed was set to 150 rpm, the hot water bath was set to 65 ° C., and the mixture was left for 30 minutes to stabilize the temperature. Next, 15 parts by mass of 10% by mass ammonia water (reagent) is added in 1 minute [neutralizing agent addition step] After mixing for 10 minutes, 7 parts by mass of ion-exchanged water (aqueous medium) kept at 65 ° C. A total of 900 parts by mass was added dropwise at a rate of parts / min to cause phase inversion to obtain an emulsion [emulsion preparation step].
After completion of the water dripping, while discharging hot water in the hot water bath, 10 ° C. cold water having the same amount as the discharged hot water was added to the hot water bath, and the flask was cooled to 20 ° C. The cooling rate to 20 ° C was 0.9 ° C / min [cooling step].
Thereafter, a crystalline polyester resin dispersion (C3) was obtained from the obtained crystalline polyester resin (C3) by the method described in the production of the crystalline polyester resin dispersion (C1). The volume average particle diameter D50v of the resin particles in this dispersion was 298 nm, and the particle size distribution index GSDv was 1.31.
In accordance with Example 1, the crystalline polyester resin dispersion was titrated to produce a developer for evaluation. A titration curve by titration of the dispersion is shown in FIG.

Example 8
<Preparation of crystalline polyester resin (C4)>
1,10-dodecanedioic acid: 50 mol%
1,6-hexanediol: 50 mol%
A crystalline polyester resin (C4) was obtained from the monomer component by the method described in the preparation of the crystalline polyester resin (C1). The crystalline polyester resin (C4) had a melting point Tc by DSC of 70.5 ° C., a weight average molecular weight Mw by GPC of 28000, a number average molecular weight Mn of 12000, and an acid value AV of 9.8 mgKOH / g.
A crystalline polyester resin dispersion (C4) was obtained from the obtained crystalline polyester resin (C4) by the method described in the production of the crystalline polyester resin dispersion (1).
In accordance with Example 1, the crystalline polyester resin dispersion was titrated to produce a developer for evaluation. The titration curve by titration of the dispersion is shown in FIG. 10 and the evaluation results are shown in Table 1 below.

Example 9
In Example 1, a crystalline polyester resin dispersion was produced according to Example 1 except that the cooling rate in [Cooling step] in the production of the crystalline polyester resin dispersion (C1) was changed to the speed shown in Table 1 below. Then, titration was performed to produce a developer, which was evaluated. A titration curve by titration of the dispersion is shown in FIG. 11 and each evaluation result is shown in Table 1 below.

[Comparative Example 1]
<Production of crystalline polyester resin dispersion (CZ1)>
In a 2 L separable flask equipped with a stirring blade, a condenser, a thermometer, and a water dropping device, 300 parts by mass of the crystalline polyester resin (C1), 105 parts by mass of methyl ethyl ketone (solvent), and 90 parts by mass of isopropyl alcohol (solvent) The mixture was heated to 70 ° C. with a hot water bath, maintained at 70 ° C., and the resin was dissolved while stirring and mixing at 100 rpm [solution preparation step]. Thereafter, the stirring rotation speed was set to 150 rpm, the hot water bath was set to 66 ° C., and the mixture was left for 30 minutes to stabilize the temperature. Next, 15 parts by mass of 10% by mass aqueous ammonia (reagent) is added in 1 minute [neutralizing agent addition step] After mixing for 10 minutes, 7 parts by mass of ion-exchanged water (aqueous medium) kept at 66 ° C. A total of 900 parts by mass was added dropwise at a rate of parts / min to cause phase inversion to obtain an emulsion [emulsion preparation step].
After completion of the dropwise addition of water, without cooling the emulsion, 800 parts by mass of the emulsion and 500 parts by mass of ion-exchanged water were placed in a 2 L eggplant flask, and an evaporator equipped with a vacuum control unit via a trap ball (Tokyo Rika Instruments Co., Ltd.) ). While rotating the eggplant flask, the mixture was heated at 60 ° C. for 30 minutes in a hot water bath to stabilize the liquid temperature, and then pressure reduction was started. Depressurization conditions are the capacity limit speed of the pump from 101 kPa to 50 kPa, and the pressure is reduced from 50 kPa to 7 kPa in 172 minutes. The solvent was recovered [solvent removal step]. When the solvent recovery amount reached 850 parts by mass, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a crystalline polyester resin dispersion (CZ1). Ion exchange water was added to the resulting dispersion to adjust the solid content concentration to 30% by mass.

