JP5223556B2 - Electrostatic latent image developing toner, electrostatic latent image developer, toner cartridge, process cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to an electrostatic latent image developing toner, an electrostatic latent image developer, a toner cartridge, a process cartridge, and an image forming apparatus.

  In electrophotography, generally, a latent image is electrically formed by various means on the surface of a photoreceptor (latent image holding member) using a photoconductive substance, and the formed latent image is used as a developer. After developing with toner, a toner image is formed, and the toner image is transferred to the surface of a transfer material such as paper via an intermediate transfer member as necessary, and fixed by heating, pressing, heating and pressing, etc. An image is formed through a plurality of processes. The toner remaining on the surface of the photoreceptor is generally cleaned by a cleaning process using a blade.

  As a fixing technique for fixing the toner image transferred to the surface of the transfer target, heat to be fixed by inserting the transfer target having the toner image transferred between a pair of rolls composed of a heating roll and a pressure roll. A roll fixing method is common. As a similar technique, a fixing method in which one or both of the rolls is replaced with a belt is also known. Since these techniques are in direct contact with the image as compared with other fixing methods, a fast and robust image can be obtained and the energy efficiency is high.

On the other hand, in recent years, toners that are particularly excellent in fixing properties (for example, low-temperature fixability and offset resistance) have been desired, and toners aimed at improving the fixing properties have been disclosed as described below.
Specifically, for example, in Patent Document 1, a low molecular weight resin and a high molecular weight resin are used as a binder resin in order to improve offset resistance, anti-winding characteristics, and charging characteristics, and a low molecular resin is used for the core. There is disclosed a toner in which a shell layer is made of a polymer resin, and the polymer resin is unevenly distributed near the surface. Further, a toner in which a release agent is unevenly distributed near the surface is disclosed.
Patent Document 2 discloses a toner characterized in that a vinyl resin is unevenly distributed in the vicinity of the toner particle surface in order to achieve both low-temperature fixability and heat-resistant storage stability and to improve offset resistance.
Further, Patent Document 3 discloses a toner that prevents filming and cleaning defects by causing compositional uneven distribution in the toner particle size distribution.

Furthermore, a toner that defines a storage elastic modulus such as a resin in order to improve the properties of the toner is disclosed. Specifically, for example, in Patent Document 4, the difference in storage elastic modulus at 150 ° C. between the binder resin and the charge control agent is a specific value for the purpose of improving the charge rising property and preventing carrier contamination by the charge control agent. Certain toners are disclosed.
JP 2000-292978 A JP 2007-248688 A JP 2008-64859 A JP-A-11-305489

  An object of the present invention is to provide a toner for developing an electrostatic latent image in which a change in glossiness due to continuous image formation is suppressed.

The above-mentioned subject is achieved by the following present invention.
That is, the invention according to claim 1
The volume average particle diameter of the whole toner is D50T, the glass transition temperature of the whole toner is Tg (° C.), the dynamic complex viscosity of Tg + 70 (° C.) of the whole toner is η ^* t (Pa · s), When the toner is classified to have a volume average particle size of (2/3) × D50T and the dynamic complex viscosity of Tg + 70 (° C.) in the classified toner is η ^* s (Pa · s), the η ^* T and η ^* s are toners for developing electrostatic latent images satisfying the relationship of the following formula (1).
200 ≦ (η ^* s / η ^* t) × 100 ≦ 1000 (1)

The invention according to claim 2
The electrostatic latent image developing toner according to claim 1, further comprising a binder resin, wherein the binder resin is a polyester resin.

The invention according to claim 3
An electrostatic latent image developer comprising at least the electrostatic latent image developing toner according to claim 1.

The invention according to claim 4
Toner that is removed from the image forming apparatus and supplied to at least developing means provided in the image forming apparatus is stored.
The toner is a toner cartridge which is the electrostatic latent image developing toner according to claim 1.

The invention according to claim 5
A process cartridge comprising at least a developer holder and containing the electrostatic latent image developer according to claim 3.

The invention according to claim 6
A latent image carrier,
An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the latent image holding member;
Developing means for developing the electrostatic latent image as a toner image with a developer;
Transfer means for transferring the toner image formed on the latent image holding member onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer object,
The image forming apparatus according to claim 3, wherein the developer is an electrostatic latent image developer.

According to the first aspect of the present invention, there is a change in glossiness due to continuous image formation as compared with the case where the η ^* t and the η ^* s do not satisfy the relationship of the above formula (1). It is suppressed.
According to the second aspect of the present invention, compared to the case where the binder resin is not a polyester resin, it is easy to produce a toner in which the η ^* t and the η ^* s satisfy the relationship of the above formula (1).
According to the third aspect of the present invention, compared to the case where the η ^* t and the η ^* s of the toner do not satisfy the relationship of the above formula (1), the change in the glossiness due to continuous image formation is suppressed. Is done.
According to the fourth aspect of the present invention, compared to the case where the η ^* t and the η ^* s of the toner do not satisfy the relationship of the above formula (1), the change in the glossiness due to continuous image formation is suppressed. Is done.
According to the fifth aspect of the present invention, compared to the case where the η ^* t and the η ^* s of the toner do not satisfy the relationship of the above formula (1), the change in glossiness due to continuous image formation is suppressed. Is done.
According to the sixth aspect of the present invention, compared to the case where the η ^* t and the η ^* s of the toner do not satisfy the relationship of the above formula (1), the change in glossiness due to continuous image formation is suppressed. Is done.

Hereinafter, the present invention will be described in detail.
<Toner for electrostatic latent image development>
The electrostatic latent image developing toner of the present embodiment (hereinafter sometimes simply referred to as “toner”) contains a binder resin, a release agent, and an aluminum element. The toner has a volume average particle diameter of D50T in the whole toner, a glass transition temperature in the whole toner as Tg (° C.), and a dynamic complex viscosity of Tg + 70 (° C.) in the whole toner as η ^* t (Pa · s). The dynamic complex viscosity of Tg + 70 (° C.) in the toner after classifying the toner to give a volume average particle diameter of (2/3) × D50T (hereinafter sometimes referred to as “small-diameter toner”). Is η ^* s (Pa · s), η ^* t and η ^* s satisfy the relationship of the following formula (1).
Formula (1): 200 ≦ (η ^* s / η ^* t) × 100 ≦ 1000

In the toner of the present exemplary embodiment, η ^* t and η ^* s satisfy the above formula (1), and thus a change in glossiness due to continuous image formation is suppressed.
Here, the value of (η ^* s / η ^* t) × 100 is larger than 100 because the small-diameter toner is a toner other than the small-diameter toner (the small-diameter toner is removed by classification from the toner before classification). This indicates that the value of the dynamic complex viscosity is higher than that of the remaining toner.

In the toner of the present exemplary embodiment, the reason why the change in glossiness due to continuous image formation is suppressed is not clear, but is estimated as follows. When the dynamic complex viscosity of the toner particles does not depend on the particle size, the toner particles having a small particle size tend to melt faster than the toner particles having a large particle size. A difference occurs in the meltability of the toner, which increases the difference in image glossiness.
However, in the toner of this embodiment, since η ^* t and η ^* s satisfy the above formula (1), the small-diameter toner is less likely to be melted as compared with the case where the dynamic complex viscosity does not depend on the particle size. In addition, the difference in melt viscosity at the fixing temperature is small between the small diameter toner and the large diameter toner. For this reason, in continuous image formation, an image formed between the initial stage where the temperature of the fixing unit is unstable (for example, the first sheet) and the stable period of the temperature of the fixing unit (for example, after the 100th sheet). It is estimated that the difference in glossiness between the two becomes smaller.

Further, in the toner of the present embodiment, η ^* t and η ^* s satisfy the above formula (1), so that change in color tone due to continuous image formation is suppressed.
As described above, when the dynamic complex viscosity of the toner particles does not depend on the particle size, a difference in meltability occurs between the small-diameter toner and the large-diameter toner, but in this embodiment, the difference in melt viscosity at the fixing temperature. Is considered to be smaller. Therefore, in this embodiment, when images based on the same image data are continuously formed, the images are formed between the initial period (for example, the first sheet) and the fixing unit temperature stable period (for example, the 100th sheet). It is presumed that the color gamut difference of the obtained image becomes small.

Furthermore, since the toner of this embodiment has η ^* t and η ^* s satisfying the above formula (1), a better fixed image is obtained as compared with the case where η ^* t and η ^* s do not satisfy the above formula (1). The temperature range to be formed is wide, and the environment dependence of the gloss unevenness of the fixed image is suppressed.
As described above, when the dynamic complex viscosity of the toner particles does not depend on the particle diameter, a difference in meltability occurs between the small diameter toner and the large diameter toner. However, in this embodiment, it is considered that the difference in the melting rate at the fixing temperature is smaller than in the case where the dynamic complex viscosity does not depend on the particle size. Therefore, in this embodiment, it is presumed that the fixing property is good regardless of the fixing temperature, and the uneven glossiness of the gradation image fixed at a high temperature (for example, 190 ° C.) is suppressed.

  As a method of classifying the toner so that the volume average particle diameter D50T is (2/3) × D50T, a classification method using an elbow jet is used. The volume average particle diameter of the toner classified by the elbow jet is determined by the cut point of the elbow jet. For example, by setting the elbow jet cut point to (5/6) × D50T, a toner having a volume average particle diameter of (2/3) × D50T (small diameter toner) can be obtained.

  The volume average particle diameter D50T is measured using Multisizer II (manufactured by Beckman-Coulter) with an aperture diameter of 50 μm. In this case, the measurement is performed after the toner is dispersed in an electrolyte aqueous solution (isoton aqueous solution) and dispersed by ultrasonic waves for 30 seconds or more. The measurement of the volume average particle diameter of the small diameter toner is similarly performed.

The dynamic complex viscosity (η ^* t and η ^* s) of the whole toner and the small-diameter toner are measured as follows. Specifically, a rheometer is used as a measuring device, and the temperature is raised from the Tg (° C.) at a heating rate of 1 ° C./min under the condition of a frequency of 1 rad / sec. Measure the complex modulus. The measurement distortion is 20% or less, and the measurement is performed using 8 mmφ and 25 mmφ parallel plates according to the measurement torque.

  Moreover, the measuring method of Tg is as follows. Specifically, using a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001), measurement is performed from room temperature (25 ° C.) at a temperature rising rate of 10 ° C./min according to JIS 7121-1987. . In the DSC curve obtained by the measurement, the temperature at the lowest temperature among the temperatures of the intersection points of the base line and the rising line in the endothermic part is defined as Tg.

As described above, η ^* t and η ^* s satisfy the relationship of the formula (1).
Further, η ^* t and η ^* s preferably satisfy the relationship of the following formula (2), and more preferably satisfy the relationship of the formula (2 ′).
Formula (2): 300 ≦ (η ^* s / η ^* t) × 100 ≦ 800
Formula (2 ′): 450 ≦ (η ^* s / η ^* t) × 100 ≦ 800

Hereinafter, the configuration of the toner in this embodiment will be described in more detail.
The toner contains at least a binder resin, a release agent, and an aluminum element, and may contain other components as necessary.

-Binder resin-
The binder resin is not particularly limited. For example, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, acrylic acid Esters having a vinyl group such as lauryl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; vinyl nitriles such as acrylonitrile and methacrylonitrile Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; monomers such as polyolefins such as ethylene, propylene and butadiene; Ranaru homopolymers or copolymers obtained by combining two or more of these, more mixtures thereof.
In addition, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc., non-vinyl condensation resins, or a mixture of these with the vinyl resin, or vinyl monomers in the presence of these resins Examples thereof include a graft polymer obtained by polymerization.
In the present embodiment, among the above binder resins, a polyester resin is desirable. By using a polyester resin as the binder resin, as will be described later, it becomes easy to produce a toner in which the η ^* t and the η ^* s satisfy the relationship of the above formula (1).

[Polyester resin]
Examples of the polyester resin include crystalline polyester resin and non-crystalline polyester resin, and those synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component. In addition, as said polyester resin, a commercial item may be used and what was synthesize | combined may be used.

Here, the “crystalline polyester resin” refers to a resin having a clear endothermic peak rather than a stepwise endothermic amount change in differential scanning calorimetry (DSC). On the other hand, a resin in which a stepwise endothermic change is recognized in DSC means “amorphous polyester resin”.
“Crystalline polyester resin” means a polymer (copolymer) obtained by polymerizing a component constituting polyester and another component in addition to a polymer having a 100% polyester structure as a constituent component. However, in the latter case, the component other than the polyester constituting the polymer (copolymer) is 50% by mass or less.

(Crystalline polyester resin)
The polymerizable monomer component constituting the crystalline resin includes a polymerizable monomer having a linear aliphatic component rather than a polymerizable monomer having an aromatic component in order to easily form a crystal structure. desirable. Furthermore, in order not to impair the crystallinity, it is desirable that the constituent component derived from the polymerizable monomer is 30 mol% or more for each single species in the polymer. In particular, when two or more kinds of polymerizable monomers are essential in a polyester resin or the like, it is desirable that each essential constituent polymerizable monomer type has the same configuration.

  As described above, the crystalline polyester resin is synthesized from, for example, a polyvalent carboxylic acid component and a polyhydric alcohol component.

  Examples of the polyvalent carboxylic acid component include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12 -Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid Aromatic dicarboxylic acids such as dibasic acids such as, and the like, and anhydrides and lower alkyl esters thereof are also included, but not limited thereto.

  Examples of the trivalent or higher carboxylic acid 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.

Moreover, as an acid component, the dicarboxylic acid component which has a sulfonic acid group other than the said aliphatic dicarboxylic acid and aromatic dicarboxylic acid may be contained.
Furthermore, in addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid component having a double bond may be contained.

  As the polyhydric alcohol component, an aliphatic diol is desirable, and a linear aliphatic diol having 7 to 20 carbon atoms in the main chain portion is more desirable. If the aliphatic diol is branched, the crystallinity of the polyester resin is lowered, and the melting point may be lowered. Further, when the main chain portion has less than 7 carbon atoms, when polycondensation with an aromatic dicarboxylic acid, the melting temperature becomes high and fixing at low temperature may be difficult, while the main chain portion has 20 carbon atoms. Exceeding the above range makes it difficult to obtain practical materials. The number of carbon atoms in the main chain portion is more preferably 14 or less.

