JP2014063055A - Toner for electrophotography, developer for electrophotography, toner cartridge, developing device, image forming device, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner for electrophotography excellent in adhesion to a recording medium.SOLUTION: Toner for electrophotography containing crystalline resin is formed by polymerizing polymerizable monomer (A) having cyclic structure, which includes a nitrogen atom in a structure serving as a structural unit of a polymer after polymerization.

Description

  The present invention relates to an electrophotographic toner, an electrophotographic developer, a toner cartridge, a developing device, an image forming apparatus, and an image forming method.

Patent Document 1 discloses an electrophotography having a shape factor SF1 of 100 to 140, which contains at least a binder resin A, a colorant, and a release agent, and further has a crystalline substance C coated with a coating resin B dispersed therein. Toner, wherein the binder resin A and the coating resin B are polyester resins, and the crystalline substance C is a polyester resin or a urethane compound, and the glass transition temperature of the coating resin B is the binder resin. An electrophotographic toner having a glass transition temperature higher than A is disclosed.
Patent Document 2 also discloses an electrophotographic toner using a crystalline polymer containing urethane or urea bond as a binder resin.

  Patent Document 3 discloses an electrostatic charge image developing toner comprising at least a binder resin and a colorant, wherein the binder resin contains a crystalline resin, and the crystalline resin has a specific structure. An electrostatic charge image developing toner which is a crystalline polyester obtained by polymerizing a polymerizable monomer is disclosed.

  In Patent Document 4, in an electrophotographic toner comprising at least a binder resin and a colorant, the binder resin contains a divalent or higher carboxylic acid having a sulfonic acid group as a copolymerization component. An electrophotographic toner containing crystalline polyester is disclosed.

JP 2007-058137 A JP-A-62-070859 JP 2007-033828 A JP 2001-305996 A

  An object of the present invention is to provide an electrophotographic toner excellent in adhesion to a recording medium.

The above problem is solved by the following means. That is,
The invention according to claim 1
An electrophotographic toner containing a polymerizable monomer (A) having a nitrogen atom and a cyclic structure in a structure which becomes a polymer structural unit after being polymerized.

The invention according to claim 2
The electrophotographic toner according to claim 1, wherein the polymerizable monomer (A) contains the nitrogen atom in at least the cyclic structure portion.

The invention according to claim 3
The crystalline resin is a resin obtained by polymerizing the polymerizable monomer (A) in an amount of 3 mol% or more and 15 mol% or less with respect to 100 mol% of the total polymerizable monomer constituting the crystalline resin. The electrophotographic toner according to claim 1, wherein the toner is an electrophotographic toner.

The invention according to claim 4
An electrophotographic developer comprising at least the electrophotographic toner according to claim 1.

The invention according to claim 5
Containing the toner for electrophotography according to claim 1;
The toner cartridge is detachable from the image forming apparatus.

The invention according to claim 6
A developing device comprising: a developing member that accommodates the electrophotographic toner according to claim 1 and develops the electrostatic image formed on the image holding member as a toner image with the electrophotographic toner.

The invention according to claim 7 provides:
An image carrier,
A charging device for charging the image carrier;
An electrostatic charge image forming apparatus for forming an electrostatic charge image on the surface of the charged image carrier;
A developing device containing the electrophotographic toner according to claim 1 and developing the electrostatic image formed on the image carrier as a toner image with the electrophotographic toner;
A transfer device for transferring a toner image formed on the image carrier onto a transfer target;
An image forming apparatus.

The invention according to claim 8 provides:
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 an electrostatic image formed on the image carrier as a toner image with the electrophotographic toner according to claim 1;
A transfer step of transferring a toner image formed on the image carrier onto a transfer target;
Is an image forming method.

  According to the invention of claim 1, it does not contain a crystalline resin obtained by polymerizing a polymerizable monomer (A) having a nitrogen atom and a cyclic structure in a structure that becomes a polymer structural unit after being polymerized. Compared to the case, an electrophotographic toner having excellent adhesion to a recording medium is provided.

  According to the second aspect of the present invention, there is provided an electrophotographic toner excellent in adhesiveness to a recording medium as compared with the case where the polymerizable monomer (A) does not contain a nitrogen atom in the cyclic structure portion.

