JP6790754B2 - Toner for static charge image development - Google Patents

Description

The present invention relates to a toner for developing an electrostatic charge image, and more particularly to a toner for developing an electrostatic charge image, which has excellent low-temperature fixability and can reduce uneven density and uneven gloss of an image.

In an electrophotographic image forming apparatus, an electrostatic charge image developing toner (hereinafter, also simply referred to as a toner) that can be thermally fixed at a lower temperature in order to save energy for the purpose of speeding up image formation and reducing an environmental load. .) Is required.
In addition to such improvement in low temperature fixability, improvement in image quality of toner images is also required. In particular, paper having a large thickness unevenness called the texture on the paper surface, such as paper made from softwood having a large fiber diameter, tends to cause uneven density in the toner image, and improvement in image quality is required.
For paper having a large uneven thickness, a toner using an amorphous polyester resin that forms an ion crosslink with an aluminum element has been proposed (see, for example, Patent Document 1). Since the pressure from the fixing member is large at the convex portion of the paper that the fixing member contacts during fixing, the toner tends to break the ion crosslink and the viscosity tends to decrease, but the pressure is small at the concave portion of the paper that the fixing member does not contact. It has a pressure dependence that ion cross-linking tends to remain and high viscosity is easily maintained. It is considered that the toner having a high viscosity in the concave portion can suppress the flow of the toner having a low viscosity in the convex portion into the concave portion, and can suppress the unevenness of the amount of toner adhered between the concave portion and the convex portion.

Patent Document 2 proposes a toner using a block polymer for a paper having a large uneven thickness. This toner uses a block polymer instead of a crystalline resin, and forms a crosslinked body of an amorphous polyester resin having an ethylenically unsaturated double bond on the surface layer of the toner particles. It is considered that the exudation of the crystalline resin is suppressed, and the external additive is less likely to be embedded to suppress the transfer unevenness. Further, according to the above configuration, the toner in the concave portion of the paper that the fixing member does not contact during fixing suppresses the flow of the toner whose viscosity has decreased in the convex portion into the concave portion, and the amount of toner adhered between the concave portion and the convex portion is uneven. Is believed to be able to suppress.

However, no consideration has been given to how the toner melts and spreads due to heating during fixing. In the recesses where the fixing member does not come into contact, the amount of heat applied during fixing is small, and the pressure-dependent toner hardly melts and does not form a film, so that low-temperature fixability is insufficiently achieved. In addition, the toner does not easily dissolve and spread in the concave portion, and the graininess of the toner remains, so that the glossiness is lowered. It was.
Further, since the situation when measuring the viscoelasticity of the toner described in Patent Document 1 is different from the situation when the toner is melted by being heated at the time of fixing, it is necessary to actually suppress uneven density and uneven gloss of the image. It is unclear whether the toner will melt.

Japanese Unexamined Patent Publication No. 2015-64449 Japanese Unexamined Patent Publication No. 2014-77887

The present invention has been made in view of the above problems and situations, and the problem to be solved is to provide a toner for static charge image development which is excellent in low temperature fixability and can reduce uneven density and uneven gloss of an image. That is.

In the process of investigating the cause of the above problem in order to solve the above problems, the present inventor has a transmittance of light having a wavelength of 490 nm and a transmission of light having a wavelength of 670 nm when the toner layer is heated under the heating conditions at the time of fixing. By setting the rate to a specific range, it is excellent in low-temperature fixability, and the toner in the convex part that comes into contact with the fixing belt of rough paper does not flow into the concave part, and the toner in the concave part melts and spreads, resulting in uneven image density. We have found that it is possible to reduce uneven gloss, and have arrived at the present invention.
That is, the above problem according to the present invention is solved by the following means.
1. 1. A toner for developing an electrostatic charge image, which is composed of toner particles containing at least an amorphous resin, a crystalline resin, and a colorant.
After forming a toner layer having an adhesion amount of 6.5 g / m ² of the toner for static charge image development on glass and applying heat at 185 ° C. for 5 seconds from a position where the distance from the surface of the toner layer is 100 μm. When the light transmittance of the toner layer is measured,
The light transmittance of 490nm wavelength is in the range of 80-90%, and the transmittance of the light having the wavelength of 670nm is Ri near the range of 0%
The toner particles include core particles and a shell layer that covers the surface of the core particles to form a core-shell structure.
The core particles contain a styrene / acrylic resin as the amorphous resin, a crystalline polyester resin as the crystalline resin, and a block polymer.
Wherein the shell layer is, the amorphous resin as amorphous polyester resin containing to toner for developing electrostatic images, wherein Rukoto.

2. 2. The toner for static charge image development according to the first item, wherein the peak top molecular weight of the resin in the toner particles is in the range of 14000 to 21000.

3 . The toner for developing an electrostatic charge image according to the first or second item, wherein the crystalline resin has a melting point in the range of 65 to 85 ° C.

4 . The toner for static charge image development according to any one of items 1 to 3 , wherein the content of the block polymer in the toner particles is in the range of 1 to 20% by mass.

5 . The toner for developing an electrostatic charge image according to any one of items 1 to 4 , wherein the block polymer has a crystalline portion and an amorphous portion.

6 . The weight average molecular weight of the crystal portion is in the range of 1000 to 3000.
The toner for developing an electrostatic charge image according to Item 5, wherein the weight average molecular weight of the amorphous portion is in the range of 1000 to 40,000.

7 . The toner for static charge image development according to item 5 or 6 , wherein the crystal part is a resin part having a structure derived from a crystalline polyester resin.

8 . The toner for electrostatic charge image development according to any one of items 1 to 7 , wherein the toner particles contain a polyester resin having a structure derived from dodecenyl succinic acid as a binder resin.

9 . The content of the styrene-acrylic resin before SL in the toner particles, toner according to any one of the first term to the eighth term, characterized in that at least 5% by mass.

10 . The toner for static charge image development according to any one of items 1 to 9 , wherein the shell layer contains a polyester resin having a structure derived from dodecenyl succinic acid.

11 . The content of structural from said dodecenylsuccinic acid resin, wherein the shell layer contains the electrostatic image developing toner according to paragraph 10, characterized in that in the range of 3 to 13 mass%.

12 . The toner for developing an electrostatic charge image according to any one of items 1 to 11, which is a cyan toner.

By the above means of the present invention, it is possible to obtain the meltability of toner which is excellent in low temperature fixability and which makes the thickness and glossiness of the toner layer uniform in the concave and convex portions of the paper, and causes uneven density and gloss of the image. It can be reduced.
Although the mechanism of expression or mechanism of action of the effects of the present invention has not been clarified, it is inferred as follows.
By including the crystalline resin in the toner, the meltability is enhanced, the film formation between the toners is promoted, and the low temperature fixability is improved. That is, the light transmittance of the toner layer at a wavelength of 490 nm is 80% or more. When the light transmittance at a wavelength of 490 nm is 80% or more, for example, the toner is easily melted and spread, the toner layer is thinned, the coverage of the toner on the white background of the paper is increased, and the coloring power is increased. Go up. Further, by setting the light transmittance of the toner layer at a wavelength of 490 nm to 90% or less, the toner existing at the boundary between the convex portion and the concave portion of the rough paper is less likely to flow into the concave portion, and the fibers of the paper are exposed on the image. However, uneven density of the image can be improved. Further, by setting the transmittance of the light at the wavelength of 670 nm of the toner layer to 10% or less in addition to the range of the transmittance of light having a wavelength of 490 nm, the difference between the transmittance of light having a wavelength of 490 nm and the wavelength of 670 nm becomes large. Since the coloring power of the concave portion is improved, uneven density and uneven gloss of the image can be improved.
From the above points, the transmittance of light having a wavelength of 490 nm of the toner layer containing a crystalline resin is in the range of 80 to 90%, and the transmittance of light having a wavelength of 670 nm is in the range of 0 to 10%. By setting it inside, it is possible to improve low-temperature fixability, reduce uneven density and uneven gloss of an image, and improve image quality.

FIG. 1A is a schematic diagram showing the spread and spread of toner on rough paper when unfixed, and FIG. 1B is a schematic diagram showing the spread and spread of toner on rough paper when fixed. FIG. 2A shows a schematic view showing the spread spread of the toner of the present invention on rough paper after fixing, and FIG. 2B shows the spread spread of the toner when uneven image density and uneven gloss occur. The schematic diagram and FIG. 2 (c) are schematic views showing the melting and spreading of toner when uneven image density occurs.