  Specific examples of the aliphatic diol suitably used for the synthesis of the crystalline polyester include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6. -Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13- Examples include, but are not limited to, tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, and the like. Among these, considering availability, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are desirable.

  Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type and may use 2 or more types together.

  Among the polyhydric alcohol components, the content of the aliphatic diol is desirably 80 mol% or more, and more desirably 90% or more. When the content of the aliphatic diol is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting temperature is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. .

  If necessary, a polycarboxylic acid or a polyhydric alcohol may be added at the final stage of the synthesis for the purpose of adjusting the acid value or the hydroxyl value. Examples of polycarboxylic acids include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid; maleic anhydride, fumaric acid, succinic acid, alkenyl Aliphatic carboxylic acids such as succinic anhydride and adipic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid.

  Examples of polyhydric alcohols include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin; cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc. And aromatic diols such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct.

The production of the crystalline polyester resin is carried out, for example, at a polymerization temperature of 180 to 230 ° C., and the reaction system is depressurized as necessary to carry out the reaction while removing water and alcohol generated during condensation.
When the polymerizable monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If there is a polymerizable monomer having poor compatibility in the copolymerization reaction, the polymerizable monomer having poor compatibility and the polymerizable monomer and the acid or alcohol to be polycondensed are condensed in advance. And then polycondensation with the main component.

  Catalysts used in the production of crystalline polyester resins include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; zinc, manganese, antimony, titanium, tin, zirconium, germanium, etc. Metal compounds; phosphorous acid compounds; phosphoric acid compounds; and amine compounds.

  Specifically, for example, 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, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, Zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide Triphenyl phosphite, tris (2,4-di -t- butyl-phenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

The melting point of the crystalline polyester resin is desirably in the range of 50 to 100 ° C, more desirably in the range of 55 to 90 ° C, and further desirably in the range of 60 to 85 ° C. When the melting point is lower than 50 ° C., toner storage properties such as blocking of the stored toner and storage properties of the fixed image after fixing may become difficult. Further, when the melting point exceeds 100 ° C., sufficient low-temperature fixability may not be obtained.
In addition, melting | fusing point of the said crystalline polyester resin was calculated | required as the peak temperature of the endothermic peak obtained by the said differential scanning calorimetry (DSC).

  The acid value of the crystalline polyester resin (the number of mg of KOH required to neutralize 1 g of resin) is desirably in the range of 3.0 to 30.0 mgKOH / g, and 6.0 to 25.0 mgKOH / g. It is more desirable to be in the range of 8.0 to 20.0 mgKOH / g.

  When the acid value is lower than 3.0 mgKOH / g, the dispersibility in water is lowered, and thus it may be very difficult to produce emulsified particles by a wet process. Further, since stability as emulsified particles during aggregation is significantly reduced, it may be difficult to produce an efficient toner. On the other hand, when the acid value exceeds 30.0 mgKOH / g, the hygroscopicity as a toner increases and the toner may be easily affected by the environment.

  The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 6,000 to 35,000. When the molecular weight (Mw) is less than 6,000, the toner may permeate the surface of a recording medium such as paper at the time of fixing to cause fixing unevenness, or the strength of the fixed image against bending resistance may be reduced. On the other hand, when the weight average molecular weight (Mw) exceeds 35,000, the viscosity at the time of melting becomes too high, and the temperature for reaching a viscosity suitable for fixing may be increased, resulting in the deterioration of the low-temperature fixability. There is a case.

  The weight average molecular weight is measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC was performed with a THF solvent using a Tosoh column / TSKgel Super HM-M (15 cm) using a Tosoh GPC / HLC-8120 as a measuring device. The weight average molecular weight is calculated from the measurement result using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

  The content of the crystalline polyester resin in the toner is preferably in the range of 3 to 40% by mass, more preferably in the range of 4 to 35% by mass, and still more preferably in the range of 5 to 30% by mass. When the content of the crystalline polyester resin is less than 3% by mass, sufficient low-temperature fixability may not be obtained. When the content is more than 40% by mass, sufficient toner strength and fixed image strength cannot be obtained. There is a case where an adverse effect on the charging property is also caused.

  The crystalline resin containing the above crystalline polyester resin is mainly composed of a crystalline polyester resin synthesized from an aliphatic polymerizable monomer (hereinafter sometimes referred to as “crystalline aliphatic polyester resin”). 50 mass% or more) is desirable. Furthermore, in this case, the constituent ratio of the aliphatic polymerizable monomer constituting the crystalline aliphatic polyester resin is preferably 60 mol% or more, and more preferably 90 mol% or more. As the aliphatic polymerizable monomer, the above-mentioned aliphatic diols and dicarboxylic acids are preferably used.

(Non-crystalline polyester resin)
Non-crystalline polyester resins are highly compatible with crystalline polyester resins, and toners containing crystalline polyesters and non-crystalline polyester resins have become non-crystalline polyester resins as the viscosity of the crystalline polyester resin decreases at the melting temperature. Reduce viscosity. Therefore, sharp melt properties (sensitive melting characteristics) as a toner can be obtained, which is advantageous for low-temperature fixability.
In addition, since the non-crystalline polyester resin has good wettability with the crystalline polyester resin, the dispersibility of the crystalline polyester resin inside the toner is improved and the exposure of the crystalline polyester resin to the toner surface is suppressed. Therefore, the adverse effect on the charging property is suppressed. For this reason, it is also desirable from the viewpoint of improving the strength of the toner and the strength of the fixed image.

The non-crystalline polyester resin is obtained, for example, by condensation polymerization of polyvalent carboxylic acids and polyhydric alcohols.
As the polyvalent carboxylic acid, an aliphatic dicarboxylic acid is desirable, and a linear dicarboxylic acid is particularly desirable. For example, succinic 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, 1,10-undecanedicarboxylic acid Acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof, An acid anhydride is mentioned, However, It is not limited to these.

  The polyvalent carboxylic acid may contain components such as a dicarboxylic acid component having a double bond and a dicarboxylic acid component having a sulfonic acid group in addition to the aliphatic dicarboxylic acid component described above. The dicarboxylic acid component having a double bond includes a component derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a double bond, in addition to a component derived from a dicarboxylic acid having a double bond. Is also included. The dicarboxylic acid component having a sulfonic acid group includes a component derived from a dicarboxylic acid having a sulfonic acid group, a lower alkyl ester of a dicarboxylic acid having a sulfonic acid group, or an acid anhydride. Is also included.

  The dicarboxylic acid having a double bond is preferably used in order to prevent hot offset at the time of fixing because the entire resin can be crosslinked using the double bond. Examples of such dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, fumaric acid, maleic acid and the like are desirable in terms of cost.

  The dicarboxylic acid having a sulfonic acid group is effective in that the dispersion of a coloring material such as a pigment becomes good. Further, if a sulfonic acid group is present when the entire resin is emulsified or suspended in water to produce particles, it is emulsified or suspended without using a surfactant as described later. Examples of the dicarboxylic acid having a sulfonic acid 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, 5-sulfoisophthalic acid sodium salt and the like are desirable in terms of cost.

  As an example of the polyhydric alcohol in the amorphous polyester resin, an aliphatic diol is desirable. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tride Examples include, but are not limited to, candiol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, and the like.

  The polyhydric alcohol may contain components such as a diol component having a double bond and a diol component having a sulfonic acid group in addition to the above-described aliphatic diol.

  Examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol and the like. On the other hand, as the diol having a sulfonic acid group, 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, 2-sulfo-1,4-butane Examples include diol sodium salt.

  When adding an alcohol (diol) component other than these linear aliphatic diol components, the content of the diol component having a double bond and the diol component having a sulfonic acid group in the alcohol (diol) component 1 to 20 component mol% is desirable, and 2 to 10 component mol% is more desirable. When the content is less than 1 component mol%, pigment dispersion may be poor, the emulsified particle size may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, when it exceeds 20 mol%, the crystallinity of the polyester resin is lowered, the melting point is lowered, the storage stability of the toner is deteriorated, and the emulsion particle size is too small to make the latex hardly aggregate in the aggregation process. Sometimes.

  In addition to the above aliphatic diols, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, bisphenol S, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct, etc. Although used, it is particularly desirable to use bisphenol S derivatives such as bisphenol S, bisphenol S ethylene oxide adduct, and bisphenol S propylene oxide adduct from the viewpoint of toner productivity, heat resistance, and transparency. Moreover, both an acid (dicarboxylic acid) component and an alcohol component may contain a plurality of components. In particular, bisphenol S has an effect of improving heat resistance.

The glass transition temperature of the amorphous polyester resin is desirably in the range of 50 to 80 ° C. If Tg is lower than 50 ° C., problems may occur in terms of toner storage stability and fixed image storage stability. On the other hand, if it is higher than 80 ° C., the low-temperature fixability may be lowered as compared with the conventional case.
The Tg of the amorphous polyester resin is more preferably 50 to 65 ° C.

  The method for producing the amorphous polyester resin is not particularly limited, and is produced by a general polyester polymerization method in which a carboxylic acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. Produced separately for different types. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The production of the amorphous polyester is carried out at a polymerization temperature of 180 to 230 ° C., and the reaction is carried out while reducing the pressure in the reaction system as necessary to remove 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 solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the monomer and the carboxylic acid component or alcohol component to be polycondensed are condensed in advance and then polycondensed together with the main component. Good.

  As a catalyst used at the time of manufacture of non-crystalline polyester, the same kind of compound as the catalyst used at the time of manufacture of the above-mentioned crystalline polyester resin is mentioned.

  In addition to the above polymerizable monomers, compounds having shorter chain alkyl groups, alkenyl groups, aromatic rings and the like are also used for the purpose of adjusting the melting point and molecular weight of the amorphous polyester.

  Specific examples include dicarboxylic acids, alkyl dicarboxylic acids such as succinic acid, malonic acid, and oxalic acid, and phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, 4,4′-dibenzoic acid, 2,6- Examples include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid, and nitrogen-containing aromatic dicarboxylic acids such as dipicolinic acid, dinicotinic acid, quinolinic acid, and 2,3-pyrazinedicarboxylic acid. Short chain alkyl diols such as succinic acid, malonic acid, acetone dicarboxylic acid and diglycolic acid. These polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

  In addition, a monofunctional monomer may be introduced into the amorphous polyester for the purpose of blocking the polar group at the terminal of the amorphous polyester and improving the environmental stability of the toner charging characteristics.

  Monofunctional monomers include benzoic acid, chlorobenzoic acid, bromobenzoic acid, sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarbonylbenzoic acid, n-dodecylaminocarbonylbenzoic acid, tertiary butyl. Benzoic acid, naphthoic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, salicylic acid, thiosalicylic acid, phenylacetic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, octanecarboxylic acid, lauric acid, stearyl acid, and lower Monocarboxylic acids such as alkyl esters; or monoalcohols such as aliphatic alcohols, aromatic alcohols, and alicyclic alcohols are used.

[Styrene resin, (meth) acrylic resin, and copolymer resins thereof]
Styrene resin, (meth) acrylic resin, and styrene- (meth) acrylic copolymer resin are, for example, the following styrene monomers and (meth) acrylic monomers, alone or in combination, by a known method. Manufactured.
Specific examples of the styrene monomer include styrene, α-methyl styrene, vinyl naphthalene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 2-ethyl styrene, and 3-ethyl styrene. , Alkyl-substituted styrene having an alkyl chain such as 4-ethylstyrene, halogen-substituted styrene such as 2-chlorostyrene, 3-chlorostyrene and 4-chlorostyrene, fluorine-substituted such as 4-fluorostyrene and 2,5-difluorostyrene Examples include styrene. Specific examples of the (meth) acrylic acid monomer include (meth) acrylic acid, n-methyl (meth) acrylate, n-ethyl (meth) acrylate, and (meth) acrylic acid. n-propyl, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, ( N-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-lauryl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate, n (meth) acrylate -Octadecyl, isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isopentyl (meth) acrylate, (meth) Amyl crylate, neopentyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, (meth ) Biphenyl acrylate, diphenylethyl (meth) acrylate, t-butylphenyl (meth) acrylate, terphenyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth ) Dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate, methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid-β-carboxyethyl, (meth) acrylonitrile, (meth ) Acrylamide Etc. These monomers are produced by a known method alone or in combination.

  When using a styrene resin, a (meth) acrylic resin, or a copolymer resin thereof as a binder resin, the weight average molecular weight Mw is 20,000 or more and 100,000 or less, and the number average molecular weight Mn is 2,000 or more and 30,000. It is desirable to use the following range. On the other hand, when a polyester resin is used as the binder resin, a resin having a weight average molecular weight Mw of 5,000 or more and 60,000 or less and a number average molecular weight Mn of 2,000 or more and 10,000 or less may be used. desirable.

  The glass transition temperature of the styrene resin, (meth) acrylic resin, and these copolymer resins is desirably in the range of 40 ° C. or higher and 80 ° C. or lower. When the glass transition temperature is in the above range, the heat-resistant blocking property and the minimum fixing temperature are maintained.

In the present embodiment, it is desirable to use two or more binder resins having different molecular weights as the binder resin (hereinafter, two resins having different molecular weights having a relatively high molecular weight are referred to as “high molecular weight resins”. The one with relatively low molecular weight is called “low molecular weight resin”). By using two or more binder resins having different molecular weights, as described later, it becomes easy to produce a toner in which the η ^* t and the η ^* s satisfy the relationship of the above formula (1).

  As the two or more binder resins having different molecular weights, the same type of binder resin may be used, or two or more different types of binder resins may be combined (for example, polyester-based high molecular weight resin and styrene-acrylic low molecular weight). Or a combination with a resin). In this embodiment, it is desirable to use two or more of the same kind of binder resins having different molecular weights as the binder resin, and it is more desirable to use two or more polyester resins having different molecular weights.

