JP2013167822A - Toner for electrostatic charge image development and manufacturing method of the same, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development capable of suppressing a change in image density due to a variation in environment.SOLUTION: A toner for electrostatic charge image development includes toner particles that contain an amorphous polyester resin having an unsaturated polyester component, and have a surface layer part containing a cross-linked material of the unsaturated polyester component and a fluorine-based monomer.

Description

  The present invention relates to a toner for developing an electrostatic image and a method for producing the same, an electrostatic image developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method.

  In recent years, image forming apparatuses such as printers and copiers have been widely used, and technologies relating to various elements constituting the image forming apparatus have also been widely used. Among image forming apparatuses that employ an electrophotographic method, a photosensitive member such as a photosensitive member (image holding member) is charged using a charging device, and an ambient potential is applied to the charged photosensitive member. In many cases, an electrostatic latent image having a different potential is formed to form a pattern to be printed. The electrostatic latent image formed in this way is developed with a developer containing toner, and then the final image is formed. Thus, the toner image is transferred onto a transfer medium such as a recording sheet.

For example, Patent Document 1 discloses a toner having a core-shell structure in which a core layer is provided with a shell layer made of particles of a low surface energy resin containing fluorine atoms.
Patent Document 2 discloses a toner obtained by treating the surface of a toner particle of a polyester resin with a fluorine-containing compound.

JP 2005-274615 A JP 2006-145561 A

  An object of the present invention is to provide an electrostatic charge image developing toner capable of suppressing a change in image density due to environmental fluctuations.

The above problem is solved by the following means. That is,
The invention according to claim 1
An electrostatic charge image developing toner comprising toner particles comprising an amorphous polyester resin having an unsaturated polyester component and having a surface layer portion containing a crosslinked product of the unsaturated polyester component and a fluorine monomer. .

The invention according to claim 2
2. The electrostatic image developing toner according to claim 1, wherein a ratio F / C of fluorine atoms to carbon atoms in a surface layer portion of the toner particles is 0.01 or more and 0.15 or less.

The invention according to claim 3
The said fluorine-type monomer is at least 1 sort (s) selected from the monomer which has a chain functional group which contains a fluorine atom and is C1-C10. This is a toner for developing an electrostatic image.

The invention according to claim 4
4. The electrostatic charge image developing toner according to claim 1, wherein the toner particles have a tetrahydrofuran (THF) insoluble content of 4.0% by mass or less. 5.

The invention according to claim 5
The electrostatic image development according to any one of claims 1 to 4, wherein the unsaturated polyester component is a component derived from at least one selected from fumaric acid, maleic acid, and maleic anhydride. Toner.

The invention according to claim 6
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1.

The invention according to claim 7 provides:
Containing the toner for developing an electrostatic charge image according to any one of claims 1 to 5,
The toner cartridge is detachable from the image forming apparatus.

The invention according to claim 8 provides:
A developing means for accommodating the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the image holding member as a toner image by the electrostatic charge image developer,
It is a process cartridge that can be attached to and detached from the image forming apparatus.

The invention according to claim 9 is:
An image carrier,
Charging means for charging the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the image carrier onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer medium;
An image forming apparatus.

The invention according to claim 10 is:
A charging step for charging the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing the electrostatic image formed on the image carrier as a toner image by the electrostatic image developer according to claim 6;
A transfer step of transferring a toner image formed on the image carrier onto a transfer target;
A fixing step of fixing the toner image transferred onto the transfer medium;
Is an image forming method.

The invention according to claim 11 is:
Preparing at least a resin particle dispersion in which resin particles are dispersed, aggregating at least resin particles to form first aggregated particles;
A first aggregated particle dispersion in which the first aggregated particles are dispersed and a polyester resin particle dispersion in which amorphous polyester resin particles having an unsaturated polyester component are dispersed are mixed, and the first aggregated particles are mixed. A step of aggregating the amorphous polyester resin particles to adhere to the surface thereof to form second agglomerated particles;
Heating the second aggregated particle dispersion in which the second aggregated particles are dispersed, fusing and coalescing the second aggregated particles to form toner particles;
A vinyl monomer and a polymerization initiator are added to the toner particle dispersion in which the toner particles are dispersed, and the unsaturated polyester component of the amorphous polyester resin and the vinyl present in the surface layer portion of the toner particles. Cross-linking with a monomer, and forming a cross-linked product by the cross-linking on the surface layer of the toner particles;
A method for producing a toner for developing an electrostatic image having

According to the first aspect of the present invention, compared to a case where the surface layer portion of the toner particles does not contain a cross-linked product of the unsaturated polyester component and the fluorine-based monomer, it is possible to suppress a change in image density due to environmental fluctuations. A toner for developing a charge image can be provided.
According to the second aspect of the invention, compared to the case where the amount of fluorine atoms in the surface layer portion of the toner particles is out of the specified range, the electrostatic charge image developing that can effectively suppress the change in image density due to environmental fluctuations. Toner can be provided.
According to the invention of claim 3, the image density due to environmental fluctuations is higher than when the fluorine-based monomer is not a monomer having a chain functional group containing a fluorine atom and having 1 to 10 carbon atoms. It is possible to provide a toner for developing an electrostatic image capable of effectively suppressing the change.
According to the fourth aspect of the present invention, it is possible to provide a toner for developing an electrostatic charge image that can effectively suppress a change in image density due to environmental fluctuations, as compared with a case where the THF insoluble content of the toner particles is outside the specified range.
According to the invention of claim 5, the change in image density due to environmental fluctuations compared to the case where the unsaturated polyester component of the amorphous polyester resin is a component not derived from fumaric acid, maleic acid, or maleic anhydride. It is possible to provide a toner for developing an electrostatic image that can effectively suppress the above.

  According to the inventions according to claims 6 to 10, the toner for developing an electrostatic charge image, wherein the surface layer portion of the toner particles does not contain a cross-linked product of the unsaturated polyester component of the amorphous polyester resin and the fluorine monomer. As compared with the case where the toner is applied, it is possible to provide an electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method that can suppress a change in image density due to environmental fluctuations.

  According to the invention of claim 11, compared with the case where the unsaturated polyester component of the toner particles and the fluorine-based monomer are cross-linked, and there is no step of forming a cross-linked product by cross-linking in the surface layer portion of the toner particles, It is possible to provide a method for producing an electrostatic image developing toner that obtains an electrostatic image developing toner capable of suppressing changes in image density due to environmental fluctuations.

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 which concerns on this embodiment.

  Embodiments of the present invention will be described in detail below with respect to an electrostatic charge image developing toner and a method for producing the same, an electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method of the present invention. .

<Toner for electrostatic image development>
The electrostatic image developing toner according to the exemplary embodiment (hereinafter, also referred to as “toner”) includes an amorphous polyester resin having an unsaturated polyester component.
The surface layer portion of the toner particles includes a crosslinked product of the unsaturated polyester component of the amorphous polyester resin and the fluorine monomer.

In image formation under an environment where the humidity and / or temperature fluctuates, particularly in the case where image formation under low temperature and low humidity is performed after low toner density image formation under high temperature and high humidity. The toner charge amount may become non-uniform.
In other words, under such environmental fluctuations as described above, a large difference in charge amount occurs between the toner supplied from the cartridge and the toner remaining in the apparatus in the developing device, and as a result, the toner The fluidity of the toner deteriorates and adheres to, for example, a toner density control sensor in the apparatus, so that the control of the image density by the toner may become unstable.
On the other hand, the surface layer of toner particles has heretofore been used in order to suppress variations in the charge amount between the toner supplied from the cartridge and the toner existing in the apparatus and the deterioration of the toner fluidity in the developing apparatus. A method of containing a fluorine atom in the part is known.
However, in the image formation under an environment where the fluorine atom in the surface layer portion contains a large difference (contained form) and the humidity and / or temperature fluctuates significantly, the charge amount of the toner in the developing device becomes uneven. It has been difficult to suppress instability of image density control due to the above.
In addition, even when image formation is performed in a state where the environment has changed from low temperature and low humidity to high temperature and high humidity, the same charge amount non-uniformity is likely to occur. In some cases, the background portion (non-image portion) of the image is fogged.

Therefore, in the toner according to the present exemplary embodiment, the surface layer portion of the toner particles includes a cross-linked product of the unsaturated polyester component of the amorphous polyester resin and the fluorine-based monomer. It came to solve.
When the surface layer portion of the toner particle contains fluorine atoms, the negatively charged charge density on the surface of the toner particle can be made uniform and the surface energy of the toner particle can be reduced. In particular, the fluorine atom in the surface layer is included as a cross-linked product with the amorphous polyester resin that constitutes the toner particles, thereby facilitating charge dissipation from the toner particle surface to some extent and maintaining an appropriate surface charge. Is considered possible.
For these reasons, even when the toner according to the present embodiment is applied to image formation under an environment where the humidity and / or temperature fluctuates significantly, there is a large change in the charge amount of the toner in the developing device. It is unlikely to occur, and it is considered that adhesion to the toner concentration control sensor in the apparatus is also suppressed.
Therefore, the toner according to the present embodiment can suppress the change in the image density due to the environmental change by adopting the above configuration. In particular, the toner according to the present exemplary embodiment is suitable as a toner capable of suppressing a change in image density when an image is formed under low temperature and low humidity after forming an image with low toner density under high temperature and high humidity. .