The static charge image development toner of the present invention is a static charge image development toner composed of toner particles containing at least an amorphous resin, a crystalline resin, and a colorant, and is the same as the static charge image development toner. A toner layer having an adhesion amount of 6.5 g / m ² is formed on glass, and heat of 185 ° C. is applied for 5 seconds from a position where the distance from the surface of the toner layer is 100 μm, and then the light transmittance of the toner layer is adjusted. When measured, the transmittance of light having a wavelength of 490 nm is in the range of 80 to 90%, and the transmittance of light having a wavelength of 670 nm is in the range of 0 to 10%. .. This feature is a technical feature common to or corresponding to the invention according to each claim.
In an embodiment of the present invention, the transmittance of light having a wavelength of 490 nm and the transmittance of light having a wavelength of 670 nm can be easily adjusted within the above ranges, and the peak top of the resin in the toner particles can be easily adjusted. It is preferable that the molecular weight is in the range of 14000 to 21000 and that the toner particles contain the amorphous resin, the crystalline resin and the block polymer as the binder resin.

Further, from the viewpoint of excellent low-temperature fixability, it is preferable that the toner particles contain a crystalline polyester resin as the crystalline resin, and the melting point of the crystalline resin is in the range of 65 to 85 ° C.
Further, the content of the block polymer in the toner particles is in the range of 1 to 20% by mass in that the meltability of the toner can be easily controlled, and the block polymer has a crystalline portion and an amorphous portion. It is preferable that the crystalline portion has a weight average molecular weight in the range of 1000 to 3000, and that the crystalline portion is a resin portion having a structure derived from a crystalline polyester resin.

Further, from the viewpoint of uneven gloss and fixability, it is preferable that the toner particles contain a polyester resin having a structure derived from dodecenyl succinic acid as a binder resin.
Further, from the viewpoint of achieving both heat-resistant storage and low-temperature fixability, the toner particles contain styrene / acrylic resin as the amorphous resin, and the content of the styrene / acrylic resin in the toner particles is 5. It is preferably mass% or more.

Further, the core particles and the shell can have different characteristics such as glass transition point, melting point, elastic modulus, etc., and the toner particles can be designed according to the purpose. It is preferable to form a core-shell structure by providing a shell layer that covers the surface of the core particles.
Further, in that the meltability of the toner can be easily adjusted, the shell layer contains a polyester resin having a structure derived from dodecenyl succinic acid, and has a structure derived from dodecenyl succinic acid in the resin contained in the shell layer. The content of the polyester resin is preferably in the range of 3 to 13% by mass.
Further, it is preferable that the toner for static charge image development of the present invention is a cyan toner because the difference in light transmittance between the wavelength of 490 nm and the wavelength of 670 nm of the toner layer becomes large.

Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the present application, "~" is used to mean that the numerical values described before and after the value are included as the lower limit value and the upper limit value.

[Toner for static charge image development]
The toner for static charge image development of the present invention (hereinafter, also simply referred to as toner) is composed of toner particles containing at least an amorphous resin, a crystalline resin, and a colorant.
Further, in the toner of the present invention, a toner layer having an adhesion amount of 6.5 g / m ² is formed on the glass, and heat of 185 ° C. is applied for 5 seconds from a position where the distance from the surface of the toner layer is 100 μm. When the light transmittance of the toner layer was measured after the addition, the transmittance of light having a wavelength of 490 nm was in the range of 80 to 90%, and the transmittance of light having a wavelength of 670 nm was 0 to 10. It is characterized by being in the range of%.

The transmittance of light having a wavelength of 490 nm represents the transparency of the toner layer. When the toner melts and spreads, the toner layer becomes thinner, making it easier for light to pass through. Further, the easier it is for the toner to melt and spread, the more grain boundaries between the toners are eliminated, and the internal scattering of light is suppressed, so that light can be easily transmitted.
Here, by setting the transmittance of light having a wavelength of 490 nm to 80% or more, the toner in the convex portions and the concave portions is easily melted and spread, the toner layer is thinned, and the coverage of the toner on the white background portion of the paper is increased. It goes up and the coloring power goes up. Further, by setting the light transmittance to 90% or less, the melting and spreading of the toner is suppressed, and the toner existing at the boundary between the convex portion and the concave portion of the rough paper is difficult to flow into the concave portion. As a result, the density unevenness of the image can be improved without exposing the paper fibers on the image.

The transmittance of light having a wavelength of 670 nm represents the absorption of light by the cyan pigment.
By setting the transmittance of the light having a wavelength of 670 nm within the range of 0 to 10% in addition to the range of the transmittance of light having a wavelength of 490 nm, the transmittance of light having a wavelength of 490 nm and the light having a wavelength of 670 nm are set. The difference from the transmittance of the concave portion becomes large, and the coloring power of the concave portion is improved. That is, when the transmittance of light having a wavelength of 490 nm increases, the toner melts and spreads to thin the toner layer, and the coverage of the toner on the white background of the paper increases, so that the coloring power increases. On the other hand, when the transmittance of light having a wavelength of 670 nm is lowered to 10% or less, the absorption of light by the pigment is increased, so that the coloring power is increased. Therefore, by increasing the transmittance of light having a wavelength of 490 nm to 80 to 90% and decreasing the transmittance of light having a wavelength of 670 nm to 0 to 10%, the coloring power is improved. As a result, uneven density and uneven gloss of the image can be improved.

The mechanism of occurrence of density unevenness and gloss unevenness in the above image will be described with reference to FIGS. 1 and 2.
FIG. 1A shows the toner in the rough paper (concave and convex paper) when it is not fixed, and the toner 100 in the convex portion 201 and the concave portion 202 is not melted and spread. From this state, when the toner 100 is fixed by the fixing belt B as shown in FIG. 1 (b), in the case of the toner of the present invention, as shown in FIG. 2 (a), the convex portion 201 and the concave portion 202 Toner 100 is appropriately melted and spread to form a toner layer 100a having the same thickness, and the light reflection intensities L in the convex portion 201 and the concave portion 202 are also about the same. Therefore, uneven density and uneven gloss of the image are suppressed.
On the other hand, in the case of FIG. 2B, the toner 100 in the concave portion 202 does not melt and spread, and there is a grainy feeling, and the light reflection intensity L in the convex portion 201 and the concave portion 202 is different. Therefore, uneven density and uneven gloss of the image occur. Further, in the case of FIG. 2C, the toner 100 of the convex portion 201 flows into the concave portion 202, the toner layer 100a of the convex portion 201 is thin, and the toner layer 100a of the concave portion 202 is thick. Therefore, uneven density of the image occurs.
Therefore, by specifying the transmittance of light having a wavelength of 490 nm and the transmittance of light having a wavelength of 670 nm within the above ranges, an ideal state in which uneven density and uneven gloss of the image as shown in FIG. 2A are suppressed. Can be.

The transmittance of light at wavelengths of 490 nm and 670 nm of the toner layer under the above heating conditions adjusts the molecular weight of the binder resin in the toner particles, contains a block polymer in the toner particles, and is derived from dodecenyl succinic acid in the toner particles. It can be adjusted within the above range by an adjustment method such as containing a polyester resin having the above structure. These adjustment methods can also be combined.

[Bundling resin]
The toner particles can contain other resins such as a block polymer as the binder resin as well as the crystalline resin and the amorphous resin.
A crystalline resin is a resin that exhibits crystallinity, and exhibiting crystallinity means that it has a clear endothermic peak at the melting point, that is, when the temperature rises, in the endothermic curve obtained by differential scanning calorimetry (DSC). Say. A clear endothermic peak means a peak having a half-value width within 15 ° C. in the endothermic curve when the temperature is raised at a heating rate of 10 ° C./min. The amorphous resin is a resin exhibiting amorphousness, and exhibiting amorphous means that it does not have a clear endothermic peak at the melting point, that is, when the temperature rises in the above-mentioned endothermic curve.
From the viewpoint of achieving both heat resistance and low-temperature fixability, the toner particles are a matrix in which an amorphous resin having excellent heat resistance is used as a matrix and a crystalline resin that imparts low-temperature fixability is dispersed in the matrix as a domain. -It is preferable to have a domain structure.

The peak top molecular weight (Mp) of the resin in the toner particles is preferably in the range of 14000 to 21000.
The peak top molecular weight (Mp) refers to the molecular weight corresponding to the peak top of the maximum peak having the largest peak area in the molecular weight distribution of the resin obtained by measuring by gel permeation chromatography (GPC). ..
When the peak top molecular weight (Mp) is within the above range, the transmittance of light having a wavelength of 490 nm in the toner layer under the above heating conditions is within the range of 80 to 90%, and the transmittance of light having a wavelength of 670 nm. The meltability of the toner can be adjusted so as to be in the range of 0 to 10%.
The peak top molecular weight (Mp) of the resin is selected from the composition of each resin used as the binder resin, the block polymer described later is used, and the polymerization initiator and chain transfer agent used when synthesizing the binder resin. It can be adjusted by a method such as adjusting the content.

From the viewpoint of achieving both better low-temperature fixability and reduction of image density unevenness, the peak top molecular weight (Mp) of the resin in the toner particles is more preferably in the range of 1500 to 19000, and 16000 to 18000. The range of is more preferable.