  In this embodiment, as two or more polyester resins having different molecular weights, two or more amorphous polyester resins may be used, two or more crystalline polyester resins may be used, an amorphous polyester resin, and a crystal. A combination of reactive polyester resins may be used. In the present embodiment, as two or more polyester resins having different molecular weights, a form using two or more non-crystalline polyester resins and a form using a combination of a non-crystalline polyester resin and a crystalline polyester resin are desirable. A form using a combination of a crystalline polyester resin and a crystalline polyester resin is more desirable.

  In the present embodiment, when two resins having different molecular weights are used, the molecular weight of the high molecular weight resin is preferably 30,000 to 60,000 and more preferably 45,000 to 60,000 in terms of weight average molecular weight. Further, the molecular weight of the low molecular weight resin is desirably 8,000 or more and less than 30,000 in terms of weight average molecular weight, and desirably 10,000 or more and 20,000 or less. Further, the ratio between the molecular weight of the high molecular weight resin and the weight average molecular weight of the low molecular weight resin, that is, the value of the weight average molecular weight of the high molecular weight resin / the weight average molecular weight of the low molecular weight resin is desirably 2.0 or more and 6.0 or less. More preferably, it is 2.5 or more and 5.0 or less.

-Release agent-
The release agent is not particularly limited as long as it is a known release agent. For example, low molecular weight polyolefin waxes such as polyethylene, polypropylene, and polybutene; carnauba wax, rice wax, candelilla wax, wood wax, jojoba Plant waxes such as oils; animal waxes such as beeswax; mineral and petroleum waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax; Can be mentioned. Desirable are paraffin wax, microcrystalline wax, or polyolefin wax, and particularly desirable are paraffin wax or polyethylene wax. Moreover, these mold release agents may be used individually by 1 type, and may be used together 2 or more types.

  The crystallinity of the release agent is desirably 80 or more. The crystallinity of the release agent is measured by, for example, a minute high temperature X-ray diffractometer “RINT-1500V” (manufactured by Rigaku Corporation).

  The melting point of the release agent is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher, from the viewpoint of storage stability. From the viewpoint of offset resistance, it is preferably 110 ° C. or lower, more preferably 100 ° C. or lower, and further preferably 90 ° C. or lower.

The melt viscosity of the release agent is desirably 1 mPa · s or more and 10 mPa · s or less at 120 ° C. More preferably, it is 2 mPa · s or more and 8 mPa · s or less under the same conditions. Within this range, the releasability when combined with fibers is good and desirable.
The viscosity of the release agent at 120 ° C. 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 thermostatic bath and a cone plate is used. A cone plate having a cone angle of 1.34 ° is used. A sample is put into the cup, the temperature of the circulation device is set to 120 ° 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 allowed to stand 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 viscosity. Moreover, these mold release agents may be used individually by 1 type, and may be used together 2 or more types.

  The content of the release agent is preferably in the range of 3 to 20 parts by mass, and more preferably in the range of 5 to 18 parts by mass with respect to 100 parts by mass of the binder resin. When the content of the release agent is less than 3 parts by mass, the effect of adding the release agent is lost, and hot offset at a high temperature may be caused. On the other hand, if the amount exceeds 20 parts by mass, the chargeability may be adversely affected, and the mechanical strength of the toner tends to decrease, and the toner is easily destroyed by stress in the developing machine, causing carrier contamination and the like. There is.

-Colorant-
The toner according to the exemplary embodiment may include a colorant. The colorant is not particularly limited as long as it is a known colorant, and may be a dye or a pigment, but a pigment is desirable from the viewpoint of light resistance and water resistance.

  Specific examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.

  Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa yellow, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow NCG. Can be given.

  Examples of the orange pigment include red chrome yellow, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK and the like.

  Examples of red pigments include bengara, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake and lake. Red C, Rose Bengal, Eoxin Red, Alizarin Lake and the like.

  Examples of blue pigments include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, indanthrene blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, and malachite. Green ox sale rater. Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.

  Examples of the green pigment include chromium oxide, chrome 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.

  Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes. Specific examples include nigrosine. Furthermore, these may be used alone, may be used by mixing them, or may be used in a solid solution state.

  These colorants are dispersed by a known method, and for example, a rotary shearing type homogenizer, a media type dispersing machine such as a ball mill, a sand mill, or an attritor, a high pressure opposed collision type dispersing machine or the like is preferably used.

  Further, these colorants are dispersed in an aqueous system by the homogenizer using a polar surfactant.

  The colorant of the present embodiment is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, and dispersibility in the toner. The added amount of the colorant is desirably 1 to 20 parts by mass with respect to 100 parts by mass of the resin. It is also effective to use a surface-treated colorant or a pigment dispersant as necessary. By selecting the type of the colorant, yellow toner, magenta toner, cyan toner, black toner and the like can be obtained.

  When a magnetic material is used for the black colorant, it is desirable to add 30 to 100 parts by mass with respect to 100 parts by mass of the resin, unlike other colorants.

-Other ingredients-
In addition to the above components, various components such as an internal additive, a charge control agent, inorganic powder (inorganic particles), and organic particles may be added to the toner as necessary.
Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, alloys, and magnetic materials such as compounds containing these metals.
When the magnetic material is used as a magnetic toner, the ferromagnetic particles preferably have an average particle size of 2 μm or less, more preferably about 0.1 to 0.5 μm. The amount contained in the toner is preferably 20 to 200 parts by mass with respect to 100 parts by mass of the resin component, and particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the resin component. Further, it is desirable that the magnetic characteristics at the application of 10K oersted are those having a coercive force (Hc) of 20 to 300 oersted, saturation magnetization (σs) of 50 to 200 emu / g, and residual magnetization (σr) of 2 to 20 emu / g.

  Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments.

  The toner may contain an inorganic powder for the purpose of adjusting viscoelasticity. Examples of inorganic powders include silica, alumina, titania, calcium carbonate, magnesium carbonate, calcium phosphate, and cerium oxide. Can be mentioned.

Specific examples of the inorganic particles and organic particles, which are external additives externally added to the toner surface, include the following.
Examples of inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, Examples include Bengala, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, and silicon nitride. Among these, silica particles and titanium oxide particles are desirable, and particles that have been subjected to hydrophobic treatment are particularly desirable.

Inorganic particles are generally used for the purpose of improving fluidity. The primary particle size of the inorganic particles is desirably in the range of 1 to 200 nm, and the addition amount is desirably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the toner.
Organic particles are generally used for the purpose of improving cleaning properties and transfer properties. Specifically, for example, fluorine resin powders such as polyvinylidene fluoride and polytetrafluoroethylene, fatty acid metal salts such as zinc stearate and calcium stearate. , Polystyrene, polymethyl methacrylate and the like.

-Toner characteristics-
The volume average particle diameter (D50T) of the entire toner is desirably in the range of 3 μm to 8 μm. When D50T is smaller than the above range, the toner fluidity is lowered, the chargeability of each particle is liable to be lowered, and the charge distribution is widened, so that fogging on the background and toner spillage from the developing device are liable to occur. If D50T is larger than the above range, the resolution decreases, so that sufficient image quality cannot be obtained, and it may be difficult to satisfy recent high image quality requirements.

The toner of this embodiment desirably has a shape factor SF1 of 100 or more and 140 or less. When the shape factor SF1 is within the above range, the transfer efficiency and the image density are improved, so that a high-quality image is formed and a high-gloss image is formed.
Examples of a method for setting the toner shape factor SF1 in the above range include a method for producing a toner by an emulsion aggregation method which is a wet manufacturing method. By manufacturing the toner using a wet manufacturing method such as an emulsion aggregation method, a toner having a shape factor SF1 in the above range is manufactured.

Here, the shape factor SF1 is obtained by the following equation (8).
SF1 = (ML ² / A) × (π / 4) × 100 (8)
In the above formula (8), 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 is calculated as follows, for example. That is, an optical microscope image of the higher alcohol particles dispersed on the surface of the slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length and projected area of 100 particles are obtained, calculated by the above equation (8), and the average Obtained by determining the value.

  In the toner of the present exemplary embodiment, the aluminum content Alt (atom%) in the whole toner is desirably 0.005 atom% or more and 0.10 atom% or less, and is 0.010 atom% or more and 0.050 atom% or less. More preferably, it is 0.010 atom% or more and 0.030 atom% or less. When Alt is in the above range, the fixing temperature dependency of fixing characteristics, image unevenness, gloss unevenness, reduction in glossiness, and the like are suppressed.

In this embodiment, it is desirable that the relationship between the aluminum content Alt (atom%) in the entire toner and the aluminum content Als (atom%) in the small diameter toner satisfies the relationship of the following formula (3). It is more desirable to satisfy the relationship of the formula (3 ′), and it is further desirable to satisfy the relationship of the following formula (3 ″).
Formula (3): 120 ≦ (Als / Alt) × 100 ≦ 200
Formula (3 ′): 150 ≦ (Als / Alt) × 100 ≦ 200
Formula (3 ″): 170 ≦ (Als / Alt) × 100 ≦ 200
When Alt and Als satisfy the relationship of the above formula, the cleaning property is improved, and uneven gloss is suppressed during high-temperature fixing.

  In the toner of the present exemplary embodiment, the weight average molecular weight MwT in the whole toner is desirably 20,000 or more and 50,000 or less, and 25,000 or more and 45,000 or less from the viewpoint of low-temperature fixability and mechanical strength. More preferably, it is more preferably 30,000 or more and 40,000 or less.

In this embodiment, it is desirable that the relationship between the weight average molecular weight MwT in the whole toner and the weight average molecular weight MwS in the small diameter toner satisfies the relationship of the following formula (4), and the relationship of the following formula (4 ′) is satisfied. It is more desirable to satisfy, and it is still more desirable to satisfy the relation of a following formula (4 '').
Formula (4): 150 ≦ (MwS / MwT) × 100 ≦ 200
Formula (4 ′): 160 ≦ (MwS / MwT) × 100 ≦ 200
Formula (4 ″): 170 ≦ (MwS / MwT) × 100 ≦ 200
When MwT and MwS satisfy the relationship of the above formula, the cleaning property is improved and the fixing characteristics at the time of high-temperature fixing are improved.

  On the other hand, if the (MwS / MwT) × 100 value is smaller than the above range, the molecular weight of the small-diameter toner becomes low and the strength of the small-diameter toner becomes low, so that the toner is easily crushed, and as a result, the cleaning characteristics may deteriorate. Also, if the (MwS / MwT) × 100 value is smaller than the above range, the value of the molecular weight is close between the small-diameter toner and the large-diameter toner, so the small-diameter toner melts faster during high-temperature fixing. The fixing characteristics of the entire toner may be deteriorated. On the other hand, if the value of (MwS / MwT) × 100 is larger than the above range, the weight average molecular weight MwS of the small diameter toner becomes too larger than the weight average molecular weight MwT of the whole toner. In some cases, the toner melts with a delay, and the fixing characteristics of the whole toner deteriorate. As a result, image unevenness due to insufficient melting of the small diameter toner may occur.

Furthermore, in the present embodiment, it is desirable that Alt and Als satisfy the relationship of the above equation, and that MwT and MwS satisfy the relationship of the above equation. When Alt and Als, and MwT and MwS satisfy the relationship of the above formula, η ^* t and η ^* s can easily satisfy the relationship of the above formula. When η ^* t and η ^* s of the toner satisfy the relationship of the above formula, the fixing characteristics and the like are further improved as described above.

The η ^* t value is preferably 3 × 10 ³ Pa · s or more, and more preferably 7 × 10 ³ Pa · s or more, from the viewpoint of anti-offset at high temperature fixing. The η ^* t value is preferably 1 × 10 ⁵ Pa · s or more from the viewpoint of offset resistance during high-temperature fixing.

Further, when a crystalline resin is used as the binder resin, from the viewpoint that the crystalline resin quickly exudes when the melting point exceeds the melting point and exhibits low-temperature fixability, when the melting point of the crystalline resin is Tm, Tm + 10 ° C. The dynamic complex viscosity is desirably 1 × 10 ⁵ Pa · s or less, and more desirably 5 × 10 ⁴ Pa · s or less. From the viewpoint of offset resistance during high-temperature fixing, the dynamic complex viscosity at Tm + 10 ° C. is desirably 3 × 10 ³ Pa · s or more.

-Toner production method-
Examples of the toner production method include a dry production method and a wet production method. From the viewpoint that it is easy to control η ^* t and η ^* s so as to satisfy the relationship of the above formula, and the toner shape factor SF1. From the viewpoint of setting the above in the above range, it is desirable to adopt a wet manufacturing method.
Examples of the wet production method include an emulsion aggregation method, a melt suspension method, and a dissolution suspension method. Among these, the emulsion aggregation method is desirable from the viewpoint of controlling the particle size distribution, particularly narrowing the distribution on the small particle size side.

  As a toner manufacturing method by a wet manufacturing method, for example, a resin particle dispersion adjusting step for adjusting a resin particle dispersion in which binder resin particles are dispersed, and a release agent particle dispersion in which release agent particles are dispersed are used. Mixing a release agent particle dispersion adjusting step to adjust, a resin particle dispersion, a release agent particle dispersion, and an aggregating agent containing aluminum element (hereinafter sometimes referred to as “aluminum-containing aggregating agent”), Aggregated particle adjustment step of aggregating resin particles and release agent particles to adjust the aggregated particles, and aggregating particle dispersion in which the aggregated particles are dispersed is heated to a temperature equal to or higher than the glass transition temperature of the binder resin. And a toner production method including a coalescence and coalescence process.

Further, as one of means for producing a toner in which η ^* t and η ^* s satisfy the relationship of the above formula, there is a method of adjusting so that Alt and Als, and MwT and MwS satisfy the relationship of the above formula.
Further, as means for adjusting Alt and Als so as to satisfy the relationship of the above formula, for example, as the above-mentioned aggregated particle adjustment step, an aggregated particle adjustment step including a first aggregated particle adjustment step and a second aggregated particle adjustment step described later The method using is mentioned.
Further, as a means for adjusting MwT and MwS so as to satisfy the relationship of the above formula, for example, as will be described later, a high molecular weight resin and a low molecular weight resin are used as a binder resin, and dispersion of high molecular weight resin particles is dispersed. The liquid and the dispersion in which the particles of the low molecular weight resin are dispersed are separately adjusted, and the coagulation value of each dispersion is controlled.
Hereinafter, each step will be described in detail.