[Configuration of toner]
The configuration of the toner according to the exemplary embodiment will be described in detail.
The toner according to the exemplary embodiment includes toner particles, and further includes an external additive as necessary.

(Toner particles)
First, toner particles will be described.
The toner particles include an amorphous polyester resin having an unsaturated polyester component as a binder resin, and, if necessary, a colorant, a release agent, and other additives (internal additives). Composed.

The toner particles have a surface layer portion containing a crosslinked product of an unsaturated polyester component of an amorphous polyester resin and a fluorine monomer.
In other words, the toner particles are, for example, those obtained by cross-linking the unsaturated polyester component of the amorphous polyester resin exposed on the surface of the toner particles and the fluorine-based monomer.
Here, the surface layer portion of the toner particles refers to a surface region having a depth of about 50 nm from the surface of the toner particles.

For this reason, the toner particles are considered that all or part of the surface layer portion is composed of a film of a crosslinked product of an unsaturated polyester component of an amorphous polyester resin and a fluorine-based monomer.
Specifically, for example, the toner particles are considered to have a structure in which a surface layer portion is covered with a film of a crosslinked product.

-Surface layer of toner particles-
In this embodiment, in order to more effectively suppress changes in image density due to environmental fluctuations, the ratio F / C of fluorine atoms to carbon atoms in the surface layer portion is 0.01 or more and 0.15 or less (more Preferably, it is 0.02 or more and 0.07 or less.
When the abundance of fluorine atoms in the surface layer portion is in the above range, changes in image density due to environmental fluctuations can be more effectively suppressed.
However, when F / C is more than 0.15, the influence of the amount of fluorine charge is large and the charge becomes extremely small. For example, when F / C changes from a low temperature and low humidity environment to a high temperature and high humidity environment, In some cases, the toner adheres to the background portion of the image.

The measurement of the ratio F / C of fluorine atoms and carbon atoms in the surface layer part is obtained by XPS (photoelectron spectrometer).
The sample was 0.2 g of toner, JPS-9000MX manufactured by JEOL Ltd. was used as the XPS measurement apparatus, the X-ray source was MgKα, the acceleration voltage was 10.0 kV, and the emission current was 20 mA. Under this condition, the ratio F / C of fluorine atoms and carbon atoms in the surface layer portion (about 5 nm) of the toner particles is confirmed.

-THF insoluble matter in toner particles-
The cross-linked product constituting the surface layer portion of the toner particles is a reaction product of the unsaturated polyester component of the amorphous polyester resin and the fluorine monomer, and becomes a tetrahydrofuran (THF) insoluble content of the toner particles.
The toner insoluble content of the toner particles is, for example, 4.0% by mass or less, and desirably 0.15% by mass to 3.5% by mass.

In this embodiment, the fluorine atoms in the surface layer portion of the toner particles are contained as a cross-linked product with the amorphous polyester resin, so that the effect of suppressing the change in image density as described above can be achieved.
Therefore, the THF-insoluble content of the toner particles is in the above range, so that the fluorine-based monomer is not left unreacted in the surface layer portion, and the fluorine atom is crosslinked with the amorphous polyester resin. It shows that it is included as a thing.

Here, the THF insoluble content of the toner particles was measured as in the following (1) to (8).
(1) 0.2 g to 0.3 g of toner particles are directly weighed into a 25 ml Erlenmeyer flask, sealed with 20 ml of THF, and allowed to stand for 24 hours.
(2) Transfer (1) to a glass tube for centrifugation.
(3) 20 ml of THF is again added to (1), the Erlenmeyer flask is washed, transferred to the glass tube of (2), and sealed.
(4) Centrifuge (3) for 30 minutes under the conditions of 20,000 rpm and -10 ° C.
(5) Take out (4) and leave it until it reaches room temperature.
(6) 5 ml of the supernatant of (5) is weighed, taken out into an aluminum pan whose mass has been measured, and the aluminum pan is heated on a pot plate to evaporate THF.
(7) (6) is dried in a vacuum dryer at 50 ° C. for 24 hours, and this is weighed together with the mass of the aluminum dish as THF-insoluble matter in 5 ml.
(8) The THF insoluble matter is calculated according to the following formula.
Formula: {toner particle sample amount − [(THF dissolved component and aluminum dish mass) −aluminum dish mass] × (40 ÷ 5)} ÷ toner particle sample amount × 100 = THF insoluble content (mass%)

-Amorphous polyester resin with unsaturated polyester component-
Next, an amorphous polyester resin having an unsaturated polyester component that is one of binder resins (hereinafter, sometimes referred to as “amorphous unsaturated polyester resin”) will be described.
In addition to the amorphous unsaturated polyester resin, the binder resin may be used in combination with other binder resins such as a crystalline polyester resin.

Here, the amorphous resin (amorphous polyester resin) is not a clear endothermic peak but only a stepwise endothermic change in thermal analysis measurement using differential scanning calorimetry (DSC). , A solid at room temperature, which is thermoplasticized at a temperature above the glass transition temperature. On the other hand, the crystalline resin (crystalline polyester resin) refers to a resin having a clear endothermic peak instead of a stepwise endothermic amount change in differential scanning calorimetry (DSC).
Specifically, for example. The crystalline resin (crystalline polyester resin) means that the half-value width of the endothermic peak when measured at a temperature rising rate of 10 ° C./min is within 10 ° C., and the amorphous resin (amorphous polyester resin) ) Means a resin having a full width at half maximum exceeding 10 ° C. or a resin in which no clear endothermic peak is observed.

The amorphous unsaturated polyester resin will be described.
The amorphous unsaturated polyester resin is an amorphous polyester resin having an unsaturated group (for example, vinyl group) as an unsaturated polyester component.
Specifically, for example, the amorphous unsaturated polyester resin is a polycondensation product of a polyvalent carboxylic acid and a polyhydric alcohol, and an unsaturated polyester component is used as at least one of the polyvalent carboxylic acid and the polyhydric alcohol. It is preferable to use a monomer having an unsaturated group (for example, a vinyl group or an acetylene group).
In particular, from the viewpoint of stability, the amorphous unsaturated polyester resin is preferably a polycondensation product of a polyvalent carboxylic acid having an unsaturated group (for example, a vinyl group) and a polyhydric alcohol. The amorphous unsaturated polyester resin is often a polycondensation product of a divalent carboxylic acid having an unsaturated group (for example, a vinyl group) and a divalent alcohol (that is, a linear polyester). Resin).

Examples of the divalent carboxylic acid having an unsaturated group include fumaric acid, maleic acid, maleic anhydride, citraconic acid, mesaconic acid, itaconic acid, glutaconic acid, allylmalonic acid, isopropylidene succinic acid, acetylenedicarboxylic acid, These lower (1 to 4 carbon atoms) alkyl esters are mentioned.
Examples of the trivalent or higher carboxylic acid having an unsaturated group include aconitic acid, 3-butene-1,2,3-tricarboxylic acid, 4-pentene-1,2,4, -tricarboxylic acid, 1-pentene-1, 1,4,4, -tetracarboxylic acid, and lower (1 to 4 carbon atoms) alkyl esters thereof.
These polyvalent carboxylic acids may be used alone or in combination of two or more.

Examples of the divalent alcohol include bisphenol A, hydrogenated bisphenol A, ethylene oxide and / or propylene oxide adduct of bisphenol A, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, propylene Examples include glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and neopentyl glycol.
Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like.
In addition to polyhydric alcohols, monovalent acids such as acetic acid and benzoic acid, and monohydric alcohols such as cyclohexanol and benzyl alcohol are also used together for the purpose of adjusting the acid value and hydroxyl value, if necessary. May be.
These polyhydric alcohols may be used alone or in combination of two or more.

Among the amorphous unsaturated polyester resins that are condensation polymers of these polycarboxylic acids and polyhydric alcohols, in particular, at least one divalent selected from fumaric acid, maleic acid, and maleic anhydride A polycondensation product of a carboxylic acid and a divalent alcohol is preferable.
That is, the unsaturated polyester component of the amorphous unsaturated polyester resin is a component derived from at least one divalent carboxylic acid selected from fumaric acid, maleic acid, and maleic anhydride from the viewpoint of crosslinking formation. It is preferable that fumaric acid and maleic acid are more effective against fogging from the viewpoint of a small change in the amount of charge accompanying an environmental change.

  The method for producing the amorphous unsaturated polyester resin is not particularly limited, and is produced by a general polyester polymerization method in which a polycarboxylic acid and a polyhydric alcohol are reacted. For example, direct polycondensation, transesterification method, etc. These are manufactured separately depending on the type of monomer.