  According to the invention of claim 3, the amount of the polymerizable monomer (A) is polymerized in the range of 3 mol% or more and 15 mol% or less with respect to 100 mol% of the total polymerizable monomer constituting the crystalline resin. Compared to a case where the resin is not a resin, an electrophotographic toner having excellent adhesion to a recording medium is provided.

  According to the invention which concerns on Claim 4, the crystalline resin in which the polymerizable monomer (A) which has a nitrogen atom and a cyclic structure is superposed | polymerized in the structure used as the structural unit of a polymer after superposition | polymerization is contained. An electrophotographic developer excellent in adhesiveness to a recording medium is provided as compared with a case where no toner is contained.

  According to the fifth aspect of the invention, the crystalline resin obtained by polymerizing the polymerizable monomer (A) having a nitrogen atom and a cyclic structure in the structure which becomes the structural unit of the polymer after being polymerized is contained. As compared with a case where no toner is accommodated, a toner cartridge is provided that is more excellent in adhesiveness to a recording medium in electrophotographic toner.

  According to the sixth aspect of the present invention, it contains a crystalline resin obtained by polymerizing a polymerizable monomer (A) having a nitrogen atom and a cyclic structure in a structure that becomes a structural unit of the polymer after being polymerized. As compared with the case where no toner is contained, a developing device having excellent adhesion between the electrophotographic toner and the recording medium is provided.

  According to the seventh aspect of the invention, it contains a crystalline resin obtained by polymerizing a polymerizable monomer (A) having a nitrogen atom and a cyclic structure in a structure that becomes a structural unit of the polymer after being polymerized. There is provided an image forming apparatus capable of obtaining an image excellent in bending resistance as compared with a case where no toner is contained.

  According to the eighth aspect of the invention, it contains a crystalline resin obtained by polymerizing a polymerizable monomer (A) having a nitrogen atom and a cyclic structure in a structure that becomes a structural unit of the polymer after being polymerized. There is provided an image forming method capable of obtaining an image excellent in bending resistance as compared with a case where no toner is contained.

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.

  Hereinafter, embodiments of an electrophotographic toner, an electrophotographic developer, a toner cartridge, a developing device, an image forming apparatus, and an image forming method of the present invention will be described in detail.

<Toner for electrophotography>
The electrophotographic toner according to the exemplary embodiment (hereinafter sometimes simply referred to as “toner”) is a polymerizable monomer having a nitrogen atom and a cyclic structure in a structure that becomes a polymer structural unit after being polymerized ( A) contains a crystalline resin obtained by polymerization.

  In recent years, in electrophotographic image formation, a method that uses film printing as a method of expressing transparency and overlaying it with printing on paper such as the cover of a base or a painting is used in combination with film printing. It is used in various fields such as book covers, magazine advertisements, and appendices.

An example of the film used for this film printing is a polyethylene terephthalate film (PET). PET is also a base material for OHP films, and has been excellent in adhesion to toners in the past. However, in film printing, it may be used by being folded, and there is no need for image defects even for strong curvature. . In recent years, a toner contains a large amount of a release agent in order to have oilless fixing suitability, and this release agent also decreases the adhesive force with the film, and the image may be peeled off when folded.
It should be noted that the toner used in the electrophotographic system is not limited to the above-described mode, and it has been desired to improve the adhesiveness when the recording medium is bent.

The toner according to the exemplary embodiment contains a crystalline resin in which a polymerizable monomer (A) having a nitrogen atom and a cyclic structure is introduced into a structure that becomes a polymer structural unit after being polymerized. Thus, the adhesive strength (folding resistance) when the recording medium is bent is improved.
In addition to containing a highly polar nitrogen atom, the crystallinity is appropriately broken by introducing a cyclic structure, and the adhesive force is improved by suppressing the volume change of the crystalline resin itself. Inferred.

In addition, it is more preferable that the polymerizable monomer (A) having a nitrogen atom and a cyclic structure in the structure which becomes a polymer structural unit after the polymerization contains at least the nitrogen atom in the cyclic structure portion.
By including a nitrogen atom in at least the cyclic structure portion, it is presumed that the polarity tends to be larger and the adhesive force is further improved.