[Resin particle dispersion adjustment process]
Examples of the resin particle dispersion adjusting step include a method of emulsifying by a mechanical shear force, a method using a transfer emulsification method, and the like.
In particular, when a polyester resin is used as the binder resin, it is desirable to use the transfer emulsification method. By using the transfer emulsification method, it is easy to adjust the coagulation value of the resin particle dispersion, and it becomes easy to produce a toner in which η ^* t and η ^* s satisfy the relationship of the above formula.

(Transfer emulsification method)
Examples of the method for adjusting the resin particle dispersion by the transfer emulsification method include the following methods. Specifically, for example, an amorphous polyester resin is dissolved in a mixed solution of an organic solvent (good solvent) and a water-soluble solvent (water-soluble poor solvent), and a neutralizer (for example, ammonia is used as necessary). Etc.) or a dispersion stabilizer and a water-soluble solvent (for example, water) is added dropwise with stirring to obtain emulsified particles, and then the solvent in the resin particle dispersion is removed to obtain an emulsion (resin particle dispersion). Liquid). The order of adding the neutralizing agent and the dispersion stabilizer may be changed.

  Examples of the organic solvent (resin dissolving solvent) for dissolving the amorphous polyester resin include formic acid esters, acetic acid esters, butyric acid esters, ketones, ethers, benzenes, and halogenated carbons. Specifically, for example, 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 , Methyl ketones such as MIBK, 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, chloroform, monochlorobenzene, dichloroethylidene, and other halogenated carbons may be used alone or in combination of two or more, but they are low boiling solvents from the standpoint of availability and ease of recovery during solvent removal. Usually, acetates, methyl ketones, and ethers are preferably used. In particular, acetone, methyl ethyl ketone, acetic acid, ethyl acetate, butyl acetate is preferred. Among the organic solvents, from the viewpoint of suppressing the organic solvent from remaining in the resin particles, it is desirable to use one having relatively high volatility.

  As the water-soluble solvent, ion-exchanged water is basically used, but a water-soluble organic solvent may be included so as not to destroy the oil droplets. Examples of the water-soluble organic solvent 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, Examples include ethylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; ethers, diols, THF, acetone and the like. The mixing ratio of these water-soluble organic solvents to ion-exchanged water is preferably 1% or more and 50% or less, and more preferably 1% or more and 30% or less by mass ratio. In addition, the water-soluble organic solvent may be added to the resin solution and used in addition to the ion-exchanged water to be added. When a water-soluble organic solvent is added, the wettability between the resin and the resin-dissolving solvent is adjusted, and a function of decreasing the liquid viscosity after dissolving the resin is expected.

  If necessary, a dispersion stabilizer may be added to the mixed solution of the resin solution and the water-soluble solvent so that the emulsion stably maintains a dispersed state. Examples of the dispersion stabilizer include those that form a hydrophilic colloid in a water-soluble solvent. For example, cellulose derivatives such as hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose; polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, Examples thereof include synthetic polymers such as polyacrylate and polymethacrylate, and dispersion stabilizers such as gelatin, gum arabic and agar. As the dispersion stabilizer, solid powders such as silica, titanium oxide, alumina, tricalcium phosphate, calcium carbonate, calcium sulfate, and barium carbonate are also used. These dispersion stabilizers are added so that the concentration in the water-soluble solvent is desirably 0% by mass to 20% by mass, and more desirably 0% by mass to 10% by mass.

  A surfactant is also used as the dispersion stabilizer. Examples of the surfactant are the same as those used in the colorant dispersion described later. For example, in addition to natural surfactant components such as saponins, 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, phosphate 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, nitric acid, hydrochloric acid, sodium hydroxide, ammonia and other general acids and alkalis are used, but sodium hydroxide is used from the viewpoint of easy adjustment of the coagulation value of the resin particle dispersion. Is desirable.

As a method for removing the organic solvent from the emulsion, a method in which the organic solvent is volatilized at room temperature (25 ° C.) or under heating, and a method in which reduced pressure is combined with this are preferably used.

(Method of emulsification by mechanical shearing force)
Examples of the method of emulsifying with a mechanical shear force include a method in which a shear force is applied to a solution obtained by mixing an aqueous medium and a binder resin with a disperser. At that time, it is desirable to form particles by heating to lower the viscosity of the resin component. A dispersant may be used for stabilizing the dispersed resin particles.

Examples of the aqueous medium include water such as distilled water and ion-exchanged water; alcohols; and the like.
Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; sodium dodecylbenzenesulfonate, sodium octadecylsulfate, olein Anionic surfactants such as sodium acid, sodium laurate, potassium stearate, cationic surfactants such as laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, zwitterionic surfactants such as lauryldimethylamine oxide , Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, etc. Surfactants such as nonionic surfactants; and the like are; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, inorganic salts such as barium carbonate.

  Examples of the disperser include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser.

(Characteristics of resin particle dispersion)
The content of the resin particles contained in the resin particle dispersion is preferably in the range of 10 to 50% by mass, more preferably in the range of 20 to 40% by mass. When the content is less than 10% by mass, the particle size distribution is widened and the toner characteristics may be deteriorated. On the other hand, if it exceeds 50% by mass, uniform stirring becomes difficult, and it may be difficult to obtain a toner having a narrow particle size distribution and uniform characteristics.

  As the size of the resin particles, the average particle size (volume average particle size) is preferably in the range of 0.08 to 0.8 μm, more preferably 0.09 to 0.6 μm, and 0.10 to 0.5 μm. More desirable.

  The volume average particle diameter of the resin particles is measured using a laser diffraction particle size distribution measuring device (LA-700: manufactured by Horiba, Ltd.). As a measuring method, the sample in the state of dispersion is adjusted so as to have a solid content of 2 g, and ion exchange water is added thereto to make 40 ml. This is put into the cell, waits for 2 minutes, and is measured when the concentration in the cell becomes stable. The obtained volume average particle diameter for each channel is accumulated from the smaller volume average particle diameter, and the place where the accumulation reaches 50% is defined as the volume average particle diameter. The volume average particle diameters of the release agent particles and the colorant particles are also measured by the same method.

  When a polyester resin is used as the binder resin, the ratio of resin particles having a particle size of 10 to 40 nm (hereinafter sometimes referred to as “fine powder”) to the entire resin particles (hereinafter referred to as “fine powder amount”) It is desirable to control). Specifically, it is desirable that the amount of fine powder of the crystalline polyester resin and the amount of fine powder of the non-crystalline polyester resin are both 0 to 5% by mass.

Since the crystalline polyester resin fine powder has a high acid value in the resin, the stability of the particles becomes high. Therefore, the stability of resin particles having a relative thickness of 60 to 300 nm is lowered, and the entire mechanism system is in an unstable state. In this state, if the amount of the fine powder of the crystalline polyester resin particles is in the range of 0 to 5% by mass, fine powder having an acid value higher than the average is decreased, so that there is no variation in the stability of the resin particles of 60 to 300 nm. For this reason, toner with stable granulation behavior is produced.
As for the non-crystalline polyester resin particles, if the amount of fine powder is in the range of 0 to 5% by mass, fine powder having an acid value higher than average is reduced, and particles of 60 to 300 nm with no variation in particle stability are obtained. As a result, the storage stability of the resin particles is improved, and the particle size distribution of the granulated toner is narrowed.

On the other hand, the amount of fine powder of the amorphous resin particles is in the range of 0 to 5% by mass, but if the amount of fine powder of the crystalline polyester resin particles is more than 5% by mass, the amount of fine powder of the crystalline polyester resin particles is large. In particular, the stability of resin particles of 60 to 300 nm is lowered. Therefore, when toner granulation is attempted by the emulsion aggregation method, a large amount of emulsified particles whose particle stability has been lowered is taken into the toner, resulting in a finely powdered toner in which non-crystalline polyester resin is unevenly distributed in the toner particles. As a result, the fixability of the toner portion may be inferior and the offset characteristics may deteriorate.
Further, the fine powder amount of the crystalline polyester resin particles is in the range of 0 to 5% by mass. If the fine powder amount of the amorphous resin particles is more than 5% by mass, the resin particles of 60 to 300 nm in the amorphous resin Stability is reduced. Therefore, when toner granulation is attempted by the emulsion aggregation method, a toner having an undefined particle granulation behavior and an expanded particle size distribution may be obtained, and it may be difficult to set GSDp-under to 1.30 or less.

Furthermore, when both the fine powder amount of the crystalline polyester resin particles and the fine powder amount of the non-crystalline resin particles exceed 5% by mass, the resin particles having decreased stability of the particles are blended together. When the toner is granulated, the particle size distribution of the toner becomes remarkably wide, and it may be more difficult to set the GSDp-under to 1.30 or less.
As described above, in order to further improve the charging property, the anti-filming property, and the cleaning property, the amount of fine particles of the resin particles in the crystalline polyester resin and the non-crystalline polyester resin should be in the range of 0 to 5% by mass. Is desirable.

In addition, as a method for confirming the amount of fine powder in each resin particle, the following procedure is used.
First, the resin particle dispersion is separated into a precipitate of resin particles and a white supernatant by separating the resin particle dispersion at 14,000 rpm over 4 hours. When this supernatant is dried and observed with a scanning electron microscope (SEM) (manufactured by Hitachi, S4700), it is confirmed that the dispersed particles have a particle size of 10 to 40 nm. Further, the supernatant is dried with a freeze dryer to obtain a solid content of fine powder, and the amount of fine powder is specified by measuring its mass.

The coagulation value of the resin particles in the resin particle dispersion is desirably in the range of 1 × 10 ⁻⁵ mol / g or more and 1 × 10 ⁻¹ mol / g or less. When the coagulation value is smaller than 1 × 10 ⁻⁵ mol / g, it becomes difficult to maintain the particles due to destabilization of the resin particles, and it becomes extremely difficult to control the particle size of the aggregated particles. On the other hand, if the coagulation value is larger than 1 × 10 ⁻¹ mol / g, the resin particles are very stabilized, aggregation between the particles hardly occurs, and control of the particle size becomes difficult.

In addition, when two or more binder resins having different molecular weights are used as the binder resin, a different resin is used for each binder resin from the viewpoint that the relationship between MwT and MwS of the manufactured toner satisfies the above formula. It is desirable to adjust the particle dispersion. Specifically, for example, when a high molecular weight resin and a low molecular weight resin are used, a high molecular weight resin particle dispersion in which particles of a high molecular weight resin are dispersed, and a low molecular weight resin particle dispersion in which particles of a low molecular weight resin are dispersed. Are preferably adjusted separately.
When a high molecular weight resin and a low molecular weight resin are used as the binder resin, the coagulation value of the resin particles in the high molecular weight resin particle dispersion is larger than the coagulation value of the resin particles in the low molecular weight resin particle dispersion. It is desirable to adjust to the value. Specifically, the coagulation value of the resin particles in the high molecular weight resin particle dispersion is desirably 1.0 × 10 ⁻³ mol / g or more and 1.0 × 10 ⁻¹ mol / g or less. It is more desirable that it is not less than × 10 ⁻² mol / g and not more than 1.0 × 10 ⁻¹ mol / g. The析値coagulation of the resin particles in the low molecular weight resin particle dispersion is desirably less 1.0 × ¹⁰ -5 mol / g or more ^{1.0 × 10 -2 mol / g,} 1.0 × 10 - It is more desirable to be ⁵ mol / g or more and 1.0 × 10 ⁻³ mol / g or less.

  Here, the coagulation value of the resin particles is the minimum amount of magnesium chloride (mol) required for agglomerating 1 g of resin particles in a resin particle dispersion (emulsion) having a solid content of 10% by mass, pH 7, and a temperature of 25 ° C. / G). The larger the coagulation value, the more stable the emulsified particles (resin particles) in the dispersion (harder to aggregate).

  When a polyester resin is used as the binder resin, examples of the method for controlling the coagulation value include a method of controlling by changing the amount of sodium hydroxide used for transfer emulsification.

[Partition agent particle dispersion adjustment process]
The release agent particle dispersion includes, for example, an ionic surfactant, a polymer electrolyte such as a polymer acid or a polymer base, and the above release agent dispersed in water, heated to a temperature higher than the melting temperature, The release agent particle dispersion containing the release agent particles is prepared by adjusting the particles by using a homogenizer or a pressure discharge type disperser.

  The volume average particle size of the release agent particles in the release agent particle dispersion is 1 μm or less in order to easily adjust the volume average particle size and particle size distribution of the toner particles to desired values. Desirably, it is more desirably 100 nm or more and 300 nm or less.

Further, a surfactant may be used for the purpose of stabilizing the dispersion of each dispersion.
Examples of the surfactant include anionic surfactants such as sulfate, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, ionic surfactants are desirable, and anionic surfactants and cationic surfactants are more desirable. The said surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the anionic surfactant include, for example, 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; Sodium alkylnaphthalene sulfonate such as lauryl sulfonate, dodecyl benzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate; naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate, etc. Sulfonates: lauryl phosphate, isopropyl phosphate, nonylphenyl Phosphoric acid esters such as chromatography ether phosphates; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate; sulfosuccinate salts such as sulfosuccinate lauryl disodium; and the like.

  Specific examples of the cationic surfactant include amine salts such as laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate; lauryltrimethylammonium chloride, dilauryl Dimethylammonium chloride, distearyldimethylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate , Alkylbenzene trimethyl ammonium chlora De, quaternary ammonium salts such as alkyl trimethyl ammonium chloride; and the like.

  Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, Alkylphenyl ethers such as polyoxyethylene nonylphenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, poly Alkylamines such as oxyethylene oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkylamides such as reoxyethylene 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, Alkanolamides such as stearic acid diethanolamide and oleic acid diethanolamide; sorbitan esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate Ethers; and the like.