The weight average molecular weight (Mw) of the amorphous unsaturated polyester resin is, for example, preferably from 30,000 to 300,000, preferably from 30,000 to 200,000, more preferably from 35,000 to 150. , 000 or less.
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 and the number average molecular weight are calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from this measurement result. The same applies hereinafter.

The glass transition temperature (Tg) of the amorphous unsaturated polyester resin is, for example, preferably from 50 ° C. to 80 ° C., and more preferably from 50 ° C. to 65 ° C.
The glass transition temperature is a value obtained as the peak temperature of the endothermic peak obtained by differential scanning calorimetry (DSC). The same applies hereinafter.

  The content of the amorphous unsaturated polyester resin is preferably 40% by mass or more and 95% by mass or less, preferably 50% by mass or more and 90% by mass or less, and more preferably 60% by mass with respect to the toner particles. It is not less than 85% by mass.

-Other binder resins-
Next, other binder resins that can be used in combination with the amorphous unsaturated polyester resin will be described.
As another binder resin, a crystalline polyester resin is preferably exemplified as a representative.

  Examples of the crystalline polyester resin include condensation polymers of polyvalent carboxylic acids and polyhydric alcohols.

Examples of the divalent carboxylic acid 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 specific aromatic carboxylic acids such as 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like. These anhydrides and their lower (1 to 3 carbon atoms) alkyl esters are exemplified.
Moreover, as polyvalent carboxylic acid, you may use together dicarboxylic acid which has a sulfonic acid group other than the said aliphatic carboxylic acid and aromatic carboxylic acid.
Furthermore, as the polyvalent carboxylic acid, in addition to the aliphatic carboxylic acid and the aromatic carboxylic acid, a dicarboxylic acid having a double bond may be used in combination.
These polyvalent carboxylic acids may be used alone or in combination of two or more.

  As the polyhydric alcohol, an aliphatic diol is desirable, and a linear aliphatic diol having a main chain portion having 7 to 20 carbon atoms is more desirable. When the aliphatic diol is branched, the crystallinity of the polyester resin is lowered and the melting temperature may be lowered. Further, when the main chain portion has less than 7 carbon atoms, when the polycondensation with the aromatic dicarboxylic acid is performed, the melting temperature becomes high and low temperature fixing may be difficult. On the other hand, when the number of carbons in the main chain portion exceeds 20, it is 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 include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol 1,18-octadecanediol, 1,14-eicosandecanediol and the like, but are not limited thereto. 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 polyhydric alcohols, the amount of aliphatic diol used is desirably 80 mol% or more, and more desirably 90 mol% or more.
When the amount of the aliphatic diol used is too low, the crystallinity of the crystalline polyester resin is lowered and the melting temperature may be lowered.

  The method for producing the crystalline polyester resin is not particularly limited, and is produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. Produced separately for different types.

If necessary, a polycarboxylic acid or a polyhydric alcohol may be further added at the final stage of the synthesis for the purpose of adjusting the acid value or the hydroxyl value.
Examples of the polyvalent carboxylic acid include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid; maleic anhydride, fumaric acid, succinic acid, Aliphatic carboxylic acids such as alkenyl succinic anhydride and adipic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid; 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4 -Aromatic carboxylic acids having at least three carboxyl groups in one molecule such as naphthalene tricarboxylic acid.
Examples of the polyhydric alcohol include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentylglycol, glycerin; cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A And aromatic diols such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct.

  The weight average molecular weight (Mw) of the crystalline polyester resin is preferably, for example, 6,000 or more and 35,000 or less.

The melting temperature of the crystalline polyester resin is, for example, preferably from 50 ° C. to 100 ° C., and preferably from 60 ° C. to 80 ° C.
In addition, melting temperature is the value calculated | required as the peak temperature of the endothermic peak obtained by the said differential scanning calorimetry (DSC). The crystalline polyester resin may show a plurality of melting peaks, but in the present embodiment, the maximum peak is regarded as the melting temperature.

  The content of the crystalline polyester resin is, for example, in the range of 3% by mass to 20% by mass with respect to the toner particles, preferably 5% by mass to 18% by mass, and more preferably 7% by mass. It is 16 mass% or less.

On the other hand, as other binder resins other than the crystalline polyester resin, other crystalline resins (crystalline vinyl resins), other amorphous resins (for example, styrene / acrylic resins, epoxy resins, polyester resins, Polyurethane resins, polyamide resins, cellulose resins, polyether resins, polyolefin resins, and the like).
These other binder resins are blended in a range that does not affect the toner characteristics.

-Fluoromonomer-
Next, a fluorine-type monomer is demonstrated.
Here, the fluorine-based monomer only needs to have a fluorine atom and an unsaturated group capable of reacting with the unsaturated polyester component of the amorphous unsaturated polyester resin in the molecule, and more specifically. Specifically, it may be configured to include a functional group containing a fluorine atom and an unsaturated group.
The functional group containing a fluorine atom constituting the fluorine-based monomer is a chain functional group containing a fluorine atom so as not to inhibit the reactivity of the amorphous unsaturated polyester resin with the unsaturated polyester component. In particular, it is preferably a chain functional group containing a fluorine atom and having 1 to 10 carbon atoms, and a chain alkyl group having 3 to 8 carbon atoms in which a hydrogen atom is substituted by a fluorine atom. Most preferably it is. When it has a chain functional group containing a fluorine atom and having 10 or more carbon atoms, the reaction may not easily proceed, and as a result, fog may easily occur. When the chain functional group is smaller, it becomes difficult to control the reaction on the surface of the toner particles, and as a result, the change in the charge amount when the environment changes becomes large, and fogging may occur.
In addition, examples of the unsaturated group constituting the fluorine-based monomer include a vinyl group, an acryloyl group, a methacryloyl group, an acetylene group, and the like, and among them, a vinyl group and a methacryloyl group are preferable.

Specific examples of the fluorine-based monomer include methacrylic acid 1H, 1H, 5H-octafluoropentyl (5), methacrylic acid 1,1,1,3,3,3-hexafluoroisopropyl (3), 2- ( (Trifluoromethyl) acrylic acid (1), 2,2,2-trifluoroethyl methacrylate (2), 2,2,3,3,3-pentafluoropropyl methacrylate (3), 2,2, methacrylate 3,4,4,4-hexafluorobutyl (4), methacrylic acid 3,3,4,4,5,5,6,6,6-nonafluorohexyl (6), methacrylic acid 3,3,4, 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (8), methacrylic acid 1H, 1H, 9H-hexadecafluorononyl (9), acrylic acid 1H, 1H, 2H, 2H-Heptadecafluo Decyl (10), methacrylic acid 2- (Henny Cosa fluoro decyl) ethyl (12) and the like (The numerical values in parentheses indicate the number of carbon atoms in the chain functional group).
Among these, from the viewpoint of reactivity with the unsaturated polyester component, methacrylic acid 1H, 1H, 5H-octafluoropentyl (5), methacrylic acid 1,1,1,3,3,3-hexafluoroisopropyl (3 ), 2,2,3,3,3-pentafluoropropyl methacrylate (3), 2,2,3,4,4,4-hexafluorobutyl (4) methacrylate, 3,3,4, methacrylate 4,5,5,6,6,6-nonafluorohexyl (6), methacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro Octyl (8) is preferred.

  These fluorine-based monomers are appropriately selected and used depending on the amount of unsaturated polyester component (the amount of unsaturated groups) contained in the toner particles and the preferable amount of fluorine atoms in the surface layer portion. That's fine.

-Colorant-
Next, the colorant contained in the toner particles will be described.
The colorant is not particularly limited as long as it is a known colorant. For example, carbon black such as furnace black, channel black, acetylene black, and thermal black, inorganic pigments such as bengara, bitumen, and titanium oxide, fast yellow, disazo Azo pigments such as yellow, pyrazolone red, chelate red, brilliant carmine, para brown, phthalocyanine pigments such as copper phthalocyanine, metal-free phthalocyanine, flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red, dioxazine violet Examples thereof include cyclic pigments.

  As the colorant, a surface-treated colorant may be used as necessary, or it may be used in combination with a dispersant. A plurality of colorants may be used in combination.

  As content of a coloring agent, the range of 1 to 30 mass parts is desirable with respect to 100 mass parts of binder resin.

-Release agent-
The release agent contained in the toner particles will be described.
Examples of mold release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; ester types such as fatty acid esters and montanic acid esters. Wax; and the like, but is not limited thereto.

  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. Further, from the viewpoint of offset resistance, the temperature is desirably 110 ° C. or less, and more desirably 100 ° C. or less.

  As content of a mold release agent, the range of 2 to 30 mass parts is desirable with respect to 100 mass parts of binder resin, for example.

-Other additives-
Other additives contained in the toner particles will be described.
Examples of other additives include magnetic substances, charge control agents, inorganic powders, and the like.
These are internal additives added to the inside of the toner particles.