The molecular weight distribution of the resin can be measured by GPC as follows.
A sample (toner) was added to tetrahydrofuran (THF) to a concentration of 1 mg / mL, dispersed at 40 ° C. for 15 minutes using an ultrasonic disperser, and then treated with a membrane filter having a pore size of 0.2 μm. , Prepare the sample solution. Using a GPC device HLC-8220GPC (manufactured by Tosoh) and a column TSKguard column + TSKgel SuperHZM-M triplet (manufactured by Tosoh), tetrahydrofuran is flowed as a carrier solvent at a flow rate of 0.2 mL / min while maintaining the column temperature at 40 ° C. .. 10 μL of the prepared sample solution was injected into the GPC device together with the carrier solvent, the sample was detected using a refractive index detector (RI detector), and a calibration line measured using monodisperse polystyrene standard particles was used. , Calculate the molecular weight distribution of the sample. The calibration curves have molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10, respectively. It is prepared by measuring 10 polystyrene standard particles (manufactured by Pressure Chemical), which are ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ and 4.48 × 10 ⁶ .

[Crystalline resin]
The toner particles preferably contain a crystalline polyester resin as the crystalline resin from the viewpoint of obtaining better low-temperature fixability.

[Crystalline polyester resin]
The crystalline polyester resin is a known polyester resin obtained by a polycondensation reaction between a divalent or higher carboxylic acid (polyvalent carboxylic acid) monomer and a divalent or higher alcohol (polyhydric alcohol) monomer. , A polyester resin exhibiting crystallinity.

The method for synthesizing the crystalline polyester resin is not particularly limited, and the crystalline polyester is polymerized (esterified) by using an esterification catalyst to polymerize (esterify) the polyvalent carboxylic acid monomer and the polyhydric alcohol monomer. Resin can be formed.

The polyvalent carboxylic acid monomer is a compound containing two or more carboxy groups in one molecule.
Examples of the polyvalent carboxylic acid monomer that can be used in the synthesis of the crystalline polyester resin include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, n-dodecylsuccinic acid, and 1,10-decandicarboxylic acid. Saturated aliphatic dicarboxylic acid such as acid (dodecanedioic acid); alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acid such as phthalic acid, isophthalic acid and terephthalic acid; trimellitic acid, pyromellitic acid and the like 3 Polyvalent carboxylic acids having a valence or higher; anhydrides of these carboxylic acid compounds, alkyl esters having 1 to 3 carbon atoms, and the like can be mentioned.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

A polyhydric alcohol monomer is a compound containing two or more hydroxy groups in one molecule.
Examples of the polyhydric alcohol monomer that can be used in the synthesis of the crystalline polyester resin include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6. Aliphatic diols such as −hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 1,4-butenediol; glycerin, pentaerythritol, trimethylolpropane, Examples thereof include trihydric or higher polyhydric alcohols such as sorbitol.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

As esterification catalysts that can be used, alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metal compounds such as aluminum, zinc, manganese, antimony, titanium, tin, zirconium and germanium; Phosphoric acid compounds; phosphoric acid compounds; amine compounds and the like can be mentioned.

The polymerization temperature is not particularly limited, but is preferably in the range of 150 to 250 ° C. The polymerization time is not particularly limited, but is preferably in the range of 0.5 to 10 hours. During the polymerization, the pressure inside the reaction system may be reduced, if necessary.

The melting point (Tm) of the crystalline resin such as the crystalline polyester resin is preferably in the range of 65 to 85 ° C. from the viewpoint of achieving both excellent low temperature fixability, heat resistance and hot offset resistance, and is 70. The range of about 80 ° C. is more preferable.

The melting point (Tm) is the temperature at the top of the endothermic peak and can be measured by DSC.
Specifically, the sample was made of aluminum pan KITNO. It is sealed in B0143013, set in a sample holder of a thermal analyzer Diamond DSC (manufactured by PerkinElmer), and the temperature is changed in the order of heating, cooling, and heating. The temperature is raised from room temperature (25 ° C.) during the first heating to 150 ° C. at a heating rate of 10 ° C./min from 0 ° C. during the second heating, and kept at 150 ° C. for 5 minutes. The temperature is lowered from 150 ° C. to 0 ° C. at a temperature lowering rate of ° C./min, and the temperature of 0 ° C. is maintained for 5 minutes. The temperature of the peak top of the endothermic peak in the endothermic curve obtained during the second heating is measured as the melting point.

The content of the crystalline resin such as the crystalline polyester resin in the toner particles is preferably in the range of 5 to 20% by mass from the viewpoint of achieving both excellent low temperature fixability, heat resistance and hot offset resistance. , 7 to 15% by mass is more preferable.

[Block polymer]
The toner particles preferably contain a block polymer as a binder resin. A block polymer is a block copolymer of two or more kinds of resins.
By adjusting the molecular weight, content, etc. of the block polymer, the transmittance of the toner layer under the above heating conditions so that the transmittance of light having a wavelength of 490 nm and the transmittance of light having a wavelength of 670 nm are within the above ranges. The meltability can be adjusted.

The content of the block polymer in the toner particles is preferably in the range of 1 to 20% by mass, more preferably in the range of 5 to 20% by mass, and even more preferably in the range of 5 to 15% by mass.
If the content of the block polymer is 1% by mass or more, the toner is prevented from being excessively melted only by heating at the time of fixing, and if it is 20% by mass or less, the toner is released without applying a large amount of heat and pressure at the time of fixing. The meltability of the toner can be adjusted so that it melts. Due to the meltability of such toner, it is possible to obtain a toner having excellent low-temperature fixability and less uneven density in an image.

The block polymer preferably has a crystalline portion and an amorphous portion.
The crystalline part means a resin part having a structure derived from a crystalline resin, and the amorphous part means a resin part having a structure derived from an amorphous resin.
The difficulty of dissolving the toner can be adjusted by the crystalline portion, and the ease of dissolving the toner can be adjusted by the amorphous portion, and the meltability of the toner can be easily controlled. Further, since such a block polymer forms a micro phase-separated state, it is possible to impart pressure dependence to the melting and spreading of the toner due to pressurization during fixing.

The above-mentioned crystalline resin can be used for forming the crystal portion of the block polymer. Above all, if the crystal portion is a resin portion having a structure derived from the crystalline polyester resin used as the binder resin for the toner particles, the compatibility with the crystalline polyester resin in the binder resin is enhanced, so that the block It is preferable because it becomes easier to control the meltability of the toner by the polymer.
The resin used for forming the crystal portion preferably has a melting point (Tm) in the range of 65 to 85 ° C. If it is within this range, good crystallinity can be obtained, it becomes easy to adjust the solubility of the toner, and the low temperature fixability of the toner becomes better.

The weight average molecular weight (Mw) of the crystal portion is preferably in the range of 1000 to 3000.
If it is within this range, good crystallinity can be obtained, it becomes easy to adjust the solubility of the toner, and the low temperature fixability of the toner is further improved.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin can be obtained from the molecular weight distribution of the resin measured by the above-mentioned GPC.

An amorphous resin such as polystyrene resin, styrene-butadiene resin, vinyl resin such as styrene / acrylic resin, and amorphous polyester resin can be used for forming the amorphous portion of the block polymer. These resins may be modified with urethane, urea, epoxy or the like.
When the amorphous portion is a resin portion having a structure derived from an amorphous resin used as a binder resin for toner particles, the compatibility with the binder resin is enhanced and the dispersibility of the block polymer is improved. Is possible and preferable.

Further, the resin used for forming the amorphous portion preferably has a glass transition point (Tg) in the range of 40 to 75 ° C.
The glass transition point (Tg) of the resin can be measured according to the method (DSC method) specified in ASTM (American Society for Testing and Materials) D3418-82. For the measurement, a DSC-7 differential scanning calorimeter (manufactured by PerkinElmer), a TAC7 / DX thermal analyzer controller (manufactured by PerkinElmer), or the like can be used.

The weight average molecular weight (Mw) of the amorphous portion is preferably in the range of 1000 to 40,000.
Within this range, it becomes easy to adjust the solubility of the toner, the robustness of the toner becomes good, and the filming on the photoconductor can be suppressed.

[Amorphous resin]
As the amorphous resin, a vinyl resin, an amorphous polyester resin, or the like can be used. The vinyl resin is a polymer of vinyl monomers. Specific examples of the vinyl resin include styrene resin, acrylic resin, styrene / acrylic resin and the like.

From the viewpoint of obtaining excellent heat-resistant storage properties, the toner particles preferably contain a styrene / acrylic resin as a binder resin, and the content of the styrene / acrylic resin in the toner particles is preferably 5% by mass or more.
From the viewpoint of achieving both heat-resistant storage and low-temperature fixability, the content of the styrene / acrylic resin in the toner particles is preferably 80% by mass or less.

The vinyl monomer is a polymerizable monomer having a vinyl group, and one type can be used alone or a plurality of types of vinyl monomers can be used in combination. The following monomers are examples of vinyl monomers. Above all, by using polyfunctional vinyls, a polymer having a crosslinked structure can be obtained. The styrene / acrylic resin may be a copolymer in which a styrene-based monomer and a (meth) acrylic acid-based monomer are further combined with another vinyl monomer.