  The content of the surfactant in each dispersion may be a level that does not hinder the effect of the present embodiment, and is generally a small amount, specifically, a range of about 0.01 to 10% by mass. More preferably, it is in the range of 0.05 to 5% by mass, and more preferably in the range of about 0.1 to 2% by mass. When the surfactant content is less than 0.01% by mass, the release agent particle dispersion becomes unstable, causing aggregation, and the stability between the particles differs during aggregation. There may be a problem such as liberation of the water. On the other hand, if the surfactant content exceeds 10% by mass, the particle size distribution of the particles may become wide, and the control of the particle size may become difficult. In general, a suspension-polymerized toner dispersion having a large particle size is stable even if the amount of the surfactant used is small.

[Other dispersion adjustment processes]
When the toner contains a colorant, the method for producing the toner may include a step of separately adjusting the colorant particle dispersion. The colorant particle dispersion is prepared by a known method. For dispersion of the colorant particles, for example, a rotary shear type homogenizer, a media type disperser such as a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersion is used. A machine or the like is preferably used.
Further, a polar ionic surfactant is used and dispersed in an aqueous solvent using a homogenizer as described above to produce a colorant particle dispersion.

  The volume average particle diameter of the colorant particles in the colorant particle dispersion is desirably 1 μm or less in order to facilitate adjusting the volume average particle diameter and particle size distribution of the toner particles to desired values. It is more desirable that the thickness be 100 nm or more and 300 nm or less.

[Aggregated particle adjustment step]
The aggregated particle adjustment step may include a first aggregated particle adjustment step and a second aggregated particle adjustment step from the viewpoint that Alt and Als of the manufactured toner and MwT and MwS satisfy the relationship of the above formula. desirable.
Specifically, in the first aggregated particle adjusting step, a resin particle dispersion, a release agent particle dispersion, and an aggregating agent containing aluminum element (hereinafter sometimes referred to as “aluminum-containing aggregating agent”) are mixed. In this step, the resin particles and the release agent particles are aggregated to adjust the first aggregated particles.
The second aggregated particle adjustment step is a step of growing the first aggregated particles at a pH higher than that of the first aggregated particle adjustment step and adjusting the second aggregated particles having a larger particle size than the first aggregated particles.
Hereinafter, the first aggregated particle adjustment step and the second aggregated particle adjustment step will be described.

In the first aggregated particle adjustment step, the dispersion obtained in the dispersion adjustment step (resin particle dispersion, release agent particle dispersion, colorant particle dispersion if necessary), and aluminum-containing aggregation The first mixed solution is prepared by adding an acid and adding an acid.
Next, the first mixed solution is heated to agglomerate particles (resin particles, release agent particles, and, if necessary, colorant particles) under stirring to form first aggregated particles.

In the second aggregated particle adjustment step, first, an alkali is added to the dispersion of the first aggregated particles formed in the first aggregated particle adjustment step, and further resin particles (or resin particle dispersion) and an aluminum-containing flocculant are added. To prepare the second mixed solution.
Next, the second aggregated particles are formed by heating the second mixed solution and growing the first aggregated particles under stirring.

  Here, examples of the aluminum-containing flocculant include metal salts such as aluminum chloride and aluminum sulfate, and inorganic metal salt polymers such as polyaluminum chloride and polyaluminum hydroxide. Moreover, as an acid added when adjusting a 1st mixed solution, nitric acid etc. are mentioned, for example. Furthermore, as an alkali added when adjusting a 2nd mixed solution, sodium hydroxide aqueous solution etc. are mentioned, for example.

As a method of adjusting the value of (Als / Alt) × 100 of the toner, for example, the value of (Als / Alt) × 100 is controlled by adjusting the pH of the first mixed solution and the second mixed solution. A method is mentioned.
The optimum values of the pH of the first mixed solution and the second mixed solution may differ depending on the aluminum-containing flocculant used. Hereinafter, a case where aluminum sulfate is used will be described as an example.

  The pH of the first mixed solution is desirably 2.0 or more and less than 3.5, more desirably 2.0 or more and 3.0 or less, and further desirably 2.0 or more and 2.5 or less. The pH of the second mixed solution is preferably 4.5 or more and 6.0 or less, more preferably 4.5 or more and 5.5 or less, and further preferably 4.5 or more and 5.0 or less.

  By setting the pH of the first mixed solution in the above range, the aggregating force of the aluminum-containing flocculant is high, so that the first agglomerated particles that are strongly agglomerated and incorporate a large amount of aluminum element are formed. The pH of the first mixed solution is adjusted to the above range by adding an acid such as nitric acid.

Further, by setting the pH of the second mixed solution in the above range, the cohesive force of the aluminum-containing flocculant becomes weak, so that the amount of aluminum element taken in during the process of growing the first aggregated particles is reduced. The second aggregated particles that did not grow so much in the second aggregated particle adjustment step (that is, small particle size) have a content of aluminum element larger than the second aggregated particles that grew large (that is, large particle size). Become more.
As described above, the value of (Als / Alt) × 100 of the toner is adjusted.

Examples of the method for adjusting the value of (MwS / MwT) × 100 of the toner include the following methods.
Specifically, for example, a high molecular weight resin particle dispersion and a low molecular weight resin particle dispersion having different resin molecular weights and coagulation values of resin particles are separately prepared, and the resin particle dispersion used in the first aggregated particle adjustment step As the resin particle dispersion used only in the second aggregated particle adjustment step, only the low molecular weight resin particle dispersion is used, and the value of (MwS / MwT) × 100 of the toner is used. The method of adjusting is mentioned.

  In such a case, it is desirable for the pH of the second mixed solution to be in the above range because the effect due to the different coagulation values becomes significant. If the pH of the second mixed solution is smaller than the above range, the cohesiveness of the resin particles does not depend on the particle size, so it is difficult to set the (MwS / MwT) × 100 value in the above range. On the other hand, if the pH of the second mixed solution is larger than the above range, the cohesiveness of the resin particles is deteriorated, so that the value of GSDp-under of the toner is increased and the amount of fine powder is increased. May occur or cleaning performance may deteriorate.

  When PAC is used as the aluminum-containing flocculant, the pH of the first mixed solution is preferably 1.5 or more and less than 3.0, more preferably 1.5 or more and 2.5 or less, and 2.0 or more. 5 or less is more desirable. The pH of the second mixed solution is preferably 3.5 or more and 5.5 or less, more preferably 4.0 or more and 5.5 or less, and further preferably 4.5 or more and 5.5 or less.

As a method for adjusting the Alt value of the toner, for example, there is a method of controlling the Alt value by adjusting the addition amount of the aluminum-containing flocculant when adjusting the first mixed solution and adjusting the second mixed solution. Can be mentioned.
For example, when aluminum sulfate is used as the aluminum-containing flocculant, the addition amount of a 10% aqueous solution of aluminum sulfate at the time of preparing the first mixed solution is 0.2 with respect to 100 parts by mass of the resin particles contained in the first mixed solution. The mass is preferably from 3.0 parts by mass to 3.0 parts by mass, and more preferably from 1.5 parts by mass to 2.5 parts by mass. Moreover, the addition amount of the 10% aqueous solution of aluminum sulfate at the time of adjusting the second mixed solution is from 0.10 parts by mass to 1.0 part by mass with respect to 100 parts by mass of the resin particles added at the time of adjusting the second mixed solution. Desirably, 0.10 mass part or more and 0.50 mass part or less are more desirable.

The heating temperature of the first mixed solution is preferably lower than the glass transition temperature of the resin, specifically, 30 ° C. or more and 40 ° C. or less is more desirable, and 35 ° C. or more and 40 ° C. or less is more desirable.
Further, the heating temperature of the second mixed solution is preferably higher than the heating temperature of the first mixed solution, specifically, 40 ° C. or more and 50 ° C. or less is more preferable, and 45 ° C. or more and 50 ° C. or less is more preferable. .

The volume average particle diameter of the first aggregated particles is preferably 3.0 μm or more and 3.5 μm or less, and more preferably 3.0 μm or more and 3.3 μm or less.
Further, the volume average particle size of the second aggregated particles is preferably 4.5 μm or more and 5.5 μm or less, and more preferably 4.7 μm or more and 5.4 μm or less.

  In the case where a crystalline resin and an amorphous resin are used in combination as the binder resin, the resin particles used in the second aggregated particle adjustment step are used as the resin particles used in the first aggregated particle adjustment step. It is desirable to use amorphous resin particles as the particles. By adopting such a method, it becomes easy to set the value of (Als / Alt) × 100 of the toner within the above range.

  After forming the second agglomerated particles, the surface of the second agglomerated particles may be coated with a binder resin by further adding resin particles (or a resin particle dispersion) as necessary. It is desirable that the resin particles to be additionally added are non-crystalline resin particles. By additionally adding non-crystalline resin particles, it becomes difficult to expose the crystalline resin on the surface of the produced toner, which is desirable from the viewpoint of chargeability and developability. Moreover, when using high molecular weight resin and low molecular weight resin as binder resin, it is desirable to use low molecular weight resin as resin for coat | covering the surface of a 2nd aggregated particle. In addition, a flocculant may be added or pH adjustment may be performed before the additional addition.

[Fusion / unification process]
In the fusion and coalescence process, the agglomeration proceeds by adding alkali to the dispersion of the second aggregated particles (or the second aggregated particles whose surfaces are coated with the binder resin) under the stirring conditions in accordance with the aggregation process. In the same manner as described above, for example, an aqueous sodium hydroxide solution may be used as the alkali to be added in the fusion and coalescence process. Further, the pH when stopping the progress of aggregation is preferably 6.5 or more and 9.0 or less, and more preferably 7.0 or more and 8.5 or less. Furthermore, as the heating temperature, for example, when the binder resin includes a crystalline resin, a temperature equal to or higher than the melting point of the crystalline resin is desirable, and specifically, for example, 70 ° C. to 95 ° C. is desirable, and 80 ° C. to 95 ° C. The following is more desirable. The heating time for fusing the agglomerated particles may be as long as the agglomerated particles are fused. Specifically, for example, 0.5 to 10 hours is desirable.

Cool after fusion to obtain fused particles. In addition, when the binder resin contains a crystalline resin, crystallization is promoted by so-called gradual cooling, in which the cooling rate is lowered in the vicinity of the melting point of the crystalline resin (melting point ± 10 ° C range) in the cooling step. May be.
The fused particles obtained by fusing become toner particles through a solid-liquid separation process such as filtration and, if necessary, a washing process and a drying process. Examples of the washing method include a method of subjecting the dispersion of fused particles to substitution washing with ion-exchanged water. As a solid-liquid separation method, suction filtration, pressure filtration, or the like is desirably used from the viewpoint of productivity. As the drying method, for example, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are desirably used.

[External addition process]
In the present embodiment, an external additive such as a fluidizing agent or an auxiliary agent may be added to the surface of the toner particles. Examples of the external additive include, as described above, inorganic particles such as silica particles, titanium oxide particles, alumina particles, cerium oxide particles, and carbon black whose surfaces have been hydrophobized, polycarbonate, polymethyl methacrylate, silicone resin, and the like. Known particles such as polymer particles are used, and at least two or more of these external additives are used, and at least one of the external additives is in the range of 30 nm to 200 nm, and further 30 nm to 180 nm. It is desirable to have an average primary particle size in the range.

  If the average primary particle size of the external additive is smaller than 30 nm, the initial toner fluidity is good, but the non-electrostatic adhesion force between the toner and the photosensitive member is not reduced, and the transfer efficiency is lowered. In some cases, the image may be blurred or the density variation of the image may be increased. Further, due to stress in the developing device over time, the particles are embedded in the toner surface and the chargeability changes, which may cause problems such as a decrease in copy density and fogging on the background. If the average primary particle size is larger than 200 nm, it may be easily detached from the toner surface and may cause deterioration of fluidity.

<Electrostatic latent image developer>
The toner for developing an electrostatic latent image of this embodiment is used as it is as a one-component developer or as a two-component developer. When used as a two-component developer, it is used by mixing with a carrier.

  The carrier that can be used in the two-component developer is not particularly limited, and a known carrier is used. Examples thereof include magnetic metals such as iron oxide, nickel and cobalt, magnetic oxides such as ferrite and magnetite, resin-coated carriers having a resin coating layer on the surface of the core material, and magnetic dispersion carriers. Further, a resin dispersion type carrier in which a conductive material or the like is dispersed in a matrix resin may be used.

  Coating resins and matrix resins used for carriers include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic. Examples include, but are not limited to, an acid copolymer, a straight silicone resin containing an organosiloxane bond or a modified product thereof, a fluororesin, a polyester, a polycarbonate, a phenol resin, and an epoxy resin.

  Examples of the conductive material include metals such as gold, silver and copper, carbon black, titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, tin oxide, and carbon black, but are not limited thereto. It is not something.

  Examples of the core material of the carrier include magnetic metals such as iron, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. However, in order to use the carrier for the magnetic brush method, it is a magnetic material. It is desirable. The volume average particle size of the core material of the carrier is generally in the range of 10 to 500 μm, and preferably in the range of 30 to 100 μm.

  In order to coat the surface of the core material of the carrier with a resin, there may be mentioned a method of coating with a coating layer forming solution prepared by dissolving the coating resin and, if necessary, various additives in an appropriate solvent. The solvent is not particularly limited, and may be selected in consideration of the coating resin to be used, coating suitability, and the like.

  Specific resin coating methods include an immersion method in which the carrier core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed onto the surface of the carrier core material, and the carrier core material is fluidized air. A fluidized bed method in which the coating layer forming solution is sprayed in a state of being suspended by the above, a kneader coater method in which the carrier core material and the coating layer forming solution are mixed in a kneader coater, and the solvent is removed.

The volume average particle size distribution index GSDv of the carrier obtained as described above is preferably in the range of 1.15 to 1.35, and more preferably in the range of 1.15 to 1.25.
If GSDv exceeds 1.35, the toner of the present embodiment may be difficult to obtain because the small particle size toner is easily developed. Moreover, it is practically difficult to make GSDv smaller than 1.15.