-Toner particle characteristics-
Subsequently, the characteristics of the toner particles will be described.
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure including a core (core particle) and a coating layer (shell layer) covering the core. May be.
In the case of toner particles having a core / shell structure, the coating layer (shell layer) includes an amorphous unsaturated polyester resin, while the core body (core particles), together with the binder resin, is optionally used. And a colorant, a release agent, and other additives.
The binder resin constituting the core (core particle) is not necessarily an amorphous unsaturated polyester resin, and other binder resins may be applied alone. A crystalline unsaturated polyester resin and a crystalline resin (preferably a crystalline polyester resin) are preferably used in combination.

The toner particles have an internal glass transition temperature (other than the surface layer portion) of the surface layer portion (portion formed by including a crosslinked product of the unsaturated polyester component of the amorphous unsaturated polyester resin and the fluorine monomer). It is preferable that the glass transition temperature is higher than the glass transition temperature.
As a result, improvement in glossiness of the fixed image (that is, suppression of aggregation of toner particles in the toner image) and low temperature fixability are realized.

The toner particles preferably have two or more endothermic peaks at 60 ° C. or more and 90 ° C. or less in a DSC curve measured by a differential scanning calorimeter (DSC).
In other words, the toner particles may include a crystalline resin (preferably a crystalline polyester resin) and a release agent together with the amorphous unsaturated polyester resin, and the two or more endothermic peaks. Corresponds to an endothermic peak derived from the crystalline resin and the release agent.
Thereby, both the low-temperature fixability of the toner and the releasability of the toner are realized.

The volume average particle diameter of the toner particles is, for example, 2.0 μm or more and 10 μm or less, and desirably 3.0 μm or more and 8.0 μm or less.
As a method for measuring the volume average particle diameter of the toner particles, 0.5 mg to 50 mg of a measurement sample is added to 2 ml of a 5% by weight aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant. The electrolyte was added to 100 ml to 150 ml. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the above-mentioned Coulter Multisizer II type (manufactured by Beckman-Coulter) is used to produce particles using an aperture having an aperture diameter of 100 μm. The particle size distribution of particles having a diameter in the range of 2.0 μm to 60 μm is measured. The number of particles to be measured is 50,000.
For the particle size range (channel) obtained by dividing the obtained particle size distribution, the volume cumulative distribution is subtracted from the small particle size side, and the particle size that becomes 50% cumulative is defined as the volume average particle size D50v.

(External additive)
The toner according to the exemplary embodiment may include an external additive.
Examples of the external additive include inorganic particles. Examples of the inorganic particles include SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, and CaO. , K ₂ O, Na ₂ O, ZrO ₂ , CaO.SiO ₂ , K ₂ O. (TiO ₂ ) _n , Al ₂ O ₃ .2SiO ₂ , CaCO ₃ , MgCO ₃ , BaSO ₄ , MgSO _{4 and the} like. .

The surface of the external additive may be hydrophobized in advance. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually about 1 part by mass or more and about 10 parts by mass with respect to 100 parts by mass of the inorganic particles, for example.

  The external addition amount of the external additive is preferably 0.5 parts by mass or more and 2.5 parts by mass or less with respect to 100 parts by mass of the toner particles.

(Toner production method)
A toner manufacturing method according to this embodiment will be described.
First, toner particles may be produced by a dry process (for example, a kneading and pulverization method), a wet process (for example, an aggregation coalescence method, a suspension polymerization method, a solution suspension granulation method, a solution suspension method, a solution emulsion aggregation method, or the like. ). There is no restriction | limiting in particular in these manufacturing methods, A well-known manufacturing method is employ | adopted.
Then, the unsaturated polyester component of the amorphous unsaturated polyester resin present in the surface layer portion of the obtained toner particles is cross-linked to form a cross-linked product by cross-linking in the surface layer portion of the toner particles.

Specifically, for example, when toner particles are produced by an aggregation coalescence method,
Preparing at least a resin particle dispersion in which resin particles are dispersed, aggregating at least resin particles to form first aggregated particles (first aggregation step);
The first aggregated particle dispersion in which the first aggregated particles are dispersed and the amorphous unsaturated polyester resin particle dispersion in which the amorphous unsaturated polyester resin particles are dispersed are mixed, and the surface of the first aggregated particles A process of agglomerating the amorphous unsaturated polyester resin particles to form second aggregated particles (second aggregating process);
Heating the second agglomerated particle dispersion in which the second agglomerated particles are dispersed, fusing and coalescing the second agglomerated particles to form toner particles (fusing and coalescing step);
A fluoromonomer and a polymerization initiator are added to the toner particle dispersion in which the toner particles are dispersed, and the unsaturated polyester component of the amorphous unsaturated polyester resin and the fluorine-based single monomer present in the surface layer portion of the toner particles. A step of cross-linking the polymer and forming a cross-linked product by cross-linking on the surface layer of the toner particles (cross-linked product forming step)
Through this process, it is preferable to produce toner particles.

Details of each step will be described below.
In the following description, a method of obtaining toner particles containing a colorant and a release agent will be described. However, the colorant and the release agent are used as necessary. Of course, you may use other additives other than a coloring agent and a mold release agent.

-First aggregated particle forming step-
First, together with a resin particle dispersion in which resin particles are dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed and a release agent dispersion in which release agent particles are dispersed are prepared.

The resin particles dispersed in the resin particle dispersion include amorphous unsaturated polyester resin or other binder resin particles. Desirably, the amorphous unsaturated polyester resin particles and the crystalline resin ( Desirably, crystalline polyester resin) particles.
In the case of applying two or more kinds of resin particles, the resin particle dispersion may be prepared as a single resin particle dispersion by preparing each resin particle dispersion and mixing each resin particle. Mixing may be performed when the dispersion swimming is mixed with the colorant particle dispersion and the release agent particle dispersion.

  The resin particle dispersion is prepared, for example, by dispersing resin particles in a dispersion medium using a surfactant.

Examples of the dispersion medium used for the resin particle dispersion include an aqueous medium.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together.

The surfactant is not particularly limited. For example, anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; amine salt type, quaternary ammonium salt type Nonionic surfactants such as polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based, and the like. Among these, an anionic surfactant and a cationic surfactant are particularly mentioned. The nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant.
Surfactant may be used individually by 1 type and may use 2 or more types together.

Examples of the method for dispersing the resin particles in the dispersion medium in the resin particle dispersion include general dispersion methods such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, and a dyno mill. Further, depending on the type of resin particles used, the resin particles may be dispersed in the resin particle dispersion using, for example, a phase inversion emulsification method.
The phase inversion emulsification method is a method in which a resin to be dispersed is dissolved in a hydrophobic organic solvent in which the resin is soluble, and a base is added to the organic continuous phase (O phase) to neutralize the aqueous medium. (W phase) is added to convert the resin from W / O to O / W (so-called phase inversion) to form a discontinuous phase and disperse the resin in an aqueous medium in the form of particles. It is.

Examples of the volume average particle diameter of the resin particles dispersed in the resin particle dispersion include a range of 0.01 μm to 1 μm, and may be 0.08 μm to 0.8 μm, or 0.1 μm to 0 μm. It may be 6 μm.
The volume average particle diameter of the resin particles is measured with a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.). Hereinafter, unless otherwise specified, the volume average particle diameter of the particles is measured in the same manner.

  As content of the resin particle contained in a resin particle dispersion liquid, 5 mass% or more and 50 mass% or less are mentioned, for example, and 10 mass% or more and 40 mass% or less may be sufficient.

  In addition, similarly to resin particle dispersion, for example, a colorant dispersion and a release agent dispersion are also prepared. In other words, regarding the volume average particle size of the particles in the resin particle dispersion, the dispersion medium, the dispersion method, and the content of the particles, the colorant particles dispersed in the colorant dispersion and the release agent dispersed in the release agent dispersion are used. The same applies to the mold agent particles.

Next, the colorant particle dispersion and the release agent dispersion are mixed together with the resin particle dispersion.
In the mixed dispersion, the resin particles, the colorant particles, and the release agent particles are hetero-aggregated, and the resin particles, the colorant particles, and the release agent particles have a diameter close to the diameter of the desired toner particles. First aggregated particles (core aggregated particles) are formed.

Specifically, for example, a flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. After that, the resin particles are heated to a glass transition temperature (specifically, for example, the glass transition temperature of the resin particles −30 ° C. or higher and the Vicat softening temperature −10 ° C. or lower) to aggregate the particles dispersed in the mixed dispersion liquid To form first agglomerated particles.
In the first agglomerated particle forming step, for example, the flocculant is added at room temperature (for example, 25 ° C.) while stirring the mixed dispersion with a rotary shearing homogenizer, and the pH of the mixed dispersion is acidic (for example, pH is 2 or more). 5 or less) and, if necessary, after adding a dispersion stabilizer, the heating may be performed.

Examples of the flocculant include surfactants having a polarity opposite to that of the surfactant used as the dispersant added to the mixed dispersion, for example, inorganic metal salts and divalent or higher-valent metal complexes. In particular, when a metal complex is used as the flocculant, the amount of the surfactant used is reduced, and the charging characteristics are improved.
If necessary, an additive that forms a complex or a similar bond with the metal ion of the flocculant may be used. As this additive, a chelating agent is preferably used.

Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include metal salt polymers.
A water-soluble chelating agent may be used as the chelating agent. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and the like.
Examples of the addition amount of the chelating agent include a range of 0.01 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the resin particles, and 0.1 parts by mass or more and less than 3.0 parts by mass. There may be.

-Second aggregated particle forming step-
Next, the obtained first aggregated particle dispersion in which the first aggregated particles are dispersed and the amorphous unsaturated polyester resin particle dispersion in which the amorphous unsaturated polyester resin particles are dispersed are mixed.
And in this mixed dispersion liquid, it aggregates so that the particle | grains of an amorphous unsaturated polyester resin may adhere to the surface of a 1st aggregation particle, and an amorphous unsaturated polyester resin particle | grain is on the surface of a 1st aggregation particle. The attached second aggregated particles are formed.

Specifically, for example, in the first aggregated particle forming step, the first aggregated particles reach the target particle size (for example, the volume average particle size is 1.5 μm or more, desirably 2.5 μm or more and 6.5 μm or less). When the first agglomerated particle dispersion is mixed with the amorphous unsaturated polyester resin particle dispersion, the glass transition of the first agglomerated particles and the amorphous unsaturated polyester resin particles is mixed with the mixed dispersion. Heating is performed below the lower glass transition temperature of the temperature.
Then, the progress of aggregation is stopped by setting the pH of the mixed dispersion to a range of, for example, about 6.5 to 8.5.

  Here, in the amorphous unsaturated polyester resin particle dispersion, the volume average particle diameter of the amorphous unsaturated polyester resin particles to be dispersed includes, for example, a range of 0.01 μm or more and 1 μm or less, and 0.05 μm or more. It may be 0.8 μm or less, and may be 0.1 μm or more and 0.6 μm, but is particularly preferably less than 0.3 μm (300 nm).

  Thereby, the 2nd aggregated particle aggregated so that the amorphous unsaturated polyester resin particle may adhere to the surface of the 1st aggregated particle is obtained.

-Fusion / unification process-
Next, the second aggregated particle dispersion in which the second aggregated particles are dispersed is, for example, not less than the glass transition temperature of the amorphous unsaturated polyester resin (for example, 10 from the glass transition temperature of the amorphous unsaturated polyester resin). To 30 ° C. or higher) to fuse and coalesce the second aggregated particles to form toner particles.

-Crosslinked product forming step-
A fluoromonomer and a polymerization initiator are added to the toner particle dispersion in which the toner particles are dispersed, and the unsaturated polyester component of the amorphous unsaturated polyester resin and the fluorine-based single monomer present in the surface layer portion of the toner particles. The polymer is cross-linked to form a cross-linked product by cross-linking in the surface layer portion of the toner particles. That is, the toner particles are seed-polymerized with a fluorine-based monomer, so that the amorphous unsaturated polyester resin (its unsaturated polyester component) and the fluorine-based monomer present in the surface layer portion of the toner particles To form a crosslinked product.

  For example, the cross-linked product is formed under the conditions of a reaction temperature of 50 ° C. or higher and 100 ° C. or lower (desirably 60 ° C. or higher and 90 ° C. or lower), a reaction time of 30 minutes or longer and 5 hours or shorter (preferably 1 hour or longer and 4 hours or shorter). Good to do.

The polymerization initiator is preferably one that dissolves in the solvent of the toner particle dispersion (water is preferably used as the solvent), and a typical example is a water-soluble polymerization initiator. select.
Examples of the water-soluble polymerization initiator include hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, and bromomethyl peroxide. Benzoyl, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, tert-butyl hydroperoxide pertriphenylacetate, Tert-butyl formate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, tert-butyl per-N- (3-toluyl) carbamate, ammonium bisulfate Um, sodium bisulfate, peroxides and the like; and others as mentioned, not limited to these.
Of these, persulfate initiators such as ammonium persulfate, potassium persulfate, and sodium persulfate are desirable. These free radical initiators may be used alone or in combination of two or more.

  Here, the addition amount of the fluorine-based monomer with respect to the toner particle dispersion (its solid content) is, for example, 0.05% by mass or more and 2.0% by mass or less (desirably 0.1% by mass or more and 1.0% by mass). % Or less), and the addition amount of the polymerization initiator may be, for example, from 0.1% by mass to 10% by mass (desirably from 0.3% by mass to 5.0% by mass).

Through the above steps, a non-crystalline unsaturated polyester resin composed of a core material including a resin composed of resin particles (resin in which resin particles are fused and united) and non-crystalline unsaturated polyester resin particles covering the core material ( Thus, toner particles (core / shell structure toner particles) composed of a coating layer containing amorphous unsaturated polyester resin in which amorphous unsaturated polyester resin particles are fused and combined are obtained.
In the surface layer portion of the toner particles, a cross-linked product of the unsaturated polyester component of the amorphous unsaturated polyester resin and the fluorine monomer is formed.

After the fusion and coalescence process, toner particles formed in the solution are dried through a known washing process, solid-liquid separation process, and drying process to obtain toner particles.
In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Further, although the drying process is not particularly limited, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

    The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to the obtained dry toner particles and mixing them. Mixing is preferably performed by, for example, a V blender, a Henschel mixer, a Ladyge mixer, or the like. Further, if necessary, coarse toner particles may be removed using a vibration classifier, a wind classifier, or the like.

<Electrostatic image developer>
The electrostatic charge image developer according to the exemplary embodiment includes at least the toner according to the exemplary embodiment described above.
The electrostatic image developer according to this embodiment may be a one-component developer including only the toner according to this embodiment, or may be a two-component developer mixed with the toner and a carrier.

  There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. Examples of the carrier include a resin-coated carrier and a magnetic dispersion type carrier.

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

<Image Forming Apparatus / Image Forming Method>
Next, the image forming apparatus / image forming method according to the present embodiment will be described.
An image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the charged image carrier, and an electrostatic image development. A developing means for accommodating the developer and developing the electrostatic image formed on the image carrier as a toner image by the electrostatic image developer, and transferring the toner image formed on the image carrier onto the transfer target And a fixing unit that fixes the toner image transferred onto the transfer target. The electrostatic image developer according to the present embodiment is applied as the electrostatic image developer.

  In the image forming apparatus according to the present embodiment, for example, the part including the developing unit may have a cartridge structure (process cartridge) that is detachable from the image forming apparatus. As the process cartridge, for example, A process cartridge that accommodates the electrostatic charge image developer according to the exemplary embodiment and includes a developing unit is preferably used.

  The image forming method according to the present embodiment contains a charging step for charging the image carrier, an electrostatic charge image forming step for forming an electrostatic charge image on the surface of the charged image carrier, and an electrostatic charge image developer. A developing step of developing the electrostatic image formed on the image carrier as a toner image with an electrostatic charge image developer, and a transfer step of transferring the toner image formed on the image carrier onto the transfer target; And a fixing step of fixing the toner image transferred onto the transfer medium. And as the electrostatic charge image developer, the electrostatic charge image developer according to the present embodiment is applied.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. 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 configuration diagram showing a four-tandem color image forming apparatus. The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter sometimes simply referred to as “units”) 10Y, 10M, 10C, and 10K are arranged in parallel at a predetermined distance from each other 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. The vehicle travels in the direction toward the unit 10K. A force is applied to the support roller 24 in a direction away from the drive roller 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the 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 has yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The toner including the four color toners can be supplied.

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

The first unit 10Y includes a photoreceptor 1Y that functions as an image holding member. The periphery of the photoreceptor 1Y is exposed by a charging roller (charging means) 2Y for charging the surface of the photoreceptor 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on the color-separated image signal. An exposure device (electrostatic image forming means) 3 for forming an electrostatic charge image, a developing device (developing means) 4Y for developing the electrostatic image by supplying toner charged to the electrostatic image, and an intermediate transfer belt for the developed toner image A primary transfer roller 5 </ b> Y (primary transfer unit) that transfers onto the image transfer unit 20 and a photoconductor cleaning device (cleaning unit) 6 </ b> Y that removes toner remaining on the surface of the photoconductor 1 </ b> Y 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 charge image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

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

  In the developing device 4Y, for example, an electrostatic charge image developer according to the present embodiment including at least yellow toner and a carrier 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 primary transfer bias is applied to the primary transfer roller 5Y, and an electrostatic force from the photoreceptor 1Y toward the primary transfer roller 5Y acts on the toner image. Then, the toner image on the photoreceptor 1Y 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

  The intermediate transfer belt 20 onto which the four color toner images have been transferred in multiple layers through the first to fourth units is arranged on the image transfer surface side of the intermediate transfer belt 20, the support roller 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roller (secondary transfer means) 26 is connected to a secondary transfer portion. On the other hand, the recording paper (transfer object) P is fed at a predetermined timing to the gap where the secondary transfer roller 26 and the intermediate transfer belt 20 are pressed against each other via the supply mechanism, and the secondary transfer bias is supported. Applied to the roller 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, so The toner image is transferred onto the recording paper P. 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 the pressure contact portions (nip portions) of the pair of fixing rolls in the fixing device (roll-type fixing unit) 28, and the toner image is fixed on the recording paper P, thereby forming a fixed image.
Examples of the transfer target to which the toner image is transferred include plain paper, OHP sheet, and the like used for electrophotographic copying machines and printers.
In order to further improve the smoothness of the image surface after fixing, it is desirable that the surface of the transfer target is as smooth as possible. For example, coated paper in which the surface of plain paper is coated with resin, art for printing Paper or the like is preferably used.