  In accordance with Example 1, the crystalline polyester resin dispersion was titrated to produce a developer and evaluated. A titration curve by titration of the dispersion is shown in FIG. 12, and each evaluation result is shown in Table 1 below. Moreover, the graph of the particle size distribution before and behind pumping is shown in FIG. 13 and FIG.

  The toners of Examples 1 to 9 exhibited a level of particle size stability that had no practical problem even during storage with temperature change, and also exhibited excellent stability with no change in particle size even under stress due to pumping. .

1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention. It is a schematic block diagram which shows an example of the process cartridge of this invention. 1 is a titration curve diagram in Example 1. FIG. 4 is a titration curve diagram in Example 2. FIG. 4 is a titration curve diagram in Example 3. FIG. 6 is a titration curve diagram in Example 4. FIG. FIG. 6 is a titration curve diagram in Example 5. FIG. 6 is a titration curve diagram in Example 6. 10 is a titration curve diagram in Example 7. FIG. FIG. 9 is a titration curve diagram in Example 8. FIG. 10 is a titration curve diagram in Example 9. 4 is a titration curve diagram in Comparative Example 1. FIG. 2 is a particle size distribution before pumping in Comparative Example 1. FIG. 2 is a particle size distribution after pumping in Comparative Example 1. FIG.

Explanation of symbols

1Y, 1M, 1C, 1K, 107 photoconductor (image carrier)
2Y, 2M, 2C, 2K, 108 Charging roller 3Y, 3M, 3C, 3K Laser beam 3 Exposure device 4Y, 4M, 4C, 4K, 111 Developing device (developing means)
5Y, 5M, 5C, 5K Primary transfer rollers 6Y, 6M, 6C, 6K, 113 Photoconductor cleaning device (cleaning means)
8Y, 8M, 8C, 8K Toner cartridge 10Y, 10M, 10C, 10K Unit 20 Intermediate transfer belt 22 Drive roller 24 Support roller 26 Secondary transfer roller (transfer means)
28, 115 Fixing device (fixing means)
30 Intermediate transfer member cleaning device 112 Transfer device 116 Mounting rail 117 Opening 118 for static elimination exposure Opening 200 for exposure Process cartridge,
P, 300 Recording paper (transfer object)

Claims (9)

The crystalline polyester resin is dispersed in an aqueous medium,
When the titration curve was drawn with the horizontal axis representing the change in pH when titrated with sodium hydroxide and the vertical axis representing the value obtained by differentiating the pH with the amount of sodium hydroxide added dropwise, the titration curve was pH 2 A crystalline polyester resin dispersion characterized by having peaks in a region of 0.5 or more and pH 4.5 or less and a region of pH 5.0 or more and pH 7.0 or less. The peak in the region of pH 2.5 or more and pH 4.5 or less is peak (1), the peak in the region of pH 5.0 or more and pH 7.0 or less is peak (2), the height P1 of peak (1), The crystalline polyester resin dispersion according to claim 1, wherein the height P2 of 2) satisfies the relationship of the following formula (I).
Formula (I) 1.0 <P1 / P2 <5.0   3. The crystal according to claim 1, wherein the crystalline polyester resin has a volume average particle diameter D50v of 100 nm to 300 nm and a particle size distribution index GSDv of 1.0 to 1.3. Polyester resin dispersion. A step of preparing a solution by stirring and dissolving a crystalline polyester resin and a solvent in a temperature range of −15 ° C. or higher and + 15 ° C. or lower of the melting point of the crystalline polyester resin and lower than the boiling point of the solvent. When,
Adding a neutralizing agent to the solution;
A step of mixing and stirring the solution to which the neutralizing agent is added and an aqueous medium to prepare an emulsion;
Cooling the emulsion to a recrystallization temperature of the crystalline polyester resin to -5 ° C or lower;
And a step of removing the solvent from the emulsion after cooling. A method for producing a crystalline polyester resin dispersion, comprising:   A toner for developing an electrostatic charge image, which is prepared using the crystalline polyester resin dispersion according to any one of claims 1 to 3.   An electrostatic image developer, comprising at least a toner, wherein the toner is the electrostatic image developing toner according to claim 5.   A toner cartridge containing at least toner, wherein the toner is the electrostatic image developing toner according to claim 5.   A process cartridge comprising at least a developer holder and containing the electrostatic charge image developer according to claim 6.   An image carrier, development means for developing the electrostatic image formed on the image carrier as a toner image with the electrostatic image developer according to claim 6, and a toner image formed on the image carrier. An image forming apparatus comprising: transfer means for transferring onto a recording medium; and fixing means for fixing a toner image transferred onto the recording medium.