(1) Styrene-based monomer styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert A single amount having a styrene structure such as −butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene and derivatives thereof. Body (2) (meth) acrylic acid-based monomer (meth) acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-butyl (meth) acrylic acid, isopropyl (meth) acrylic acid, ( Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, (meth) Monomers having (meth) acrylic groups such as phenyl acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and derivatives thereof (3) Vinyl esters Vinyl propionate, vinyl acetate, benzoe Vinyl acid acid, etc. (4) Vinyl ethers Vinyl methyl ether, vinyl ethyl ether, etc. (5) Vinyl ketones Vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone, etc. (6) N-vinyl compounds N-vinylcarbazole, N-vinylindole , N-vinylpyrrolidone, etc. (7) Others Vinyl compounds such as vinylnaphthalene and vinylpyridine, acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc. (8) Polyfunctional vinyls Divinylbenzene, ethylene glycol Dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, etc.

Above all, the vinyl monomer having an acid group is preferable because the vinyl resins can be easily ion-crosslinked with each other and the degree of ion-crosslinking can be easily controlled by adjusting the content of the acid group in the vinyl resin. ..
The acid group refers to an ionic dissociating group such as a carboxy group, a sulfonic acid group, and a phosphoric acid group.
For example, examples of the vinyl monomer having a carboxy group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, silicic acid, fumaric acid, maleic acid monoalkyl ester, and itaconic acid monoalkyl ester.
Examples of the vinyl monomer having a sulfonic acid group include styrene sulfonic acid, allylsulfosuccinic acid, 2-acrylamide-2-methylpropanesulfonic acid and the like.
Examples of the vinyl monomer having a phosphoric acid group include acid phosphooxyethyl methacrylate and the like.

The glass transition point (Tg) of the vinyl resin is preferably in the range of 20 to 70 ° C. from the viewpoint of achieving both low-temperature fixability and heat-resistant storage.

The content of the vinyl resin in the toner particles is preferably 5% by mass or more, more preferably in the range of 20 to 60% by mass, and 35 to 60% by mass from the viewpoint of obtaining excellent heat resistance. It is more preferable that it is within the range of.

[Amorphous polyester resin]
The amorphous polyester resin refers to a resin exhibiting amorphousness among polyester resins obtained by a polymerization reaction of a polyvalent carboxylic acid monomer and a polyhydric alcohol monomer.
The amorphous polyester resin can be synthesized by polymerizing a polyvalent carboxylic acid monomer and a polyhydric alcohol monomer using an esterification catalyst in the same manner as the above-mentioned crystalline polyester resin.

Examples of the polyvalent carboxylic acid monomer that can be used in the synthesis of the amorphous polyester resin include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid, and isophthalic acid. Examples thereof include dimethyl acid acid, fumaric acid, dodecenyl succinic acid, 1,10-decandicarboxylic acid and the like. Of these, dimethyl isophthalate, terephthalic acid, dodecenyl succinic acid or trimellitic acid is preferable.

Examples of the polyhydric alcohol monomer that can be used in the synthesis of the amorphous polyester resin include ethylene glycol, propylene glycol, 1,4-butanediol, and 2,3-butanediol as divalent or trivalent alcohols. Ethylene oxide adducts of diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, bisphenol A ( BPA-EO), propylene oxide adduct of bisphenol A (BPA-PO), glycerin, sorbitol, 1,4-sorbitane, trimethylolpropane and the like. Among these, an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A are preferable.

Above all, the amorphous polyester resin preferably has a structure derived from dodecenyl succinic acid.
By having a polyester resin having a structure derived from dodecenyl succinic acid having a long-chain alkyl group, the polyester resin having a structure derived from dodecenyl succinic acid is selectively selected from the crystalline polyester resin when heat is applied to the recesses of the rough paper. Since the toner is instantly melted and spread, the difference in gloss between the convex and concave images can be reduced and uneven gloss can be improved. Further, the adhesive strength between the toner and the paper is improved in the recess, and the fixability can be improved.

[Colorant]
The toner of the present invention is preferably cyan toner, and examples of the colorant contained in the cyan toner include C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 3, 15: 4, 60, phthalocyanine pigments whose central metal is zinc, titanium, magnesium or the like can be used, and mixtures thereof can also be used.
As a dye, C.I. I. Solvent blue 25, 36, 60, 70, 93, 95 and the like can be used, and mixtures thereof can also be used.
The number average primary particle size of the colorant varies depending on the type, but it is preferably about 10 to 200 nm.
The content ratio of the colorant in the toner is preferably in the range of 1 to 30% by mass, more preferably in the range of 2 to 20% by mass, based on the total mass of the binder resin in the toner.

The toner particles can contain additives such as a mold release agent and a charge control agent, if necessary. 〔Release agent〕
The release agent is not particularly limited, and various known waxes can be used. Examples of the release agent that can be used include polyolefin waxes such as polyethylene wax and polypropylene wax, branched chain hydrocarbon waxes such as microcrysterin wax, long chain hydrocarbon waxes such as paraffin wax and sazole wax, and distearyl ketones. Dialkylketone waxes such as carnauba wax, montan wax, behenate behenate, trimethylpropan tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18- Examples thereof include ester waxes such as octadecanediol distearate, tristearyl trimellitic acid and distealyl maleate, and amide waxes such as ethylenediamine behenylamide and tristealylamide trimellitic acid.

The content of the release agent in the toner particles is preferably in the range of 3 to 15 parts by mass from the viewpoint of obtaining sufficient fixing separability.

[Charge control agent]
As the charge control agent, known compounds such as niglosin dyes, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, quaternary ammonium salts, azo metal complexes, and salicylate metal salts can be used. By adding a charge control agent, a toner having excellent charge characteristics can be obtained.
The content of the charge control agent can be usually in the range of 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the binder resin.

[Core / shell structure]
The above-mentioned toner particles can be used as they are as toner, but the toner particles may be core particles and may have a shell layer that covers the surface of the core particles to form a core-shell structure.
The shell layer may cover at least a part of the core particles, and the core particles may be partially exposed. The cross section of the core-shell structure can be confirmed by a known observation means such as a transmission electron microscope (TEM) or a scanning probe microscope (SPM).

In the case of the core-shell structure, the core particles and the shell layer can have different characteristics such as the glass transition point, melting point, and elastic modulus, and the toner particles can be designed according to the purpose. For example, a resin having a relatively high glass transition point (Tg) is aggregated and fused to the surface of core particles containing a binder resin, a colorant, a mold release agent, etc. and having a relatively low glass transition point (Tg). The shell layer can be formed.

In the case of a core-shell structure, it is preferable that the shell layer contains a polyester resin having a structure derived from dodecenyl succinic acid.
As a result, the long-chain alkyl groups on the surface layer of the toner particles can be increased, and the elastic modulus of the toner can be instantly lowered only on the surface layer without changing the elastic modulus as a whole when heat is applied. The meltability of the toner can be easily adjusted so that the convex portion of the paper that comes into contact with the fixing member is difficult to melt and the concave portion of the paper that does not come into contact with the fixing member is easy to melt.

The content of the polyester resin having a structure derived from dodecenyl succinic acid in the resin contained in the shell layer is preferably in the range of 3 to 13% by mass, and more preferably in the range of 5 to 10% by mass. preferable.
Within this range, it is easy to obtain a meltable toner that is difficult to melt in the convex portion of the paper that contacts the fixing member and easily melts in the concave portion of the paper that does not contact the fixing member.

In a toner having a core-shell structure, by adding a block polymer to the core particles, the toner existing at the boundary between the convex portion and the concave portion of the rough paper is less likely to flow into the concave portion, the exposure of the paper fiber is suppressed, and the image Can improve the density unevenness of. In addition, by containing a polyester resin having a structure derived from dodecenyl succinic acid in the shell layer, the crystalline polyester contained in the core selectively blends with the shell when heat is applied to the recesses of the rough paper, and the toner surface layer is formed. Since it melts and spreads instantly, it is possible to reduce the difference in glossiness between the convex and concave images and improve the uneven gloss. Further, the adhesive strength between the toner and the paper is improved in the recess, and the fixability can be improved. That is, it is preferable that the core particles have pressure dependence during heating and the shell layer is positively melted.

The glass transition point (Tg) of the toner is preferably in the range of 40 to 60 ° C, more preferably in the range of 45 to 55 ° C.
Within this range, sufficient low-temperature fixability and heat-resistant storage property can be reliably obtained at the same time. Further, when the glass transition point of the toner is in the above range, the heat resistance (thermal strength) of the toner is maintained, and as a result, sufficient heat storage resistance and hot offset resistance can be surely obtained.

[External agent]
The toner particles can be used as toner as they are, but in order to improve the fluidity, chargeability, cleaning property, etc., an external additive such as a fluidizing agent or a cleaning aid may be added to the surface thereof.