  The toner particles in the present embodiment may contain a polymerizable monomer (A) or other additive having a nitrogen atom and a cyclic structure in a structure that becomes a polymer structural unit after being polymerized.

First, the binder resin will be described.
As the binder resin, a polymerizable monomer (A) having a nitrogen atom and a cyclic structure is polymerized at least in a structure which becomes a structural unit of the polymer after being polymerized. The polymerizable monomer (A) having a nitrogen atom and a cyclic structure in the structure that becomes a polymer structural unit after being polymerized more preferably contains the nitrogen atom in at least the cyclic structure portion.

Examples of those having a nitrogen element in the cyclic structure include 2,6-pyridinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,4-pyridinediacid. Carboxylic acid, 2,3-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,3-pyridinedicarboxylic acid anhydride, 3,5- Pyrazole dicarboxylic acid, 2,3-pyrazine dicarboxyl acid, Diethyl-1,4-Dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate, 2,2'-Bipyridine-4,4'-dicarboxylic acid And a compound having a carboxyl group or a derivative thereof.
2,6-pyridinedimethanol, 4,5-imidazolimethanol, 1- (2-Hydroxyethyl) -4- (3-hydroxypropyl) piperidine, 1,3-Bis (1- (2-hydroxyethyl) -4 -piperidyl) Alcohols such as propane are also included.

  Examples of the nitrogen element in a portion other than the cyclic structure include azobenzene 4,4-dicarboxylic acid.

  The crystalline resin obtained by polymerizing the polymerizable monomer (A) having a nitrogen atom and a cyclic structure in the structure that becomes the structural unit of the polymer after polymerization is not particularly limited. A crystalline polyester resin is preferred.

-Polyester resin The polyester resin includes those obtained mainly by condensation polymerization of polyvalent carboxylic acids and polyhydric alcohols, and the polyester resin may be composed of one kind of polyester resin. A mixture of polyester resins may be used.
In this embodiment, a resin obtained by polymerizing a polymerizable monomer (A) having a nitrogen atom and a cyclic structure in a structure that becomes a structural unit of the polymer after being polymerized as a crystalline polyester resin is used. .

  The polyvalent carboxylic acid other than the polymerizable monomer is not particularly limited. For example, the polymerizable monomer component described in “Polymer Data Handbook: Basic Edition” (Edition of Polymer Society, Baifukan) (A conventionally known divalent or trivalent or higher carboxylic acid) may be used.

  Among the polyvalent carboxylic acids, examples of the divalent carboxylic acid include alkyl succinic acid, alkenyl succinic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid. Acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, mesaconic acid and other dibasic acids, their anhydrides and their lower alkyl esters, and maleic acid And aliphatic unsaturated dicarboxylic acids such as fumaric acid, itaconic acid and citraconic acid.

  Examples of the alkyl succinic acid and alkenyl succinic acid include n-butyl succinic acid, n-butenyl succinic acid, isobutyl succinic acid, isobutenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, n-dodecyl succinic acid, n -Dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid and the like.

Among polyvalent carboxylic acids, examples of the trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid, and 1,2,4-naphthalene. Examples thereof include tricarboxylic acids, anhydrides thereof, and lower alkyl esters thereof.
Polyvalent carboxylic acid may be used individually by 1 type, and may use 2 or more types together.

  In particular, as the polyvalent carboxylic acid, adipic acid, alkenyl succinic acid, and terephthalic acid are preferable, and alkenyl succinic acid and terephthalic acid are desirable.

  The polyhydric alcohol other than the polymerizable monomer is not particularly limited. For example, the polymerizable monomer component described in “Polymer Data Handbook: Basic Edition” (Edition of Polymer Society, Baifukan) ( Conventionally known divalent or trivalent or higher alcohols) may be used.

Examples of polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin, and other aliphatic diols, cyclohexanediol, cyclohexanedimethanol, hydrogenated Examples thereof include aromatic diols such as alicyclic diols such as bisphenol A, ethylene oxide adducts of bisphenol A, and propylene oxide adducts of bisphenol A.
Examples of trihydric or higher alcohols among polyhydric alcohols include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

  In particular, as the polyhydric alcohol, bisphenol A is desirable, and specifically, an alkylene oxide adduct of bisphenol A (such as an ethylene oxide adduct of bisphenol A, a propylene oxide of bisphenol A) is desirable.