The GSDv value of the carrier was measured and calculated as follows. First, for the carrier size distribution (channel) measured using Multisizer II (manufactured by Beckman-Coulter) as a measuring instrument, the cumulative distribution is drawn from the small diameter side for each carrier volume. In addition, the particle size that is cumulative 16% is defined as the volume average particle size D16v, and the particle size that is cumulative 84% is defined as the volume average particle size D84v. Using these, the volume average particle size distribution index GSDv is defined as (D84v / D16v) ^1/2 .

  The mixing ratio (mass ratio) of the toner of the present embodiment and the carrier in the two-component developer is preferably in the range of toner: carrier = 1: 100 to 30: 100, and about 3: 100 to 20: 100. Range is more desirable.

<Image forming apparatus>
Next, an image forming apparatus using the electrostatic latent image developing toner of this embodiment will be described.
The image forming apparatus of the present embodiment is formed on a latent image holding body, developing means for developing the electrostatic latent image formed on the latent image holding body as a toner image with a developer, and the latent image holding body. A transfer unit that transfers the toner image onto the transfer member, a fixing unit that fixes the toner image transferred onto the transfer member, and a cleaning member that rubs the latent image holding member with a cleaning member to remove residual transfer components. And the electrostatic latent image developer of this embodiment is used as the developer.

In this image forming apparatus, for example, the part including the developing unit may have a cartridge structure (process cartridge) that is not detachable from the main body of the image forming apparatus. As the process cartridge, a developer holder And the process cartridge of this embodiment that contains the electrostatic latent image developer of this embodiment is preferably used.
Hereinafter, although an example of the image forming apparatus of this embodiment is shown, it is not necessarily 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 the first of the electrophotographic systems 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 biased in a direction 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 both. 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 colors of toner are supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K have the same configuration, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction here. 10Y will be described as a representative. Note that the second to fourth units are given the same 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 latent image is formed by exposing the surface of the photoreceptor 1Y to a predetermined potential by a charging roller 2Y and exposing the charged surface to a laser beam 3Y based on the color-separated image signal. An exposure device 3 for developing, a developing device (developing means) 4Y for developing the electrostatic latent image by supplying charged toner to the electrostatic latent image, and a primary transfer roller 5Y for transferring the developed toner image onto the intermediate transfer belt 20 A (primary 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 are sequentially arranged.
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 latent image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic latent 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 is reduced. On the other hand, it is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic latent image formed on the photoreceptor 1Y in this way is rotated to a predetermined development position as the photoreceptor 1Y travels. Then, at this development position, the electrostatic latent image on the photoreceptor 1Y is converted into a visible image (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 a multiple manner through the first to fourth units is disposed on the intermediate transfer belt 20, the support roller 24 in contact with the inner surface of the intermediate transfer belt 20, and the image holding surface side 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, and the transfer bias is applied to the intermediate transfer belt 20. The toner image is transferred onto the recording paper P. Note that the secondary transfer bias at this time is determined according to the resistance detected by a resistance detecting 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.

<Process cartridge, toner cartridge>
FIG. 2 is a schematic configuration diagram showing a preferred example of a process cartridge containing the electrostatic latent image developer according to the present embodiment. In the process cartridge 200, a charging roller 108, a developing device 111, a photoconductor cleaning device (cleaning means) 113, an opening 118 for exposure, and an opening 117 for static elimination exposure are attached to a rail 116 together with the photoconductor 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, and is recorded together with the image forming apparatus main body. The image forming apparatus forms an image on the paper 300.

  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. Are selectively combined. In the process cartridge of this embodiment, in addition to the photoconductor 107, the charging device 108, the developing device 111, the cleaning device (cleaning means) 113, the opening 118 for exposure, and the opening 117 for static elimination exposure. At least one selected from the group consisting of:

  Next, the toner cartridge of this embodiment will be described. The toner cartridge is mounted so as to be detachable from the image forming apparatus, and at least the toner cartridge for storing toner to be supplied to the developing means provided in the image forming apparatus. The toner is in the form. It should be noted that at least the toner may be accommodated in the toner cartridge of the present embodiment, and for example, a developer may be accommodated depending on the mechanism of the image forming apparatus.

  Therefore, in the image forming apparatus having a configuration in which the toner cartridge is detachable, the toner of the present embodiment is easily supplied to the developing device by using the toner cartridge containing the toner of the present embodiment. Excellent cleaning properties and filming resistance are maintained in the image formation.

  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 are attached to and detached from each other. The developing devices 4Y, 4M, 4C, and 4K each have their respective developing devices (colors). And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge is low, this toner cartridge may be replaced.

  Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples. In the following description, “part” represents “part by mass” and “%” represents “% by mass” unless otherwise specified.

<Measurement method>
-Measurement of volume average particle size of whole toner and small-diameter toner-
The volume average particle size of the whole toner and the small-diameter toner was measured using Multisizer II (manufactured by Beckman-Coulter) 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) and dispersed by ultrasonic waves for 30 seconds or more. The volume average particle size of the aggregated particles generated in the toner manufacturing process was also measured by the same method.

-Measurement of aluminum content in whole toner and small-diameter toner-
The content of aluminum element (Alt and Als) in the entire toner and the small-diameter toner was determined by quantitatively analyzing the fluorescent X-ray intensity.
Specifically, for example, first, 200 mg of a mixture of polyester resin and aluminum sulfate having a known concentration is pelleted using an IR tablet molding machine having a diameter of 13 mm, and the mass is precisely weighed. Measurement was performed to determine the peak intensity. Similarly, measurements were performed on samples in which the amount of aluminum sulfate added was changed, a calibration curve was created from these results, and quantitative analysis of the aluminum content in the actual measurement sample was performed using this calibration curve. The fluorescent X-ray intensity is measured using, for example, a fluorescent X-ray analyzer (manufactured by Shimadzu Corporation, XRF-1500) under the conditions of an X-ray output of 40 V-70 mA, a measurement area of 10 mmφ, and a measurement time of 15 minutes. It was measured.

-Measurement of shape factor SF1-
The toner shape factor SF1 is quantified by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer. Specifically, an optical microscope image of the higher alcohol particles dispersed on the surface of the slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length and projected area of 100 particles are obtained. Obtained by determining the value.
Formula: SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, ML represents the absolute maximum length of the toner particles, and A represents the projected area of the toner particles.

-Measurement of glass transition temperature and melting point-
The glass transition temperature and melting point were measured according to JIS 7121-1987 using a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001). The melting point of a mixture of indium and zinc was used for temperature correction of the detection part of this apparatus, and the heat of fusion of indium was used for correction of heat quantity. The sample was put in an aluminum pan, an aluminum pan containing the sample and an empty aluminum pan for control were set, and the measurement was performed at a heating rate of 10 ° C./min.
About melting | fusing point, it was set as melting | fusing point with the temperature of the peak of the largest endothermic peak among the endothermic peaks of the DSC curve obtained by measurement.
Moreover, about the glass transition temperature, it was set as the glass transition temperature with the temperature of the intersection of the extended line of the base line in the endothermic part of the DSC curve obtained by the measurement, and the rising line.

-Method of measuring acid value-
2 g of a sample was weighed and dissolved in 160 ml of acetone-toluene, or a sample with insufficient solubility was heated and dissolved, and then measured by the potentiometric titration method of JIS K0070-1992.

-Method for measuring weight average molecular weight-
The weight average molecular weight is measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC was performed with a THF solvent using a Tosoh column / TSKgel Super HM-M (15 cm) using a Tosoh GPC / HLC-8120 as a measuring device. The weight average molecular weight is calculated from the measurement result using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

-Measurement method of average particle diameter of resin particles / release agent particles / colorant particles-
Using a laser diffraction particle size distribution measuring device (LA-700: manufactured by Horiba, Ltd.), the volume average particle size of resin particles, release agent particles, and pigment particles was measured.

  As a measuring method, the sample in the state of dispersion is adjusted so as to have a solid content of 2 g, and ion exchange water is added thereto to make 40 ml. This was added to the cell until the appropriate concentration was reached, waited for 2 minutes, and measured when the concentration in the cell became stable.

  The obtained volume average particle diameter for each channel was accumulated from the smaller volume average particle diameter, and the volume average particle diameter was determined to be 50%.

  When measuring powder, 2 g of a measurement sample is added to 50 ml of a 5% aqueous solution of a surfactant (sodium dodecylbenzenesulfonate), and dispersed for 2 minutes with an ultrasonic disperser (1,000 Hz). A sample was prepared and measured by the same method as the above-mentioned dispersion.

-Measurement method of coagulation value of resin particles-
(Preparation of test emulsion)
First, an emulsion (resin particle dispersion) serving as a sample is prepared at a solid content concentration of 12.5% by mass, pH 7, and 25 ° C. Nitric acid and sodium hydroxide were used for pH adjustment.

(Preparation of magnesium chloride aqueous solution)
Magnesium chloride dihydrate was dissolved in ion-exchanged water to prepare magnesium chloride aqueous solutions of various concentrations (1.0 × 10 ⁻⁵ to 5.0 mol / l).

(Coagulation test)
The emulsion, the magnesium chloride aqueous solution of each concentration, and a mass ratio of 8: 2 (emulsion: magnesium chloride aqueous solution) were mixed and stirred so that the total solid content was 10% by mass. Subsequently, the particle size of each sample was measured by a particle size distribution measuring device (LS Coulter, manufactured by Coulter). The results were graphed with the horizontal axis representing the magnesium chloride concentration and the vertical axis representing the particle size, and the inflection point of the graph was the coagulation value.

<Example A>
[Synthesis of each resin]
-Preparation of low molecular weight amorphous polyester resin (LA1)-
Dimethyl adipate: 74 parts Dimethyl terephthalate: 192 parts Bisphenol A ethylene oxide adduct: 216 parts Ethylene glycol: 38 parts Tetrabutoxy titanate (catalyst): 0.037 parts

The above components are placed in a heat-dried two-necked flask, and nitrogen gas is introduced into the container and heated while stirring in an inert atmosphere, and then subjected to a copolycondensation reaction at 160 ° C. for 7 hours, and then gradually up to 10 Torr. The temperature was raised to 220 ° C. while reducing the pressure to 4 hours. Once the pressure was returned to normal pressure, 9 parts of trimellitic anhydride was added, and the pressure was gradually reduced again to 10 Torr and maintained for 1 hour to synthesize a low molecular weight amorphous polyester resin (LA1).
It was 65 degreeC when the glass transition temperature of the obtained low molecular weight non-crystalline polyester resin (LA1) was measured by the above-mentioned measuring method using the differential scanning calorimetry system (DSC). When the molecular weight of the obtained low molecular weight non-crystalline polyester resin (LA1) was measured using GPC by the aforementioned measurement method, the weight average molecular weight (Mw) was 12,000, and the number average molecular weight was 4,000. there were.

-Preparation of low molecular weight crystalline polyester resin (LC2)-
-1,9-nonanediol: 47 mol parts-Dodecanedicarboxylic acid: 53 mol parts-Dibutyltin oxide: 0.05 mol parts

  The above components were put into a heat-dried three-necked flask, and the air in the container was brought into an inert atmosphere with nitrogen gas by a depressurization operation, followed by mechanical stirring at 180 ° C. for 2 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 5 hours. When it became viscous, it was air-cooled, the reaction was stopped, and a low molecular weight crystalline polyester resin (LC2) was synthesized. This resin had a weight average molecular weight Mw of 30,000 and a melting point Tm of 73 ° C.

-Preparation of high molecular weight non-crystalline polyester resin (HA3)-
-Bisphenol A ethylene oxide 2 mol adduct: 38 parts by mass-Bisphenol A propylene oxide 2 mol adduct: 27.0 parts by mass-Dimethyl terephthalate: 26 parts by mass-Dodecenyl succinic acid: 6.5 parts by mass-Trimellitic acid : 2.5 parts by mass

The above components were put into a 5 liter flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a rectifying tower, the temperature was raised to 190 ° C. over 1 hour, and the reaction system was stirred, 1.0 part by mass of dibutyltin oxide was added. Further, while distilling off the water produced, it took 5 hours to increase the temperature from 190 ° C. to 240 ° C., and continued the dehydration condensation reaction at 240 ° C. for another 2 hours to obtain a high molecular weight amorphous polyester resin (HA3). Synthesized.
The obtained high molecular weight amorphous polyester resin (HA3) had a glass transition temperature of 56 ° C., an acid value of 14.4 mg KOH / g, a weight average molecular weight of 51,000, and a number average molecular weight of 4,800.

-Preparation of low molecular weight non-crystalline polyester resin (LA4)-
Dimethyl adipate: 71 parts Dimethyl terephthalate: 185 parts Bisphenol A ethylene oxide adduct: 210 parts Ethylene glycol: 38 parts Tetrabutoxy titanate (catalyst): 0.037 parts

The above components are placed in a heat-dried two-necked flask, and nitrogen gas is introduced into the container, and the temperature is raised while stirring in an inert atmosphere. Then, a copolycondensation reaction is performed at 160 ° C. for 10 hours, and then gradually until 10 Torr. The temperature was raised to 220 ° C. while reducing the pressure to 8 hours. Once the pressure was returned to normal pressure, 9 parts of trimellitic anhydride was added, and the pressure was gradually reduced again to 10 Torr and maintained for 1 hour to synthesize a low molecular weight amorphous polyester resin (LA4).
It was 61 degreeC when the glass transition temperature of the obtained low molecular weight non-crystalline polyester resin (LA4) was measured using the differential scanning calorific value system (DSC) by the above-mentioned measuring method. When the molecular weight of the obtained low molecular weight non-crystalline polyester resin (LA4) was measured using GPC by the above-described measurement method, the weight average molecular weight (Mw) was 15,000, and the number average molecular weight was 4,500. there were.