Examples of the external additive include inorganic oxide fine particles such as silica fine particles, alumina fine particles, and titanium oxide fine particles, inorganic stearic acid compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, strontium titanate, and zinc titanate. Examples thereof include inorganic titanic acid compound fine particles, and one type can be used alone or two or more types can be used in combination.
From the viewpoint of improving heat-resistant storage and environmental stability, these inorganic particles are preferably gloss-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil, or the like.

The amount of the external additive added (when a plurality of external agents are used, the total amount added) is preferably in the range of 0.05 to 5 parts by mass with respect to 100 parts by mass of the toner, and is 0.1. More preferably, it is in the range of ~ 3 parts by mass.

[Developer]
The toner for electrostatic latent image developing of the present invention can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer.
When the toner is used as a two-component developer, the carrier uses magnetic particles made of a conventionally known material such as a metal such as iron, ferrite, or magnetite, or an alloy between the metal and a metal such as aluminum or lead. It is possible, and ferrite particles are particularly preferable.

Further, as the carrier, a coat carrier in which the surface of the magnetic particles is coated with a coating agent such as a resin, a dispersed carrier in which the magnetic fine powder is dispersed in a binder resin, or the like may be used.
The average particle size of the carriers is preferably in the range of 20 to 100 μm, more preferably in the range of 25 to 80 μm in terms of volume-based median diameter.
The median diameter based on the volume of the carrier can be typically measured by a laser diffraction type particle size distribution measuring device Heros (HELOS, manufactured by Sympathetic) equipped with a wet disperser.

[Manufacturing method of toner for electrostatic charge development]
Examples of the method for producing the toner for developing an electrostatic charge image of the present invention include a suspension polymerization method, an emulsion agglutination method, and other known methods. From the viewpoint of production cost and production stability, it is preferable to use an emulsification agglutination method in which the particle size of the toner particles can be easily reduced.

The method for producing the toner particles by the emulsion aggregation method is to mix the aqueous dispersion of the binder resin particles and the aqueous dispersion of the colorant particles and aggregate the binder resin particles and the colorant particles to aggregate the toner particles. Is a method of forming.

Here, the aqueous dispersion means that the particles are dispersed in the aqueous medium, and the aqueous medium means that the main component of the aqueous medium is 50% by mass or more of water.
Examples of components other than water in the aqueous medium include organic solvents that are soluble in water, and examples thereof include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Of these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, are preferable.

Hereinafter, an example of the process of the toner manufacturing method by the emulsion aggregation method will be described.
(Step (1))
In step (1), dispersions of binder resin particles such as crystalline resin, block polymer, and amorphous resin are prepared.

For example, when a crystalline polyester resin is used as the crystalline resin, a crystalline polyester resin is synthesized, dissolved or dispersed in an organic solvent to prepare an oil phase liquid, and this oil phase liquid is inversion emulsified. Disperse polyester resin particles in an aqueous medium. An aqueous dispersion of a polyester resin can be obtained by controlling the particle size of the oil droplets to a desired particle size and then removing the organic solvent.

The organic solvent used in the oil phase solution is preferably one having a low boiling point and low solubility in water from the viewpoint of easy removal treatment after formation of oil droplets. Specific examples thereof include methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene and xylene. These may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of the organic solvent used is usually in the range of 1 to 300 parts by mass with respect to 100 parts by mass of the crystalline polyester resin.
The emulsification and dispersion of the oil phase liquid can be carried out by utilizing mechanical energy.

The amount of the aqueous medium used is preferably in the range of 50 to 2000 parts by mass, and more preferably in the range of 100 to 1000 parts by mass with respect to 100 parts by mass of the oil phase liquid.
A surfactant or the like may be added to the aqueous medium for the purpose of improving the dispersion stability of oil droplets.

The average particle size of the crystalline polyester resin particles is preferably in the range of 100 to 400 nm in terms of volume-based median diameter (D50).
The volume-based median diameter (D50) of the crystalline polyester resin particles can be measured using Microtrack UPA-150 (manufactured by Nikkiso Co., Ltd.).

The block polymer can be obtained by reacting the terminal functional groups of a plurality of types of resins used as the crystalline part and the amorphous part, or by reacting with a binder. As the binder, a polyvalent carboxylic acid, a polyhydric alcohol, a polyvalent isocyanate, a polyfunctional epoxy, a polyacid anhydride and the like can be used.
When a binder is not used, for example, in the case of polyester resins, polymerization can be carried out by heating and reducing the pressure and proceeding with the condensation reaction. Other than polyester resins, if the ends of each resin have acid and alcohol functional groups, they can be synthesized by the same method.

When a vinyl resin is used as the binder resin, an aqueous dispersion of vinyl resin particles can be prepared by a miniemulsion polymerization method. Specifically, a vinyl monomer and a water-soluble radical polymerization initiator are added to an aqueous medium containing a surfactant, and mechanical energy is applied to form droplets. The radicals from the radical polymerization initiator promote the polymerization reaction in the droplets. An oil-soluble polymerization initiator may be contained in the droplets.

The vinyl resin particles may have a multilayer structure of two or more layers in which the composition of each layer is different. A dispersion of vinyl resin particles having a multi-layer structure can be obtained by a multi-step polymerization reaction. For example, in a vinyl resin dispersion having a two-layer structure, a polymerization initiator and a vinyl monomer are further added after preparing a dispersion of vinyl resin particles by polymerizing vinyl monomers (first stage polymerization). It can be obtained by polymerizing (second stage polymerization).

(Surfactant)
Examples of the surfactant include cationic surfactants such as dodecyl ammonium bromide and dodecyl trimethyl ammonium bromide, dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, norylphenyl polykioshiethylene ether, and lauryl polyoxyethylene ether. Known surfactants such as anionic surfactants such as sorbitan monooleate polyoxyethylene ether, nonionic surfactants such as sodium stearate, sodium laurate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, and sodium dodecyl sulfate. Agents can be used.

(Polymerization initiator)
As the polymerization initiator, various conventionally known ones can be used. As the polymerization initiator, persulfate (potassium persulfate, ammonium persulfate, etc.) can be preferably used, but 4,4'-azobis (4-cyanovaleric acid) and a salt thereof, 2,2'-azobis (2-). Azo-based compounds such as amidinopropane) salt, peroxide compounds, azobisisobutyronitrile and the like may be used.

(Chain transfer agent)
A commonly used chain transfer agent can be added to the aqueous medium for the purpose of adjusting the molecular weight of the vinyl resin. The chain transfer agent is not particularly limited, and examples thereof include mercaptans such as 2-chloroethanol, octyl mercaptan, dodecyl mercaptan, t-dodecyl mercaptan, n-octyl-3-mercaptopropionate, and styrene dimers. be able to.

When producing toner particles containing an additive such as a mold release agent or a charge control agent, the additive is introduced into the toner particles by dissolving or dispersing the additive in a solution of vinyl monomer in advance. can do.
In this way, it is preferable to disperse the additive with the vinyl resin particles in advance, but a dispersion of the additive particles is prepared separately from the vinyl resin and mixed with another dispersion such as polyester resin particles. It can also be introduced into the toner particles by aggregating the additive particles together with the polyester resin particles and the like.

The average particle size of the vinyl resin particles in the dispersion is preferably in the range of 100 to 400 nm in terms of volume-based median diameter (D50).
The volume-based median diameter (D50) of the vinyl resin particles can be measured using Microtrac UPA-150 (manufactured by Nikkiso Co., Ltd.).

(Step (2))
In the step (2), the colorant is dispersed in the aqueous medium in the form of fine particles to prepare an aqueous dispersion of the colorant particles.

The aqueous dispersion of the colorant particles can be obtained by dispersing the colorant in an aqueous medium in which the surfactant is added at a critical micelle concentration (CMC) or higher.
The colorant can be dispersed by using mechanical energy, and the disperser to be used is not particularly limited, but preferably an ultrasonic disperser, a mechanical homogenizer, a manton gorin, a pressure homogenizer, or the like is added. Examples include medium-type dispersers such as pressure dispersers, sand grinders, Getzman mills, and diamond fine mills.

The volume-based median diameter (D50) of the colorant particles in the aqueous dispersion is preferably in the range of 10 to 300 nm, more preferably in the range of 100 to 200 nm, and in the range of 100 to 150 nm. Is particularly preferable.
The volume-based median diameter (D50) of the colorant particles can be measured using an electrophoretic light scattering photometer ELS-800 (manufactured by Otsuka Electronics Co., Ltd.).

(Step (3))
In the step (3), the binder resin particles such as vinyl resin particles and polyester resin particles, the colorant particles, and the particles of other toner constituents are aggregated in the presence of the flocculant to form the toner particles.
Specifically, a flocculant having a critical aggregation concentration or higher is added to a system in which an aqueous medium and an aqueous dispersion of each particle are mixed, and the temperature is set to a temperature equal to or higher than the glass transition point (Tg) of the vinyl resin to cause the agglomeration.