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 is not limited to this configuration, and the toner image is directly transferred from the photoreceptor. It may be a structure that is transferred to a recording sheet.

<Process cartridge, toner cartridge>
FIG. 2 is a schematic configuration diagram showing an embodiment of a preferred example of a process cartridge containing an electrostatic charge image developer according to this embodiment. In the process cartridge 200, a charging roller 108, a developing device 111, a photoconductor cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure are combined using a mounting rail 116 together with the photoconductor 107. , And integrated. In FIG. 2, reference numeral 300 denotes a transfer target.
The process cartridge 200 is detachable from an image forming apparatus including a transfer device 112, a fixing device 115, and other components not shown.

  The process cartridge 200 shown in FIG. 2 includes a charging device 108, a developing device 111, a cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. Can be combined. In the process cartridge according to the present embodiment, in addition to the photosensitive member 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 according to this embodiment will be described. The toner cartridge according to the present exemplary embodiment is a toner cartridge that is detachably attached to the image forming apparatus and stores at least a replenishment electrostatic image developing toner to be supplied to a developing unit provided in the image forming apparatus.

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

  Hereinafter, although an embodiment explains this embodiment in detail, this embodiment is not limited to these examples at all. In the following description, “part” and “%” are all based on mass unless otherwise specified.

[Preparation of resin particle dispersion]
(Preparation of amorphous unsaturated polyester resin particle dispersion A)
In a heat-dried two-necked flask, 10 mol parts of polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2,2) -2,2-bis (4- Hydroxyphenyl) propane 90 mol, terephthalic acid 10 mol, fumaric acid 65 mol, n-dodecenyl succinic acid 3 mol, acid component (total mol of terephthalic acid, fumaric acid, n-dodecenyl succinic acid) 0 .05 mol part of dibutyltin oxide is added, nitrogen gas is introduced into the container and heated in an inert atmosphere, and then subjected to a copolycondensation reaction at 150 ° C. to 230 ° C. for 12 to 20 hours. The pressure was gradually reduced at 250 ° C. to synthesize amorphous unsaturated polyester resin A.
The obtained amorphous unsaturated polyester resin A 3000 parts by mass, ion exchanged water 10000 parts by mass, and sodium dodecylbenzenesulfonate 90 parts by mass were charged into an emulsification tank of a high-temperature, high-pressure emulsifier (Cavitron CD1010), and then 130 ° C. After being heated and melted, it was dispersed at 110 ° C. at a flow rate of 3 L / m at 10,000 rpm for 30 minutes, passed through a cooling tank, and 30% solid content and an amorphous unsaturated polyester resin particle dispersion A having a volume average particle diameter D50v of 115 nm. Was made.

(Preparation of amorphous unsaturated polyester resin particle dispersion B)
Amorphous unsaturated polyester resin B was synthesized in the same manner as in the preparation of amorphous unsaturated polyester resin particle dispersion A, except that 65 mol parts of fumaric acid was changed to 65 mol parts of maleic acid. %, An amorphous unsaturated polyester resin particle dispersion B having a volume average particle diameter D50v of 116 nm was obtained.

(Preparation of amorphous unsaturated polyester resin particle dispersion C)
Amorphous unsaturated polyester resin C was synthesized and solidified in the same manner as in the preparation of amorphous unsaturated polyester resin particle dispersion A, except that 65 mol parts of fumaric acid was changed to 65 mol parts of maleic anhydride. An amorphous unsaturated polyester resin particle dispersion C having a 30% content and a volume average particle diameter D50v of 114 nm was obtained.

(Preparation of amorphous saturated polyester resin particle dispersion D)
Except for changing 65 mol parts of fumaric acid and 3 mol parts of n-dodecenyl succinic acid to 68 mol parts of succinic acid, it does not have an unsaturated polyester component in the same manner as in the preparation of the amorphous unsaturated polyester resin particle dispersion A. Amorphous saturated polyester resin D was synthesized to obtain amorphous saturated polyester resin particle dispersion D having a solid content of 30% and a volume average particle diameter D50v of 113 nm.

(Preparation of crystalline polyester resin particle dispersion)
Into a heat-dried three-necked flask, 44 mol parts of 1,9-nonanediol, 56 mol parts of dodecanedicarboxylic acid and 0.05 mol parts of dibutyltin oxide were introduced, and nitrogen gas was introduced into the container to maintain an inert atmosphere. After the temperature was raised, the copolycondensation reaction was carried out at 150 ° C. to 230 ° C. for 2 hours, then the temperature was raised gradually to 230 ° C. and stirred for 5 hours. When the mixture became viscous, the reaction was stopped by air cooling. A crystalline polyester resin was synthesized.
3000 parts by mass of the obtained crystalline polyester resin, 10000 parts by mass of ion-exchanged water, and 90 parts by mass of sodium dodecylbenzenesulfonate are charged into an emulsification tank of a high-temperature, high-pressure emulsifier (Cavitron CD1010), and then heated to 130 ° C. Then, it was dispersed at 110 ° C. and a flow rate of 3 L / m at 10,000 rpm for 30 minutes and passed through a cooling tank to prepare a crystalline polyester resin particle dispersion having a solid content of 30% and a volume average particle diameter D50v of 125 nm.

[Preparation of colorant dispersion]
Carbon black (Regal 330 Cabot) 45 parts by mass, ionic surfactant Neogen R (Daiichi Kogyo Seiyaku) 5 parts by mass, ion-exchanged water 200 parts by mass are mixed and dissolved, and homogenizer (IKA Ultra Tarrax) is used for 10 minutes. Dispersion was then performed using an optimizer to obtain a colorant dispersion having a solid content of 20% and a center particle size of 245 nm.

[Preparation of release agent dispersion]
Paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP0190) 45 parts by mass of ionic surfactant Neogen R (Daiichi Kogyo Seiyaku) and 200 parts by mass of ion-exchanged water are heated to 120 ° C., and pressure discharge type gorin homogenizer is used. Dispersion treatment was performed to obtain a release agent dispersion having a solid content of 20% and a center particle size of 219 nm.

[Preparation of fluorine component-containing resin particle dispersion]
100 parts by mass of styrene, 2 parts by mass of methyl methacrylate, 2 parts by mass of methacrylic acid 1H, 1H, 5H-octafluoropentyl (manufactured by Kanto Chemical Co., Inc.), 2 parts by mass of a nonionic surfactant (manufactured by Sanyo Chemical Industries, Nonibol 400) And anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) in a reaction kettle in which 510 parts by mass of ion-exchanged water is dissolved, and 4 parts by mass of ammonium persulfate is dissolved while stirring and mixing for 20 minutes. 50 parts by mass of ion-exchanged water was added. Thereafter, the reaction kettle was purged with nitrogen, and then the kettle was heated to 70 ° C. and emulsion polymerization was continued for 5 hours. As a result, a fluorine component-containing resin particle dispersion having a solid content of 20% and a volume average particle diameter D50 of 220 nm was obtained.

[Production of toner particles]
(Preparation of toner particles A1)
320 parts by weight of amorphous unsaturated polyester resin particle dispersion A, 80 parts by weight of crystalline polyester resin particle dispersion, 50 parts by weight of colorant dispersion, 50 parts by weight of release agent dispersion, aluminum sulfate (Wako Pure Chemical Industries, Ltd.) ) 5 parts by mass, 10 parts by mass of sodium dodecylbenzenesulfonate, 50 parts by mass of 0.3M nitric acid aqueous solution, 500 parts by mass of ion-exchanged water were placed in a round stainless steel flask, and homogenizer (Ultra Turrax T manufactured by IKA). -50) and then heated to 48 ° C. with stirring in a heating oil bath. After maintaining at 48 ° C. and confirming that aggregated particles having a volume average particle size of about 5.3 μm are formed, an additional 100 parts by mass of the amorphous unsaturated polyester resin particle dispersion A is added, and then 30 more Held for a minute.
Subsequently, a 1N aqueous sodium hydroxide solution was slowly added until the pH reached 7.0, and then the mixture was heated to 80 ° C. while continuing stirring and maintained for 3 hours. A solution prepared by dissolving 0.5 parts by mass of ammonium persulfate in 10 parts by mass of ion-exchanged water was added to the obtained dispersion, and at a temperature of 80 ° C., 1H, 1H, 5H-octafluoropentyl methacrylate (Kanto Chemical Co., Inc.) was added. (Manufactured) A mixture of 3.4 parts by mass with 50 parts by mass of ion-exchanged water and 3 parts by mass of sodium dodecylbenzenesulfonate was added dropwise over 30 minutes and polymerized at 80 ° C. for 2 hours. The reaction product was filtered, washed with ion exchange water, and then dried using a vacuum dryer to obtain toner particles A1.