-Preparation of high molecular weight non-crystalline polyester resin (HA5)-
-Bisphenol A ethylene oxide 2 mol adduct: 38.0 parts by mass-Bisphenol A propylene oxide 2 mol adduct: 28.0 parts by mass-Terephthalic acid dimethyl ester: 25 parts by mass-Dodecenyl succinic acid: 6.5 parts by mass Merit acid: 2.5 parts by mass

The above components were put into a 5 liter flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a rectifying tower, the temperature was raised to 190 ° C. over 1 hour, and the reaction system was stirred, 1.0 part by mass of dibutyltin oxide was added. Further, 6 hours were required while distilling off the generated water, the temperature was increased from 190 ° C. to 240 ° C., and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours to obtain a high molecular weight amorphous polyester resin (HA5). Synthesized.
The high molecular weight amorphous polyester resin (HA5) obtained had a glass transition temperature of 57 ° C., an acid value of 15.0 mgKOH / g, a weight average molecular weight of 58,000, and a number average molecular weight of 5,600.

[Adjustment of each dispersion]
-Preparation of low molecular weight amorphous resin particle dispersion (LA1)-
Low molecular weight non-crystalline polyester resin (LA1) (Mw: 12,000): 160 parts by mass Ethyl acetate: 233 parts Sodium hydroxide aqueous solution (0.3N): 0.1 parts

The above components were put into a 500 ml separable flask, heated at 70 ° C., and stirred by a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion-exchanged water is gradually added, phase-inversion emulsification and solvent removal are carried out to remove a low molecular weight amorphous resin particle dispersion (LA1) (solid content concentration: 30%). Got. The coagulation value was 4.5 × 10 ⁻⁴ . The volume average particle size of the resin particles in the dispersion was 160 nm.

-Preparation of low molecular weight crystalline resin particle dispersion (LC2)-
Low molecular weight non-crystalline, except that low molecular weight crystalline polyester resin (LC2) is used instead of low molecular weight non-crystalline polyester resin (LA1) and the amount of 0.3N sodium hydroxide aqueous solution added is 0.05 parts. A low molecular weight crystalline resin particle dispersion (LC2) (solid content concentration: 30%) was prepared in the same manner as the resin particle dispersion (LA1). The coagulation value was 5.6 × 10 ⁻³ , and the volume average particle size of the resin particles in the dispersion was 160 nm.

-Preparation of high molecular weight amorphous resin particle dispersion (HA3)-
Low molecular weight amorphous, except that high molecular weight amorphous polyester resin (HA3) is used instead of low molecular weight amorphous polyester resin (LA1) and the amount of 0.3N sodium hydroxide aqueous solution added is 0.2 parts. High molecular weight non-crystalline resin particle dispersion (HA3) (solid content concentration: 30%) was prepared in the same manner as the conductive resin particle dispersion (LA1). The coagulation value was 6.7 × 10 ⁻³ , and the volume average particle size of the resin particles in the dispersion was 160 nm.

-Preparation of high molecular weight amorphous resin particle dispersion (HA3-2)-
Low molecular weight non-crystalline, except that high molecular weight non-crystalline polyester resin (HA3) is used instead of low molecular weight non-crystalline polyester resin (LA1) and the amount of 0.3N sodium hydroxide aqueous solution added is 0.4 parts. High molecular weight non-crystalline resin particle dispersion (HA3-2) (solid content concentration: 30%) was prepared in the same manner as the conductive resin particle dispersion (LA1). The coagulation value was 3.2 × 10 ⁻⁵ , and the volume average particle size of the resin particles in the dispersion was 160 nm.

-Preparation of low molecular weight non-crystalline resin particle dispersion (LA4)-
Low molecular weight non-crystalline, except that low molecular weight non-crystalline polyester resin (LA4) is used instead of low molecular weight non-crystalline polyester resin (LA1) and the amount of 0.3N sodium hydroxide aqueous solution added is 0.4 parts. The low molecular weight crystalline resin particle dispersion (LA4) (solid content concentration: 30%) was prepared in the same manner as the conductive resin particle dispersion (LA1). The coagulation value was 4.5 × 10 ⁻⁵ and the volume average particle size of the resin particles in the dispersion was 160 nm.

-Preparation of low molecular weight non-crystalline resin particle dispersion (LA4-2)-
Low molecular weight non-crystalline, except that low molecular weight non-crystalline polyester resin (LA4) is used instead of low molecular weight non-crystalline polyester resin (LA1) and the amount of 0.3N sodium hydroxide aqueous solution added is 0.5 parts. The low molecular weight crystalline resin particle dispersion (LA4-2) (solid content concentration: 30%) was prepared in the same manner as the conductive resin particle dispersion (LA1). The coagulation value was 5.2 × 10 ⁻⁶ , and the volume average particle size of the resin particles in the dispersion was 160 nm.

-Preparation of high molecular weight amorphous resin particle dispersion (HA5)-
Low molecular weight non-crystalline, except that high molecular weight non-crystalline polyester resin (HA5) is used instead of low molecular weight non-crystalline polyester resin (LA1) and the amount of 0.3N sodium hydroxide aqueous solution added is 0.1 part. High molecular weight non-crystalline resin particle dispersion (HA5) (solid content concentration: 30%) was prepared in the same manner as the conductive resin particle dispersion (LA1). The coagulation value was 2.5 × 10 ⁻⁵ , and the volume average particle size of the resin particles in the dispersion was 160 nm.

-Release agent particle dispersion-
Paraffin wax (Nippon Seiwa Co., Ltd., HNP-9, melting point: 75 ° C.): 50 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 0.5 parts Exchanged water: 200 parts

  The above mixture was mixed and heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then dispersed with a Manton Gorin high-pressure homogenizer (Gorin) to have a volume average particle size of 0.23 μm. A release agent particle dispersion (solid content concentration: 20%) was prepared by dispersing release agent particles.

-Colorant particle dispersion-
-Magenta pigment (Daiichi Seika Co., Ltd., CI Pigment Red 122): 1000 parts-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R): 15 parts-Ion-exchanged water: 3300 parts

  Colorant particles obtained by mixing and dissolving the above and dispersing the colorant (carbon black) particles for about 1 hour using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). A dispersion was prepared. The volume average particle size of the colorant (carbon black) particles in the colorant particle dispersion was 0.16 μm, and the solid content concentration was 23%.

[Production of toner]
-Example A1-
[Preparation of Toner A1]
(First Aggregated Particle Adjustment Step)
-High molecular weight amorphous resin particle dispersion (HA3): 300 parts-Colorant particle dispersion (solid content concentration: 23 wt%): 43.48 parts-Release agent particle dispersion (solid content concentration: 20 wt%) %): 100 parts Nonionic surfactant aqueous solution (IGEPAL CA897): 3 parts 0.3 M nitric acid aqueous solution: 50 parts Ion-exchanged water: 500 parts

The above components were placed in a 3 L round stainless steel flask and dispersed and mixed for 10 minutes while applying shear at 4,000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50).
Next, nitric acid was added to the flask to adjust the pH to 2.5, and then 2 parts by mass of a 10% aqueous solution of aluminum sulfate as a flocculant was gradually dropped to disperse the homogenizer at 5,000 rpm for 15 minutes. It mixed and it was set as the raw material dispersion liquid.
Thereafter, the raw material dispersion was transferred to a polymerization kettle equipped with a stirrer and a thermometer, started to be heated with a mantle heater, heated to 35 ° C., and held for 1 hour. The volume average particle diameter of the aggregated particles (first aggregated particles) formed at this time was 3.3 μm.

(Second Aggregated Particle Adjustment Step)
Thereafter, an aqueous sodium hydroxide solution is added as an alkali to adjust the pH to 3.3, 150 parts of a low molecular weight amorphous resin particle dispersion (LA1) and 1 part of a 10% aluminum sulfate aqueous solution are added, and aggregated particles grow at 45 ° C. Promoted. While maintaining the above pH, the mixture was held for about 2 hours to form aggregated particles. At this time, the volume average particle diameter of the aggregated particles (second aggregated particles) was 5.3 μm.
Next, 117 parts of low molecular weight amorphous resin particle dispersion (LA1) is additionally added, and the low molecular weight amorphous polyester resin resin particles are adhered (shell structure) to the surface of the aggregated particles (second aggregated particles). It was.

(Fusion / unification process)
Subsequently, 10% by weight of EDTA (ethylenediaminetetraacetic acid) metal salt aqueous solution (Cyrest Mg · 40 manufactured by Kyrest Co., Ltd.): After adding 24 parts, gently 1N sodium hydroxide aqueous solution until reaching pH 8.5 After the addition, the mixture was heated to 95 ° C while maintaining stirring, and maintained for 1 hour. Thereafter, the mixture was cooled at a temperature drop rate of 1.0 ° C./min, sieved with a 20 μm mesh, repeatedly washed with water, and then dried with a vacuum dryer to obtain toner particles (1).

(External addition process)
To 100 parts of the toner particles (1), as an external additive, 1.0% of silica particles having a primary particle size of 40 nm (Nippon Aerosil Co., Ltd., hydrophobic silica: RX50) subjected to surface hydrophobization treatment, metatitanic acid 100 parts of a reaction product obtained by treating 40 parts of isobutyltrimethoxysilane and 10 parts of trifluoropropyltrimethoxysilane and 1.0% of metatitanic acid compound particles having an average primary particle diameter of 20 nm were added to the mixture. Mixed for minutes. Furthermore, the toner A1 was obtained by passing through an ultrasonic vibration sieve (Dalton).

(Preparation of small diameter toner a1)
The toner A1 was classified by an elbow jet classifier (cut point: (5/6) × D50T) to produce a small-diameter toner a1 having a volume average particle diameter of 4.1 μm.
The dynamic complex viscosity η ^* t (Pa · s) and (η ^* s / η ^* t) × 100 of the toner A1, the aluminum element content Alt (atom%), and (Als / Alt) × 100 Table 2 shows values, weight average molecular weight MwT, (MwS / MwT) × 100, glass transition temperature Tg (° C.), volume average particle diameter D50T (μm), and GSDp-under.

-Example A2-
Toner A2 and small-diameter toner a2 were prepared in the same manner as toner A1 and small-diameter toner a1, except that the pH was adjusted to 4.2 instead of pH 3.3 in the second aggregated particle adjustment step. Table 2 shows the characteristics of the toner A2.

-Example A3-
Toner A3 and small-diameter toner a3 were prepared in the same manner as toner A2 and small-diameter toner a2, except that the resin used was as shown in Table 1. Table 2 shows the characteristics of the toner A3.

-Example A4-
Toner A4 and small-diameter toner a4 were prepared in the same manner as toner A3 and small-diameter toner a3, except that the pH was adjusted to 4.4 instead of pH 3.3 in the second aggregated particle adjustment step. Table 2 shows the characteristics of the toner A4.

-Example A5-
Toner A5 and small-diameter toner a5 were prepared in the same manner as toner A3 and small-diameter toner a3, except that the pH was adjusted to 4.5 instead of pH 3.3 in the second aggregated particle adjustment step. Table 2 shows the characteristics of the toner A5.

-Example A6-
Toner A6 and small-diameter toner a6 were prepared in the same manner as toner A3 and small-diameter toner a3, except that the pH was adjusted to 5.0 instead of pH 3.3 in the second aggregated particle adjustment step. Table 2 shows the characteristics of the toner A6.

-Example A7-
Toner A7 and small-diameter toner a7 were produced in the same manner as toner A6 and small-diameter toner a6, except that the resin used was as shown in Table 1. Table 2 shows the characteristics of the toner A7.

-Example A8-
Toner A8 and small-diameter toner a8 were produced in the same manner as toner A5 and small-diameter toner a5 except that the resin used was as shown in Table 1. Table 2 shows the characteristics of the toner A8.

-Example A9-
[Preparation of Toner A9]
-High molecular weight amorphous resin particle dispersion (HA5): 265 parts-Low molecular weight crystalline resin particle dispersion (LC2): 35 parts-Colorant particle dispersion: 43.48 parts-Release agent particle dispersion: 100 parts-Nonionic surfactant aqueous solution (IGEPAL CA897): 3 parts-0.3 M nitric acid aqueous solution: 50 parts-Ion exchange water: 350 parts

(First Aggregated Particle Adjustment Step)
The above components were placed in a 3 L round stainless steel flask and dispersed and mixed for 10 minutes while applying shear at 4,000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50). Next, nitric acid was added to the flask to adjust the pH to 2.5, and then 2 parts by mass of a 10% aqueous solution of aluminum sulfate as a flocculant was gradually dropped to disperse the homogenizer at 5,000 rpm for 15 minutes. It mixed and it was set as the raw material dispersion liquid.
Thereafter, the raw material dispersion was transferred to a polymerization kettle equipped with a stirrer and a thermometer, started to be heated with a mantle heater, heated to 35 ° C., and held for 1 hour. The volume average particle diameter of the aggregated particles (first aggregated particles) formed at this time was 2.6 μm.

(Second Aggregated Particle Adjustment Step)
Then, an aqueous sodium hydroxide solution was added as an alkali to adjust the pH to 4.5, 150 parts of a low molecular weight amorphous resin particle dispersion (LA1) and 1 part by weight of an aluminum sulfate 10% aqueous solution were added, and the aggregated particles were Promoted growth. While maintaining the above pH, the mixture was held for about 2 hours to form aggregated particles. At this time, the volume average particle diameter of the aggregated particles (second aggregated particles) was 3.1 μm.
Subsequently, 117 parts by mass of a low molecular weight amorphous resin particle dispersion (LA1) was additionally added, and the resin particles of the amorphous polyester resin were adhered to the surface of the aggregated particles.

  The toner A9 and the small-diameter toner a9 were produced in the same manner as the toner A1 and the small-diameter toner a1 for the processes after the fusion / unification process. Table 2 shows the characteristics of the toner A9.

-Comparative Example A1-
Toner B1 and small-diameter toner b1 were prepared in the same manner as toner A5 and small-diameter toner a5, except that the following aggregation process was performed instead of the first aggregated particle adjusting step and the second aggregated particle adjusting step. Table 2 shows the characteristics of the toner B1.

(Aggregation process)
・ Ion exchange water: 450 parts ・ High molecular weight amorphous resin particle dispersion (HA3): 300 parts ・ Low molecular weight amorphous resin particle dispersion (LA1): 150 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku) Co., Ltd .: Neogen RK, 20% by mass): 2.8 parts

  The above components were placed in a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer, and the temperature was controlled from the outside with a mantle heater, and maintained at a temperature of 30 ° C. and a stirring speed of 150 rpm for 30 minutes.