(Coagulant)
The coagulant is not particularly limited, but one selected from metal salts such as alkali metal salts and alkaline earth metal salts is preferably used. Examples of the metal salt include monovalent metal salts such as sodium, potassium and lithium, divalent metal salts such as calcium, magnesium, manganese and copper, and trivalent metal salts such as iron and aluminum. Specific examples of the metal salt include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, etc., among which agglomerates in a smaller amount. It is particularly preferable to use a divalent metal salt because the above can be promoted. These may be used individually by 1 type, and may be used in combination of 2 or more type.

(Step (4))
In the step (4), the toner particles formed in the step (3) are aged and controlled into a desired shape. Step (4) can be performed as needed.
Specifically, the dispersion liquid of the toner particles obtained in the step (3) is heated and stirred, and the heating temperature, stirring speed, heating time and the like are adjusted so that the toner particles have a desired circularity.

(Step (4B))
In the step (4B), the toner particles obtained in the step (3) or (4) are used as core particles to form a shell layer that covers at least a part of the surface of the core particles. Step (4B) may be performed when forming toner particles having a core-shell structure.

When forming toner particles having a core-shell structure, the resin constituting the shell layer is dispersed in an aqueous medium to prepare a dispersion liquid of the resin particles of the shell layer, which is obtained by the above steps (4) or (5). The resin particles of the shell layer are aggregated and fused to the surface of the toner particles by adding to the dispersion liquid of the obtained toner particles. Thereby, a dispersion liquid of toner particles having a core-shell structure can be obtained.
In order to more firmly agglomerate and fuse the resin particles of the shell layer to the core particles, a heat treatment can be performed following the shelling step. The heat treatment may be performed until the toner particles having the desired circularity are obtained.

(Step (5))
In the step (5), the dispersion liquid of the toner particles is cooled, and the toner particles are solid-liquid separated from the dispersion liquid of the toner particles. Adhesives such as surfactants and flocculants are removed from the toner cake (cake-shaped wet toner particles) obtained by solid-liquid separation, and the toner cake is washed, and the washed toner cake is dried.

(Step (6))
In step (6), an external additive is added to the toner particles. Step (6) can be performed as needed.
A mechanical mixing device such as a Henschel mixer or a coffee mill can be used for adding the external additive.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Although the indication of "part" or "%" is used in the examples, it represents "part by mass" or "% by mass" unless otherwise specified.

Further, in the examples, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin are obtained from the molecular weight distribution obtained by the above-mentioned GPC, and the melting point (Tm) or the glass transition point (Tg) of the resin is described above. It was obtained from the heat absorption curve of DSC. The softening point (Tsp) of the resin was measured by the above-mentioned melting temperature measuring method of the heating method.

[Dispersion of styrene / acrylic resin particles]
(First stage polymerization)
2.0 parts by mass of sodium lauryl sulfate, which is an anionic surfactant, was previously dissolved in 2900 parts by mass of ion-exchanged water in a reaction vessel equipped with a stirrer, a temperature sensor, a temperature control device, a cooling tube and a nitrogen introduction device. An anionic surfactant was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream.

9.0 parts by mass of potassium persulfate (KPS), which is a polymerization initiator, was added to this surfactant solution to bring the internal temperature to 78 ° C. Next, a monomer solution having the following composition was added dropwise over 3 hours, and after the addition was completed, polymerization (first-stage polymerization) was carried out by heating and stirring at 78 ° C. for 1 hour to obtain styrene / acrylic resin particles. The dispersion (I) was prepared.
Styrene 540 parts by mass n-Butyl acrylate 270 parts by mass Methacrylic acid 65 parts by mass n-octyl mercaptan 17 parts by mass

(Second stage polymerization)
In a flask equipped with a stirrer, 51 parts by mass of an ester wax (melting point: 73 ° C.) was added as a release agent to a monomer solution having the following composition, and the mixture was heated to 85 ° C. to dissolve the wax. The solution was prepared.
Styrene 94 parts by mass n-butyl acrylate 30 parts by mass 2-ethylhexyl acrylate 30 parts by mass Methacrylic acid 11 parts by mass n-octyl mercaptan 5 parts by mass

On the other hand, a surfactant solution prepared by dissolving 2 parts by mass of sodium lauryl sulfate, which is an anionic surfactant, in 1100 parts by mass of ion-exchanged water was heated to 90 ° C. To this surfactant solution, 28 parts by mass of the dispersion liquid (I) of the styrene / acrylic resin particles was added in terms of the solid content of the styrene / acrylic resin. Then, the wax solution was mixed and dispersed for 1 hour by a mechanical disperser Clairemix (manufactured by M-Technique Co., Ltd.) having a circulation path to prepare a dispersion containing emulsified particles having a dispersed particle diameter of 350 nm. To this dispersion, an aqueous polymerization initiator solution prepared by dissolving 2.5 parts by mass of potassium persulfate (KPS) as a polymerization initiator in 110 parts by mass of ion-exchanged water is added, and the mixture is heated and stirred at 90 ° C. for 2 hours. As a result, polymerization (second-stage polymerization) was carried out to prepare a dispersion liquid (II) of styrene / acrylic resin particles.

To the prepared dispersion of styrene / acrylic resin particles (II), an aqueous polymerization initiator solution prepared by dissolving 2.5 parts by mass of potassium persulfate (KPS) as a polymerization initiator in 110 parts by mass of ion-exchanged water was added. Under the temperature condition of 80 ° C., a monomer solution having the following composition was added dropwise over 1 hour. Polymerization (third-stage polymerization) was carried out by heating and stirring for 3 hours after the completion of the dropping.
Styrene 230 parts by mass n-Butyl acrylate 100 parts by mass Methacrylic acid 19 parts by mass n-octyl mercaptan 5 parts by mass

Then, the mixture was cooled to 28 ° C. to obtain a dispersion of styrene / acrylic resin particles.
The weight average molecular weight (Mw) of the styrene / acrylic resin in this dispersion was 30900, and the number average molecular weight (Mn) was 10200.

[Dispersion of crystalline polyester resin particles]
In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube and a nitrogen introduction device, 300 parts by mass of sebacic acid, which is a polyvalent carboxylic acid, and 170 parts by mass of 1,6-hexanediol, which is a polyhydric alcohol, were charged. The internal temperature was raised to 190 ° C. over 1 hour with stirring. After confirming that the mixture was uniformly stirred, Ti (OBu) ₄ was added as a catalyst in an amount of 0.003% by mass based on the amount of the polyvalent carboxylic acid charged. While distilling off the generated water, the internal temperature was raised from 190 ° C. to 240 ° C. over 6 hours, and the dehydration condensation reaction was continued for 6 hours under the condition of a temperature of 240 ° C. to carry out polymerization. A sex polyester resin was obtained. The melting point (Tm) of this crystalline polyester resin was 66.8 ° C., and the number average molecular weight (Mn) was 6300.

In a 3-liter reaction tank with a jacket (manufactured by Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, a thermometer, a water dropping device, and an anchor wing, 300 parts by mass of the above crystalline polyester resin and 160 mass of methyl ethyl ketone (solvent). A part and 100 parts by mass of isopropyl alcohol (solvent) were added, and the resin was dissolved while stirring and mixing at 100 rpm while maintaining the temperature at 70 ° C. in a water circulation type constant temperature bath.
After that, the stirring speed was set to 150 rpm, the water circulation type constant temperature bath was set to 66 ° C., 17 parts by mass of 10% by mass ammonia water (reagent) was added over 10 minutes, and then ion-exchanged water kept at 66 ° C. was added. A total of 900 parts by mass was added dropwise at a rate of 7 parts by mass / minute to invert the phase to obtain an emulsion.
Immediately, 800 parts by mass of the obtained emulsion and 700 parts by mass of ion-exchanged water were placed in a 2 liter eggplant flask and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. .. While rotating the eggplant flask, it was heated in a hot water bath at 60 ° C., and the pressure was reduced to 7 kPa while paying attention to sudden boiling to remove the solvent. When the amount of solvent recovered reached 1100 parts by mass, the pressure was returned to normal pressure, and the eggplant flask was water-cooled to obtain a dispersion. The obtained dispersion had no solvent odor. The volume-based median diameter (D50) of the resin particles in this dispersion was 130 nm. Then, ion-exchanged water was added to adjust the solid content concentration to 20% by mass, and this was used as a crystalline polyester resin dispersion.