(Preparation of toner particles A2)
Preparation of toner particles A1 except that “methacrylic acid 1H, 1H, 5H-octafluoropentyl” was changed to “1,1,1,3,3,3-hexafluoroisopropyl methacrylate (manufactured by Kanto Chemical Co., Inc.)” In the same manner, toner particles A2 were obtained.

(Preparation of toner particles A3)
Except for changing “1H, 1H, 5H-octafluoropentyl methacrylate” to “2,2,3,3,3-pentafluoropropyl methacrylate” (manufactured by Kanto Chemical Co., Inc.), the same as the production of toner particles A1. Thus, toner particles A3 were obtained.

(Preparation of toner particles A4)
Preparation of toner particles A1 except that “methacrylic acid 1H, 1H, 5H-octafluoropentyl” was changed to “2,2,3,4,4,4-hexafluorobutyl methacrylate (manufactured by Kanto Chemical Co., Inc.)” In the same manner, toner particles A4 were obtained.

(Preparation of toner particles A5)
Except for changing “methacrylic acid 1H, 1H, 5H-octafluoropentyl” to “methacrylic acid 3,3,4,4,5,5,6,6,6-nonafluorohexyl (manufactured by Kanto Chemical Co., Inc.)” The toner particles A5 were obtained in the same manner as in the preparation of the toner particles A1.

(Preparation of toner particles A6)
"Methacrylic acid 1H, 1H, 5H-octafluoropentyl" is replaced with "3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate (Kanto Chemical) The toner particles A6 were obtained in the same manner as in the preparation of the toner particles A1 except that the toner particles A1 were manufactured.

(Preparation of toner particles A7)
Toner particles in the same manner as in the preparation of toner particles A1, except that “1H, 1H, 5H-octafluoropentyl methacrylate” was changed to “2,2,2-trifluoroethyl methacrylate (manufactured by Kanto Chemical Co.)”. A7 was obtained.

(Preparation of toner particles A8)
Except for changing “1H, 1H, 5H-octafluoropentyl methacrylate” to “1H, 1H, 9H-hexadecafluorononyl methacrylate” (manufactured by Wako Pure Chemical Industries, Ltd.), the same as the production of toner particles A1. As a result, toner particles A8 were obtained.

(Preparation of toner particles A9)
Except for changing “1H, 1H, 5H-octafluoropentyl methacrylate” to “1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate” (manufactured by Kanto Chemical Co., Inc.), the same as the production of toner particles A1. As a result, toner particles A9 were obtained.

(Preparation of toner particles A10)
Toner particles A10 are produced in the same manner as in the preparation of toner particles A1, except that “methacrylic acid 1H, 1H, 5H-octafluoropentyl” is changed to “2- (trifluoromethyl) acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)”. Got.

(Preparation of toner particles A11)
Toner particles in the same manner as in the preparation of toner particles A1, except that “1H, 1H, 5H-octafluoropentyl methacrylate” was changed to “2- (henicosfluorodecyl) ethyl methacrylate (manufactured by Kanto Chemical Co.)”. A11 was obtained.

(Preparation of toner particles A12)
Toner particles were prepared in the same manner as in the preparation of toner particles A1, except that “methacrylic acid 1H, 1H, 5H-octafluoropentyl” used in the preparation of toner A1 was changed from 3.4 parts by mass to 1.7 parts by mass. A12 was obtained.

(Preparation of toner particles A13)
Toner particles in the same manner as in the preparation of toner particles A1, except that “methacrylic acid 1H, 1H, 5H-octafluoropentyl” used in preparation of toner A1 was changed from 3.4 parts by weight to 1.3 parts by weight. A13 was obtained.

(Preparation of toner particles A14)
Toner particles in the same manner as in the preparation of toner particles A1, except that “methacrylic acid 1H, 1H, 5H-octafluoropentyl” used in preparation of toner A1 was changed from 3.4 parts by weight to 1.0 part by weight. A14 was obtained.

(Preparation of toner particles A15)
Toner particles in the same manner as in the preparation of toner particles A1, except that “methacrylic acid 1H, 1H, 5H-octafluoropentyl” used in preparation of toner A1 was changed from 3.4 parts by weight to 0.7 parts by weight. A15 was obtained.

(Preparation of toner particle A16)
Toner particles in the same manner as in the preparation of toner particles A1, except that “methacrylic acid 1H, 1H, 5H-octafluoropentyl” used in preparation of toner A1 was changed from 3.4 parts by weight to 0.5 parts by weight. A16 was obtained.

(Preparation of toner particle A17)
Toner particles in the same manner as in the preparation of toner particles A1, except that “methacrylic acid 1H, 1H, 5H-octafluoropentyl” used in preparation of toner A1 was changed from 3.4 parts by weight to 6.6 parts by weight. A17 was obtained.

(Preparation of toner particles A18)
“Methacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl” used in the preparation of the toner A6 was changed from 3.4 parts by mass to 7 parts. The toner particles A18 were obtained in the same manner as in the preparation of the toner particles A6 except that the amount was changed to 4 parts by mass.

(Preparation of toner particles A19)
“Methacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl” used in the preparation of the toner A6 was changed from 3.4 parts by mass to 7 parts. A toner particle A19 was obtained in the same manner as in the preparation of the toner particle A6 except that the amount was changed to 0.7 parts by mass.

(Preparation of toner particle A20)
The toner particles A20 were prepared in the same manner as in the preparation of the toner particles A1, except that “methacrylic acid 1H, 1H, 5H-octafluoropentyl” used in the preparation of the toner A1 was changed from 3.4 parts by mass to 7 parts by mass. Obtained.

(Preparation of toner particles A21)
The amount of “methacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl used in the preparation of the toner A6 was changed from 3.4 parts by mass to 0.5%. A toner particle A21 was obtained in the same manner as in the preparation of the toner particle A6, except that the mass part was changed.

(Preparation of toner particle A22)
Toner particles were prepared in the same manner as in the preparation of toner particles A11, except that “2- (henicosfluorodecyl) ethyl methacrylate” used in preparation of toner A11 was changed from 3.4 parts by weight to 0.6 parts by weight. A22 was obtained.

(Preparation of toner particles A23)
The toner was prepared in the same manner as in the preparation of the toner particles A1, except that the “amorphous unsaturated polyester resin particle dispersion A” used in the preparation of the toner A1 was changed to the “amorphous unsaturated polyester resin particle dispersion B”. Particle A23 was obtained.

(Preparation of toner particles A24)
The toner was prepared in the same manner as in the preparation of the toner particles A1, except that the “amorphous unsaturated polyester resin particle dispersion A” used in the preparation of the toner A1 was changed to the “amorphous unsaturated polyester resin particle dispersion C”. Particle A24 was obtained.

(Preparation of toner particle A25)
800 parts by mass of the amorphous unsaturated polyester resin A, 70 parts by mass of the crystalline polyester resin, 50 parts by mass of the carbon black (Regal 330), and 80 parts by mass of the paraffin wax (HNP0190) were mixed with a Banbury mixer (manufactured by Kobe Steel). Then, pressure was applied so that the internal temperature became 110 ± 5 ° C., and kneading was performed at 80 rpm for 10 minutes. The obtained kneaded product is cooled, coarsely pulverized with a hammer mill, finely pulverized to about 6.8 μm with a jet mill, and then classified with an elbow jet classifier (manufactured by Matsuzaka Trading Co., Ltd.). To 120 parts of the obtained powder, 10 parts by mass of sodium dodecylbenzenesulfonate, 50 parts by mass of 0.3M nitric acid aqueous solution, and 500 parts by mass of ion-exchanged water were placed in a flask and dispersed.
Subsequently, a 1N aqueous sodium hydroxide solution was slowly added until the pH reached 7.0, and then the mixture was heated to 80 ° C. while continuing stirring and maintained for 3 hours. A solution prepared by dissolving 0.5 parts by mass of ammonium persulfate in 10 parts by mass of ion-exchanged water was added to the obtained dispersion, and at a temperature of 80 ° C., 1H, 1H, 5H-octafluoropentyl methacrylate (Kanto Chemical Co., Inc.) was added. (Manufactured) A mixture of 3.4 parts by mass with 50 parts by mass of ion-exchanged water and 3 parts by mass of sodium dodecylbenzenesulfonate was added dropwise over 30 minutes and polymerized at 80 ° C. for 2 hours. The reaction product was filtered, washed with ion exchange water, and then dried using a vacuum dryer to obtain toner particles A25.

(Preparation of toner particles R1)
Toner particles in the same manner as in the preparation of toner particles A1, except that the step of adding (dropping) 1H, 1H, 5H-octafluoropentyl methacrylate, ammonium persulfate, and ion-exchanged water at the time of preparation of toner A1 is not performed. R1 was obtained.

(Preparation of toner particle R2)
Except for changing “3.4 parts by weight of methacrylic acid 1H, 1H, 5H-octafluoropentyl” used in preparation of toner A1 to “3.4 parts by weight of methyl methacrylate”, the same as the preparation of toner particles A1. Thus, toner particles R2 were obtained.