  Next, 60 parts by weight of the colorant particle dispersion and 100 parts by weight of the release agent particle dispersion were charged into the reaction vessel and held for 5 minutes, and then 10 parts of a 1.0% by weight nitric acid aqueous solution was added. The pH in the aggregation process was adjusted to 5.5.

Further, 0.4 parts by mass of polyaluminum chloride was added while being dispersed with a homogenizer (manufactured by IKA Japan, Inc .: Ultra Tarax T50), then heated to 50 ° C. while stirring, and held for 1 hour to form aggregated particles. . At this time, the volume average particle diameter of the aggregated particles was 5.5 μm.
Subsequently, 117 parts of low molecular weight amorphous resin particle dispersion (LA1) was additionally added, and low molecular weight amorphous polyester resin resin particles were adhered (shell structure) to the surface of the aggregated particles.

-Comparative Example A2-
The toner C1 and the small diameter toner are the same as the toner A5 and the small diameter toner a5 except that the high molecular weight noncrystalline resin particle dispersion (HA5) is used instead of the high molecular weight noncrystalline resin particle dispersion (HA5). c1 was produced. Table 2 shows the characteristics of the toner C1.

-Comparative Example A3-
The toner D1 and the small-diameter toner are the same as the toner A7 and the small-diameter toner a7 except that the low-molecular weight non-crystalline resin particle dispersion (LA4) is used instead of the low-molecular weight amorphous resin particle dispersion (LA4). d1 was produced. Table 2 shows the characteristics of the toner D1.

<Example E>
[Adjustment of large diameter toner particles]
-Preparation of low molecular weight styrene-acrylic resin particle dispersion (LS1)-
-308 parts by weight of styrene-100 parts by weight of n-butyl acrylate-4 parts by weight of acrylic acid-8 parts by weight of dodecanethiol-1.5 parts by weight of propanediol acrylate

The above components are mixed and dissolved. On the other hand, 4 parts by weight of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by weight of ion-exchanged water is placed in a flask. Was added, dispersed and emulsified, and 50 parts by weight of an ion exchange aqueous solution in which 6 parts by weight of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.
Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 75 ° C. to carry out emulsion polymerization.
Thus, a low molecular weight styrene-acrylic resin particle dispersion (LS1) having a central particle diameter (volume average particle diameter) of 178 nm, a glass transition temperature of 52 ° C., and a weight average molecular weight Mw of 24,000 (solid content concentration: 42%). Got.

Low molecular weight styrene-acrylic resin particle dispersion (LS1): 187 parts by weight Colorant particle dispersion: 42.7 parts by weight Release agent particle dispersion: 60.0 parts by weight Polyaluminum chloride (10% aqueous solution) ): 1.2 parts by mass / ion exchange water: 375 parts by mass

  The above components were thoroughly mixed and dispersed in a round stainless steel flask using an Ultra Turrax T50 manufactured by IKA, and then heated to 52 ° C. while stirring the flask in an oil bath for heating. After maintaining at 52 ° C. (initial heating temperature) to a volume average particle size of 6.0 μm, 92 parts by mass of a low molecular weight styrene-acrylic resin particle dispersion (LS1) was gradually added thereto.

Then, after adjusting the pH in the system to 6.5 using a 0.5 mol / L sodium hydroxide aqueous solution, the stainless steel flask was sealed, and the stirring shaft seal was magnetically sealed while continuing stirring. Heated to 97 ° C. After completion of the reaction, the reaction mixture was cooled, filtered, sufficiently washed with ion exchange water, and solid-liquid separation was performed by Nutsche suction filtration. This was further redispersed with 3 L of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 5 times, and No. 1 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain large toner particles.
The volume average particle diameter of the large toner particles at this time was measured and found to be 6.8 μm.

[Adjustment of small diameter toner particles]
-Preparation of high molecular weight styrene-acrylic resin particle dispersion (HS2)-
-Styrene 308 parts-N-butyl acrylate 100 parts-Acrylic acid 4 parts-Dodecanethiol 4 parts-Propanediol acrylate 1.5 parts

The above components are mixed and dissolved. On the other hand, 4 parts by weight of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by weight of ion-exchanged water is placed in a flask. Was added, dispersed and emulsified, and 50 parts by weight of an ion exchange aqueous solution in which 6 parts by weight of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.
Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
Thus, a high molecular weight styrene-acrylic resin particle dispersion (HS2) having a central particle diameter (volume average particle diameter) of 178 nm, a glass transition temperature of 52 ° C., and a weight average molecular weight Mw of 43,000 (solid content concentration: 42%). Got.

High molecular weight styrene-acrylic resin particle dispersion (HS2): 187 parts by weight Colorant particle dispersion: 42.7 parts by weight Release agent particle dispersion: 60.0 parts by weight Polyaluminum chloride (10% aqueous solution) ): 2.4 parts by mass / ion exchange water: 375 parts by mass

  The above components were thoroughly mixed and dispersed in a round stainless steel flask using an Ultra Turrax T50 manufactured by IKA, and then heated to 52 ° C. while stirring the flask in an oil bath for heating. After maintaining at 52 ° C. (initial heating temperature) to a volume average particle size of 3.9 μm, 92 parts by mass of a low molecular weight styrene-acrylic resin particle dispersion (LS1) was gradually added thereto.

Then, after adjusting the pH in the system to 6.5 using a 0.5 mol / L sodium hydroxide aqueous solution, the stainless steel flask was sealed, and the stirring shaft seal was magnetically sealed while continuing stirring. Heated to 97 ° C. After completion of the reaction, the reaction mixture was cooled, filtered, sufficiently washed with ion exchange water, and solid-liquid separation was performed by Nutsche suction filtration. This was further redispersed with 3 L of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 5 times, and No. 1 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain small-diameter toner particles.
The volume average particle size of the small toner particles at this time was measured and found to be 4.6 μm.

[Production of toner]
-Example E1-
Silica particles having a primary particle size of 40 nm subjected to surface hydrophobization treatment (hydrophobic silica: RX50, manufactured by Nippon Aerosil Co., Ltd.) 1.0% as an external additive with respect to 50 parts of large toner particles and 50 parts of small toner particles Then, 1.0 part of metatitanic acid compound particles having an average primary particle diameter of 20 nm, which is a reaction product obtained by treating 40 parts of isobutyltrimethoxysilane and 10 parts of trifluoropropyltrimethoxysilane to 100 parts of metatitanic acid, Mix for 5 minutes with a Henschel mixer. Furthermore, the toner E1 was obtained by passing through an ultrasonic vibration sieve (Dalton).

The toner E1 was classified by an elbow jet classifier (cut point: (5/6) × D50T) to prepare a small-diameter toner e1 having a volume average particle diameter of 3.8 μm.
The dynamic complex viscosity η ^* t (Pa · s) of the toner E1 is 2.1 × 10 ⁶ (Pa · s), the value of (η ^* s / η ^* t) × 100 is 670, and the content of the aluminum element Alt (atom%) is 0.130 (atom%), (Als / Alt) × 100 is 184, weight average molecular weight MwT, (MwS / MwT) × 100 is 187, glass transition temperature Tg (° C.) Was 51 (° C.), the volume average particle diameter D50T (μm) was 5.7 (μm), and the GSDp-under was 1.23.

<Production of developer>
-Production of carrier-
Ferrite particles (volume average particle diameter: 35 μm, GSDv: 1.20): 100 parts Toluene: 14 parts Methyl methacrylate-perfluorooctylethyl acrylate copolymer (copolymerization ratio 8: 2, Mw 80000, critical surface tension : 24 dyn / cm): 1.6 parts carbon black (trade name: VXC-72, manufactured by Cabot, volume resistivity: 100 Ωcm or less): 0.12 parts crosslinked melamine resin particles (average particle size: 0.3 μm) , Toluene insoluble): 0.3 parts

First, carbon black was diluted in toluene and added to a perfluoroacrylate copolymer and dispersed with a sand mill. Next, the above components other than the ferrite particles were dispersed therein with a stirrer for 10 minutes to prepare a coating layer forming solution. Next, this coating layer forming liquid and ferrite particles were put into a vacuum degassing type kneader and stirred at a temperature of 60 ° C. for 30 minutes, and then the pressure was reduced and toluene was distilled off to form a resin coating layer to obtain a carrier. .
The volume average particle size distribution index GSDv of the carrier was 1.20.

-Production of developer-
36 parts of the obtained toner and 414 parts of the carrier were put in a 2 liter V blender, stirred for 20 minutes, and then sieved at 212 μm to prepare a developer.

<Various toner evaluation>
[Evaluation of change in glossiness of continuously formed images]
The developer obtained in the environment room of room temperature 32 ° C. and humidity 85% is converted into a quadruple tandem-type Fuji Xerox Co., Ltd. DocuCentreColor 400CP remodeling machine (fixing device temperature control with external power supply control) In the range of 100 ° C. to 180 ° C. and fixed at intervals of 20 ° C., and the resulting image has a constant reflection density (paper C2 paper, manufactured by Fuji Xerox Co., Ltd.). An X-Rite 404 densitometer, manufactured by X-Rite, formed 100 images continuously so as to have a density of 1.5 to 1.8, and a gloss meter (BYK micro trigloss gloss meter (20 + 60 + 85 °)), The glossiness of the image formed using Gardner was measured. The process speed is 650 mm / s. The evaluation criteria are as follows, and up to Δ is allowed. The results are shown in Table 3.

-Evaluation criteria for glossiness change of continuously formed images-
◎: Glossiness average value of 1st to 10th sheets and 100th glossiness difference is 2 or less ○ Glossiness average value of 1st to 10th sheets and Glossiness difference of 100th sheet exceeds 2 and 4 or less Δ: Glossiness average value of 1st to 10th sheet and glossiness difference of 100th sheet exceed 4 and less than 6 ×: Glossiness average value of 1st to 10th sheet and glossiness difference of 100th sheet are 6 Exceed

[Evaluation of color gamut change of continuously formed images]
The developer obtained in the environment room of room temperature 32 ° C. and humidity 85% is converted into a quadruple tandem-type Fuji Xerox Co., Ltd. DocuCentreColor 400CP remodeling machine (fixing device temperature control with external power supply control) In a developing device), and continuously forming 100 images (paper: C2 paper, manufactured by Fuji Xerox Co., Ltd.) at a fixing temperature of 160 ° C. and a process speed of 650 mm / s. The color gamut was measured with an X-Rite 939 densitometer (manufactured by X-Rite, measurement conditions: observation light source D50, viewing angle 2 °). The “color gamut” means a color space in which the chromaticity (a *, b *) and the lightness (L) are represented by coordinate axes. The average of a * of the 1st to 10th sheets is a * 1, the average of b * is b * 2, the average of L is L1, the a * 2, b * 2, and L2 of the 30000th sheet, and ΔE = ((( ^{a * 1-a * 2)} 2 + (b * 1-b * 2) 2 + (L1-L2) 2) was calculated ^1/2. The evaluation criteria are as follows, and up to Δ is allowed. The results are shown in Table 3.

-Evaluation criteria for color gamut changes in continuously formed images-
◎: Color gamut average value from 1st to 10th sheet and color gamut difference of 100th sheet are ΔE0.4 or less ○ Color gamut average value of 1st to 10th sheet and color gamut difference of 100th sheet are ΔE0.4 More than, ΔE1.0 or less Δ: 1 to 10th color gamut average value and 100th color gamut difference exceeds ΔE1.0 ΔE1.5 or less ×: 1st to 10th color gamut average value and 100 The color gamut difference of the first sheet is greater than ΔE1.5

[Evaluation of gloss unevenness at high temperature fixing]
The developer thus obtained is filled in a four-tandem system DocuCentreColor 400CP developer manufactured by Fuji Xerox Co., Ltd., and the fixing temperature is 190 ° C. on recording paper (C2 paper, manufactured by Fuji Xerox). A 4 × 5 cm ² solid image was formed. For the image portion of the formed solid image, gloss unevenness was evaluated using a 75-degree specular gloss meter GM-26D (product of Murakami Color Research Laboratory Co., Ltd.). The evaluation criteria are as follows, and the results are shown in Table 3.

-Evaluation criteria for gloss unevenness-
○: Glossiness difference is less than 5% △: Glossiness difference is 5% or more and less than 10%
X: Gloss difference is 10% or more

  From the results shown in Table 3, it can be seen that in the example, the change in the glossiness of the continuously formed image is suppressed as compared with the comparative example.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge of this embodiment.

Explanation of symbols

1Y, 1M, 1C, 1K, 107 photoconductor (latent image holder)
2Y, 2M, 2C, 2K, 108 Charging roller 3Y, 3M, 3C, 3K Laser beam (electrostatic latent image forming means)
3 Exposure devices 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,
300, P Recording paper (transfer object)

Claims (6)

The volume average particle diameter of the whole toner is D50T, the glass transition temperature of the whole toner is Tg (° C.), the dynamic complex viscosity of Tg + 70 (° C.) of the whole toner is η ^* t (Pa · s), When the toner is classified to have a volume average particle size of (2/3) × D50T and the dynamic complex viscosity of Tg + 70 (° C.) in the classified toner is η ^* s (Pa · s), the η ^An electrostatic latent image developing toner in which ^* t and η ^* s satisfy the relationship of the following formula (1).
200 ≦ (η ^* s / η ^* t) × 100 ≦ 1000 (1)   The toner for developing an electrostatic latent image according to claim 1, comprising a binder resin, wherein the binder resin is a polyester resin.   An electrostatic latent image developer comprising at least the electrostatic latent image developing toner according to claim 1. Toner that is removed from the image forming apparatus and supplied to at least developing means provided in the image forming apparatus is stored.
The toner cartridge according to claim 1, wherein the toner is a toner for developing an electrostatic latent image.   A process cartridge comprising at least a developer holder and containing the electrostatic latent image developer according to claim 3. A latent image carrier,
An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the latent image holding member;
Developing means for developing the electrostatic latent image as a toner image with a developer;
Transfer means for transferring the toner image formed on the latent image holding member onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer object,
The image forming apparatus according to claim 3, wherein the developer is an electrostatic latent image developer.