[Dispersion of block polymer particles]
173 parts of dodecanedioic acid, 174 parts of 1,10-decanediol, and 0.08 part of dibutyltin oxide were placed in a nitrogen-substituted flask and reacted at 170 ° C. for 2 hours and further under reduced pressure at 200 ° C. for 0.5 hours. A crystalline resin having an average molecular weight (Mw) of 1500, a number average molecular weight (Mn) of 700, and a melting point (Tm) of 74 ° C. was obtained.
On the other hand, 97 parts of dimethyl terephthalate, 78 parts of dimethyl isophthalate, 27 parts of dodecenyl succinic anhydride, 111 parts of bisphenol A-ethylene oxide adduct, 249 parts of bisphenol A-propylene oxide adduct, and 0.08 part of dibutyltin oxide were substituted with nitrogen. The mixture was placed in a flask and reacted at 170 ° C. for 4 hours and then at 220 ° C. under reduced pressure for 2 hours. The weight average molecular weight (Mw) was 20000, the number average molecular weight (Mn) was 9000, and the glass transition point (Tg) was 59 ° C. Amorphous resin was obtained.

100 parts of the obtained crystalline resin and 400 parts of the amorphous resin were reacted at 200 ° C. for 2 hours under a nitrogen stream in a flask, and then reacted for another 2 hours under reduced pressure to obtain a weight average molecular weight (Mw). 490 parts of a block polymer having 23200, a number average molecular weight (Mn) of 11200, and a melting point (Tm) of 64 ° C. was obtained.

To 100 parts of the obtained block polymer, 0.5 part of soft sodium dodecylbenzenesulfonate was added as a surfactant, and 300 parts of ion-exchanged water was further added, and a homogenizer was added in a round glass flask while heating at 80 ° C. It was sufficiently mixed and dispersed with Ultratarax T50 (manufactured by IKA). After adjusting the pH in the system to 5.0 with a 0.5 mol / liter aqueous sodium hydroxide solution, heat to 90 ° C. while continuing stirring with a homogenizer to disperse a block polymer having a solid content of 20%. Got
The volume-based median diameter (D50) of the block polymer particles in the dispersion was 200 nm.

[Dispersion of amorphous polyester resin particles]
In a 10-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple, 500 parts by mass of bisphenol A propylene oxide 2 mol addition, 102 parts by mass of terephthalic acid, 72 parts by mass of fumaric acid, dodecenyl succinic acid An amorphous polyester resin was obtained by adding 59 parts by mass of an acid anhydride and 2 parts by mass of an esterification catalyst (tin octylate), carrying out a polycondensation reaction at 230 ° C. for 8 hours, and further reacting at 8 kPa for 1 hour. The glass transition point (Tg) of this amorphous polyester resin was 57 ° C., the softening point (Tsp) was 101 ° C., and the weight average molecular weight (Mw) was 26000.

Next, the 3 liter reaction tank with a jacket (manufactured by Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, a thermometer, a water dropping device, and an anchor blade was maintained at 40 ° C. in a water circulation type constant temperature bath. A mixed solvent of 160 parts by mass of ethyl acetate and 100 parts by mass of isopropyl alcohol was charged into the reaction vessel. Further, 300 parts by mass of the amorphous polyester resin was added, and the mixture was stirred by a three-one motor at 150 rpm and dissolved to obtain an oil phase. 14 parts by mass of a 10 mass% aqueous ammonia solution was added dropwise to the stirred oil phase in a dropping time of 5 minutes, and after mixing for 10 minutes, 900 parts by mass of ion-exchanged water was added dropwise at a rate of 7 parts by mass per minute. The phase was changed to obtain an emulsion.

Immediately, 800 parts by mass of the obtained emulsion and 700 parts by mass of ion-exchanged water were placed in a 2 liter eggplant flask and set in an evaporator (Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. .. While rotating the eggplant flask, it was heated in a hot water bath at 60 ° C., and the pressure was reduced to 7 kPa while paying attention to sudden boiling to remove the solvent. When the amount of solvent recovered reached 1100 parts by mass, the pressure was returned to normal pressure, and the eggplant flask was water-cooled to obtain a dispersion. The obtained dispersion had no solvent odor. The volume-based median diameter (D50) of the resin particles in this dispersion was 130 nm. Then, ion-exchanged water was added so that the solid content concentration became 20% by mass to obtain a dispersion of amorphous polyester resin particles.

[Dispersion of colorant particles]
90 parts by mass of sodium dodecyl sulfate was stirred and dissolved in 1600 parts by mass of ion-exchanged water, and 420 parts by mass of copper phthalocyanine was gradually added while stirring this solution.
Next, a dispersion of colorant particles was prepared by dispersion treatment using a stirrer Clairemix (manufactured by M Technique). The average particle size of the colorant particles in the dispersion was 110 nm in terms of volume-based median diameter.

[Toner (1)]
260 parts by mass of the dispersion liquid of the styrene / acrylic resin particles and 2000 parts by mass of ion-exchanged water were put into a reaction vessel equipped with a stirrer, a temperature sensor and a cooling tube. After adjusting the pH to 10 by adding a 5 mol / liter aqueous sodium hydroxide solution, 40 parts by mass of the dispersion of the colorant particles was added in terms of solid content. Next, an aqueous solution prepared by dissolving 60 parts by mass of magnesium chloride in 60 parts by mass of ion-exchanged water was added under stirring at 30 ° C. over 10 minutes. After leaving for 3 minutes, the temperature was started, and the temperature of this system was raised to 80 ° C. over 60 minutes. A dispersion prepared by mixing 20 parts by mass of a dispersion of crystalline polyester resin particles and 40 parts by mass of a block polymer particle dispersion in terms of solid content was added over 30 minutes and maintained at 80 ° C. The growth reaction of the core particles was continued.

In this state, the particle size of the core particles was measured with a Coulter Multisizer 3 (manufactured by Beckman Coulter), and when the volume-based median diameter (D50) reached 6.0 μm, the amorphous polyester resin particles became 40 parts by mass of the dispersion liquid in terms of solid content was added over 30 minutes to form a shell layer. When the supernatant of the reaction solution became transparent, an aqueous solution prepared by dissolving 190 parts by mass of sodium chloride in 760 parts by mass of ion-exchanged water was added to stop particle growth. After that, the temperature is raised and the particles are heated and stirred at 90 ° C. to advance the fusion of the particles, and the average circularity of the toner particles is measured using the measuring device FPIA-2100 (manufactured by Sysmex) (HPF detection number). Was measured as 4000 pieces), and when the average circularity reached 0.960, the mixture was cooled to 30 ° C. to obtain an aqueous dispersion of toner particles having a core-shell structure.

The obtained aqueous dispersion of toner particles is solid-liquid separated by a centrifuge to form a wet cake of toner particles, which is then ionized at 35 ° C. until the electrical conductivity of the filtrate reaches 5 μS / cm by the centrifuge. Washed with replacement water. After washing, it was transferred to a flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.) and dried until the water content became 0.5% by mass.
To the dried toner particles, add 1% by mass of hydrophobic silica (number average primary particle size = 12 nm) and 0.3% by mass of hydrophobic titania (number average primary particle size = 20 nm), and mix them with a Henschel mixer. To obtain the toner (1).

[Toner (2) to (17)]
In the production of the toner (1), the amount of the dispersion liquid added was adjusted, and as shown in Table 1 below, the amount of n-octyl mercaptan during the third stage polymerization, the content of the block polymer in the core particles, and the shell. Toners (2) to (17) are obtained in the same manner except that the content of the resin having a structure derived from dodecenyl succinic acid in the layer, the content of the resin in the shell layer in all the resins of the toner particles, etc. are changed. It was.

[Toner (18)]
The toner (18) was obtained in the same manner except that the dispersion liquid of the crystalline polyester resin particles was not added to the toner (1).

[Developers (1) to (18)]
By adding a ferrite carrier coated with a silicone resin and having a volume average particle size of 60 μm to each of the toners (1) to (18) so that the toner concentration becomes 6% by mass and mixing them, the developers (1) to (18) 18) was manufactured.

In Table 1 below, the weight average molecular weight (Mw) of the resin in the core particles is the dispersion of the core particles when the median diameter (D50) based on the volume of the particle size becomes 6.0 μm in the toner manufacturing process. The solution was measured as a sample. The weight average molecular weight (Mw) of the resin in the shell layer was measured using a dispersion of amorphous polyester resin particles as a sample.
Further, in Table 1 below, StAc represents styrene / acrylic. CPEs represent crystalline polyesters and APEs represent amorphous polyesters.

[Peak top molecular weight (Mp) of resin in toner]
The peak top molecular weight of the resin in each of the toners (1) to (18) was determined as follows.
A sample (toner) was added to tetrahydrofuran (THF) to a concentration of 1 mg / mL, dispersed at 40 ° C. for 15 minutes using an ultrasonic disperser, and then treated with a membrane filter having a pore size of 0.2 μm. , Sample solution was prepared. Using a GPC device HLC-8220GPC (manufactured by Tosoh) and a column TSKguard column + TSKgel SuperHZ-M triplet (manufactured by Tosoh), tetrahydrofuran was flowed as a carrier solvent at a flow rate of 0.2 mL / min while maintaining the column temperature at 40 ° C. did. 10 μL of the prepared sample solution was injected into the GPC device together with the carrier solvent, the sample was detected using a refractive index detector (RI detector), and a calibration line measured using monodisperse polystyrene standard particles was used. , The molecular weight distribution of the sample was calculated. The calibration curves have molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10, respectively. ^{5, 8.6 × 10 5, 2} × 10 6, by measuring the polystyrene standard particle of 10 is 4.48 × 10 ⁶ (Pressure Chemical Co.) was prepared.
In the calculated molecular weight distribution, the molecular weight corresponding to the peak top of the maximum peak having the largest peak area was defined as the peak top molecular weight (Mp).