(Preparation of toner particle R3)
Toner particles are produced in the same manner as in the preparation of toner particles A1, except that “amorphous unsaturated polyester resin particle dispersion A” used in preparation of toner A1 is changed to “amorphous saturated polyester resin particle dispersion D”. R3 was obtained.

(Preparation of toner particles R4)
The “additional amorphous unsaturated polyester resin particle dispersion A100 parts by mass” used in the preparation of the toner A1 was changed to “100 parts by mass of the fluorine component-containing resin particle dispersion” and the toner A1 was prepared. Toner particles R4 were obtained in the same manner as in the preparation of toner particles A1, except that the step of adding (dropping) methacrylic acid 1H, 1H, 5H-octafluoropentyl, ammonium persulfate, and ion-exchanged water was not performed.

[Production of toner]
(Production of toners T1 to T25, TR1 to TR4)
To 50 parts by mass of each of the toner particles (A1 to A25, R1 to R4) obtained as described above, 1.5 parts by mass of hydrophobic silica (manufactured by Cabot, TS720) is added, and a Henschel mixer is used. The toner was mixed at a peripheral speed of 30 m / s for 3 minutes to obtain toners T1 to T25 and TR1 to TR4 as external toners.

[Production of developer]
(Developers T1 to T25 and TR1 to TR4)
A pressure kneader with 500 parts of toluene together with 100 parts of ferrite particles (manufactured by Powder Tech Co., Ltd., average particle size 50 μm) and 1.5 parts of methyl methacrylate resin (manufactured by Mitsubishi Rayon Co., Ltd., molecular weight 95,000, component ratio of 10,000 or less). The mixture was stirred and mixed at room temperature for 15 minutes, then heated to 70 ° C. while mixing under reduced pressure to distill off toluene, then cooled, and classified using a 105 μm sieve to obtain a resin-coated ferrite carrier.
This resin-coated ferrite carrier is mixed with toners T1 to T25 and TR1 to TR4, which are the above-mentioned externally added toners, respectively, and two-component electrostatic charge image developers T1 to T25 and TR1 to TR4 having a toner concentration of 7% by mass. Was made.

[Examples 1 to 25, Comparative Examples 1 to 4]
The obtained toners and developers were used as toners and developers of Examples 1 to 25 and Comparative Examples 1 to 4, and the following evaluations were performed.
The evaluation results are shown in Table 1.

<Evaluation>
(Ratio F / C of the amount of fluorine atoms and the amount of carbon atoms in the surface layer of the toner particles)
The ratio F / C of the amount of fluorine atoms and the amount of carbon atoms in the surface layer of the toner particles was measured by the method described above. The results are shown in Table 1. What is described as “-” in Table 1 means that it is below the measurement limit.

(THF insoluble matter in toner particles)
The THF insoluble content (crosslinked product) of the toner particles was measured by the method described above. The results are shown in Table 1.

(Evaluation by image formation)
Each developer is housed in a modified Color DocuTech 60V machine manufactured by Fuji Xerox Co., Ltd. Using this modified machine, a solid image of 5 g × 5 cm and a toner loading of 6 g / m ^{2 on} 5,000 sheets of Fuji Xerox J paper. An image having a halftone image of 5 cm × 5 cm and a toner loading of 0.2 g / m ² was formed.
The amount of applied toner was determined by turning off the power of the apparatus before the toner was transferred and fixed on the paper, taking out the unfixed image, and cutting out the solid image and the halftone image. Thereafter, the toner was blown off with air or the like, and each paper was then weighed to measure the mass of the toner, and this was divided by the area where the image was formed. After toner amount in the range of 5.9~6.1g / ^{m 2} at solid image, a halftone image is a tolerance range of 0.18~0.22g / ^{m 2,} was adjusted to the range The evaluation started.
The image is first formed in a high temperature and high humidity ring with a temperature of 28 ° C. and a relative humidity of 85%, and the same developer is used as it is, and is changed to a low temperature and low humidity environment with a temperature of 10 ° C. and a relative humidity of 15%. Other than that, 5000 images were further formed under the same conditions. Thereafter, the temperature was returned again to a high-temperature and high-humidity ring having a temperature of 28 ° C. and a relative humidity of 85%, and left for 12 hours, and then 100 images were formed.

-Evaluation of image density-
In the above-described image formation, the image density of the 10th image in the first high-temperature and high-humidity environment was measured. This is image density A. Further, the image was changed to a low temperature and low humidity environment, and the image density was measured for the tenth image. Further, the image was changed from the low-temperature and low-humidity environment to the high-temperature and high-humidity environment again, and the image density of the tenth image was measured.
In addition, the image density was measured at n = 5 for both the solid image and the halftone image using X-Rite 968 (manufactured by X-Rite), and the average value was defined as the image density.
The evaluation of the image density is based on image density A-image density B (may be referred to as AB) between solid images or halftone images, and image density A-image between solid images or halftone images. It is performed by obtaining the concentration C (may be described as AC), and the evaluation criteria are as follows. It should be noted that the image density differences of AB and AC are both expressed as absolute values, and the larger value of the solid image and the halftone image is adopted.
A: The image density difference is 0.05 or less.
A: The image density difference is larger than 0.05 and smaller than 0.1.
Δ: The image density difference is greater than 0.1 and 0.2 or less.
X: The image density difference is larger than 0.2.

-Evaluation of fogging-
In the above-mentioned image formation, the first image to the tenth image when the image is formed by changing from the high temperature imperial environment to the low temperature and low humidity environment, and again from the low temperature and low humidity environment to the high temperature and high humidity environment. The fogging was evaluated for the first to tenth images when the image was formed by changing to.
The evaluation standard for fogging was the number of sheets from which fogging could not be confirmed for the first to tenth images after the environment changed. That is, when the fogging could not be confirmed from the first sheet, it was described as 1; Needless to say, an allowable range is one in which the fog cannot be confirmed by the 10th sheet, and the smaller the value, the better.

From the above results, it can be seen that the change in the image density due to the environmental change is suppressed in the present embodiment as compared with the comparative example.
In addition, it can be seen that in this example, the occurrence of fog was suppressed as compared with the comparative example, and good results were obtained.

1Y, 1M, 1C, 1K, 107 photoconductor (image carrier)
2Y, 2M, 2C, 2K, 108 Charging roller (charging unit)
3Y, 3M, 3C, 3K Laser beam 3, 110 Exposure device ((electrostatic charge image forming means))
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 Developer 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 portion 118 for static elimination exposure Opening portion 200 for exposure Process cartridge P, 300 Recording paper (transfer object)

Claims (11)

  An electrostatic charge image developing toner comprising toner particles comprising an amorphous polyester resin having an unsaturated polyester component and having a surface layer portion containing a crosslinked product of the unsaturated polyester component and a fluorinated monomer.   2. The electrostatic image developing toner according to claim 1, wherein a ratio F / C of fluorine atoms to carbon atoms in a surface layer portion of the toner particles is 0.01 or more and 0.15 or less.   The said fluorine-type monomer is at least 1 sort (s) selected from the monomer which has a chain functional group which contains a fluorine atom and is C1-C10. Toner for developing electrostatic images.   4. The electrostatic image developing toner according to claim 1, wherein the toner particles have an insoluble content in tetrahydrofuran (THF) of 4.0% by mass or less. 5.   The electrostatic image development according to any one of claims 1 to 4, wherein the unsaturated polyester component is a component derived from at least one selected from fumaric acid, maleic acid, and maleic anhydride. Toner.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1. Containing the toner for developing an electrostatic charge image according to any one of claims 1 to 5,
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for accommodating the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the image holding member as a toner image by the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus. An image carrier,
Charging means for charging the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the image carrier onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer medium;
An image forming apparatus comprising: A charging step for charging the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing the electrostatic image formed on the image carrier as a toner image by the electrostatic image developer according to claim 6;
A transfer step of transferring a toner image formed on the image carrier onto a transfer target;
A fixing step of fixing the toner image transferred onto the transfer medium;
An image forming method comprising: Preparing at least a resin particle dispersion in which resin particles are dispersed, aggregating at least resin particles to form first aggregated particles;
A first aggregated particle dispersion in which the first aggregated particles are dispersed and a polyester resin particle dispersion in which amorphous polyester resin particles having an unsaturated polyester component are dispersed are mixed, and the first aggregated particles are mixed. A step of aggregating the amorphous polyester resin particles to adhere to the surface thereof to form second agglomerated particles;
Heating the second aggregated particle dispersion in which the second aggregated particles are dispersed, fusing and coalescing the second aggregated particles to form toner particles;
A fluorine-based monomer and a polymerization initiator are added to the toner particle dispersion in which the toner particles are dispersed, and the unsaturated polyester component of the amorphous polyester resin and the fluorine present in the surface layer portion of the toner particles. Cross-linking with a monomer, and forming a cross-linked product by the cross-linking on the surface layer of the toner particles;
A method for producing a toner for developing an electrostatic charge image.