[Light transmittance of toner layer]
As an image forming apparatus, on a commercially available copying machine bizhub PRO C6550 (manufactured by Konica Minolta), the side that is developed and transferred directly from the developing sleeve onto the glass substrate and is developed and transferred from the developing sleeve so that the thick glass substrate can pass through. The paper path was modified so that the distance to the glass substrate could be changed, and the glass substrate was not deformed. MICRO COVER GLASS, 18 mm x 18 mm, manufactured by Muto Kagaku Co., Ltd., which is equipped with developers (1) to (18) as developing agents and is in a normal temperature and humidity (temperature 20 ° C., humidity 50% RH) environment. A toner layer having a toner adhesion amount of 6.5 ± 0.1 g / m ² was formed on the layer. On this toner layer, an OK top coat 128 gsm (18 mm × 18 mm, thickness 100 ± 10 μm) having a hole of 6 mmφ in the center was placed. Place this cover glass on a hot plate heated to 50 ° C, and place an OIML type standard weight (cylindrical, 1 kg, M1 grade) heated to 185 ° C from above so as to cover all the holes in the OK top coat. After a second, the cover glass was immediately removed and allowed to cool to room temperature. Within 30 minutes after cooling, in a normal temperature and humidity (temperature 20 ° C., humidity 50% RH) environment, using an ultraviolet visible near infrared spectrophotometer UH4150 (manufactured by Hitachi), light with a wavelength of 670 nm in the toner layer The transmittance (%) was measured. The light transmittance of only the cover glass as a blank is measured in the same manner, and the ratio of the light transmittance (%) of the toner layer when the light transmittance of the cover glass is 100% is the light transmittance of the toner layer. Obtained as (%). The light transmittance (%) of the toner layers of the toners (1) to (18) at 670 nm is shown in Table 2 below.
Further, in the same manner as described above, the transmittance (%) of light having a wavelength of 490 nm in the toner layer was measured. The light transmittance of only the cover glass as a blank is measured in the same manner, and the ratio of the light transmittance (%) of the toner layer when the light transmittance of the cover glass is 100% is the light transmittance of the toner layer. Obtained as (%). The light transmittance (%) of the toner layers of the toners (1) to (18) at 490 nm is shown in Table 2 below.
Further, the difference between the transmittance of light having a wavelength of 490 nm and the transmittance of light having a wavelength of 670 nm was determined and shown in Table 2 below.

[Evaluation]
The following evaluations were performed using the toner and developer obtained above, and the results are shown in Table 2.

[Low temperature fixability]
A commercially available color copier, bizhub PRO C6500 (manufactured by Konica Minolta), was modified so that the fixing temperature, toner adhesion amount, and system speed could be set freely. Each developer was sequentially loaded into this modified machine, and a fixing test was conducted in an environment of normal temperature and humidity (temperature 20 ° C., humidity 50% RH). Specifically, in the remodeling machine, a solid image with a toner adhesion amount of 11.3 g / m ² is formed on NPi woodfree paper 128 g / m ² (manufactured by Nippon Paper Industries), and the fixing belt is within the range of 150 to 200 ° C. The temperature was changed every 5 ° C., the lower fixing roller was set 20 ° C. lower than the fixing upper belt, and the fixing treatment was performed at a fixing speed of 300 mm / sec. Among the temperatures of the fixing upper belt in which the cold offset did not occur, the lowest temperature was determined as the fixing lower limit temperature.
The lower the lower limit temperature for fixing, the better the low temperature fixability. Therefore, the low temperature fixability was ranked as follows from the lower limit temperature for fixing. If the fixing lower limit temperature is less than 165 ° C., there is no practical problem and it is judged to pass.
⊚: Lower limit temperature for fixing is less than 150 ° C ○: Lower limit temperature for fixing is 150 ° C or higher and less than 165 ° C ×: Lower limit temperature for fixing is 165 ° C or higher

[Uneven density and uneven gloss]
In the commercially available color multifunction device bizhub PRESS C1100 (manufactured by Konica Minolta), the fixing device is changed so that the surface temperature of the fixing upper belt is in the range of 140 to 220 ° C and the surface temperature of the fixing lower roller is changed in the range of 120 to 200 ° C. Modified so that it can be done. Each developer is sequentially loaded into this modified machine, and the amount of toner adhered to rough paper Hammermill tidal (manufactured by Hammermill) is 8.0 g / m under normal temperature and humidity (temperature 20 ° C, humidity 50% RH). A solid image of ² was formed and fixed. The fixing speed during the fixing process was 460 mm / sec, and the fixing temperature (surface temperature of the fixing belt) was the under-offset temperature + 15 ° C.
The density unevenness and glossy unevenness of the obtained solid image were visually evaluated for rank as follows.
⊚: No density unevenness or gloss unevenness is confirmed ○: Density unevenness or gloss unevenness is slightly confirmed, but there is no problem in quality ×: Density unevenness or gloss unevenness is confirmed and is not practical

[Reflection density]
Using the Macbeth reflection densitometer "RD-918", a toner layer is formed on the cover glass (MICRO COVER GLASS, 18 mm x 18 mm, manufactured by Muto Chemical Co., Ltd.) in the same manner as in the above measurement of the light transmittance, and the toner layer is formed on the toner layer. 128 gsm of OK top coat was placed on the surface, and the reflection density of the toner layer was measured. If the reflection density is 2.00 or more, there is no practical problem and it is judged to pass. The reflection density corresponds to the difference in light transmittance between the wavelength of 490 nm and the wavelength of 670 nm, and when the difference in light transmittance is large, the coloring power becomes large and the reflection density becomes large.

From the results shown in Table 2, when the toner of the present invention was used, there was less density unevenness and gloss unevenness in the image, excellent low-temperature fixability, and reflection density as compared with the case where the toner of the comparative example was used. Was big.

100 Toner 100a Toner Layer 201 Convex 202 Concave B Fixing Belt

Claims (12)

A toner for developing an electrostatic charge image, which is composed of toner particles containing at least an amorphous resin, a crystalline resin, and a colorant.
After forming a toner layer having an adhesion amount of 6.5 g / m ² of the toner for static charge image development on glass and applying heat at 185 ° C. for 5 seconds from a position where the distance from the surface of the toner layer is 100 μm. When the light transmittance of the toner layer is measured,
The light transmittance of 490nm wavelength is in the range of 80-90%, and the transmittance of the light having the wavelength of 670nm is Ri near the range of 0%
The toner particles include core particles and a shell layer that covers the surface of the core particles to form a core-shell structure.
The core particles contain a styrene / acrylic resin as the amorphous resin, a crystalline polyester resin as the crystalline resin, and a block polymer.
Wherein the shell layer is, the amorphous resin as amorphous polyester resin containing to toner for developing electrostatic images, wherein Rukoto. The toner for static charge image development according to claim 1, wherein the peak top molecular weight of the resin in the toner particles is in the range of 14000 to 21000. The toner for static charge image development according to claim 1 or 2 , wherein the melting point of the crystalline resin is in the range of 65 to 85 ° C. The toner for static charge image development according to any one of claims 1 to 3 , wherein the content of the block polymer in the toner particles is in the range of 1 to 20% by mass. The toner for developing an electrostatic charge image according to any one of claims 1 to 4 , wherein the block polymer has a crystalline portion and an amorphous portion. The weight average molecular weight of the crystal portion is in the range of 1000 to 3000.
The toner for developing an electrostatic charge image according to claim 5 , wherein the weight average molecular weight of the amorphous portion is in the range of 1000 to 40,000. The toner for static charge image development according to claim 5 or 6 , wherein the crystal portion is a resin portion having a structure derived from a crystalline polyester resin. The toner for electrostatic charge image development according to any one of claims 1 to 7 , wherein the toner particles contain a polyester resin having a structure derived from dodecenyl succinic acid as a binder resin. Before SL content of the styrene-acrylic resin in the toner particles, toner according to any one of claims 1 to 8, characterized in that at least 5% by mass. The toner for static charge image development according to any one of claims 1 to 9 , wherein the shell layer contains a polyester resin having a structure derived from dodecenyl succinic acid. The content of structural from said dodecenylsuccinic acid resin, wherein the shell layer contains the electrostatic image developing toner according to claim 10, characterized in that in the range of 3 to 13 mass%. The toner for developing an electrostatic charge image according to any one of claims 1 to 11 , wherein the toner is a cyan toner.

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