As a weight average molecular weight (Mw) of a polyester resin, the range of 12000 or more and 200000 or less is mentioned, for example, the range of 14000 or more and 14000 or less may be sufficient, and the range of 16000 or more and 120,000 or less may be sufficient.
As a number average molecular weight (Mn) of a polyester resin, the range of 4000-20000 is mentioned, for example, The range of 5000-12000 may be sufficient.
Moreover, as molecular weight distribution of a polyester resin, the value of Mw / Mn which is a parameter | index of molecular weight distribution has the range of 2-15.

  Examples of the glass transition temperature of the polyester resin include a range of 30 ° C. to 90 ° C., a range of 30 ° C. to 80 ° C., and a range of 50 ° C. to 70 ° C. may be used.

The crystalline resin is a polymerizable unit having a nitrogen atom and a cyclic structure in a structure that becomes a structural unit of the polymer after the polymerization with respect to 100 mol% of the total polymerizable monomer constituting the crystalline resin. It is preferable that the polymer is a resin polymerized in the range of 3 mol% to 15 mol% of the monomer (A). Furthermore, 4 mol% or more and 12 mol% or less are more preferable, and 5 mol% or more and 10 mol% or less are still more preferable.
The content of the crystalline resin as the binder resin is, for example, in the range of 2% by mass to 25% by mass with respect to the entire toner particles, and more preferably in the range of 5% by mass to 15% by mass. desirable.

Colorant Examples of the colorant include known organic or inorganic pigments and dyes, and oil-soluble dyes.
For example, examples of black pigments include carbon black and magnetic powder.
Examples of the yellow pigment include Hansa Yellow, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Slen Yellow, Quinoline Yellow, Permanent Yellow NCG, C.I. I. And CI Pigment Yellow 74.
Red pigments include Bengala, Watch Young Red, Permanent Red 4R, Resol Red, Brilliantamine 3B, Brilliantamine 6B, Dupont Oil Red, Pyrazolone Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Eoxin Red, Alizarin Lake Etc.
Blue pigments include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, chalcoil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate and so on.

Examples of the colorant include C.I. I. Pigment Yellow 74 is a preferred example.
These colorants may be mixed and further used in a solid solution state.

  The content of the colorant is, for example, in the range of 2% by mass to 20% by mass and preferably in the range of 3% by mass to 15% by mass among the components constituting the toner particles.

-Mold release agent Although there is no restriction | limiting in particular as a mold release agent, For example, petroleum wax, mineral wax; Animal and plant wax; Synthetic waxes, such as polyolefin wax, oxidized polyolefin wax, and Fischer-Tropsch wax; The melting temperature of the release agent is, for example, preferably 40 ° C. or more and 150 ° C. or less, and desirably 50 ° C. or more and 100 ° C. or less.
The content of the release agent is, for example, in the range of 1% by mass to 20% by mass among the components constituting the toner particles, and preferably in the range of 2% by mass to 12% by mass.

Other components In addition to the above, other components may be included. Examples of the other components include various components such as an internal additive, a charge control agent, and inorganic powder (inorganic particles).
Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, alloys, and magnetic materials such as compounds containing these metals.
Examples of the charge control agent include a metal salt of benzoic acid, a metal salt of salicylic acid, a metal salt of alkylsalicylic acid, a metal salt of catechol, a metal-containing bisazo dye, a tetraphenylborate derivative, a quaternary ammonium salt, and an alkylpyridinium salt. A compound selected from the group consisting of: a resin-type charge control agent containing a polar group: and the like.
Examples of the inorganic particles include known inorganic particles such as silica particles, titanium oxide particles, alumina particles, cerium oxide particles, or particles obtained by subjecting these surfaces to hydrophobic treatment. These inorganic particles may be subjected to various surface treatments. For example, the inorganic particles may be subjected to surface treatment with a silane coupling agent, a titanium coupling agent, silicone oil, or the like.

-Physical properties of toner particles The volume average particle size of the toner particles is, for example, 2.0 μm or more and 10 μm or less, and preferably 3.5 μm or more and 8.0 μm or less.
In addition, the following method is mentioned as a measuring method of the volume average particle diameter of toner particles. First, 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, and this is added to 100 ml to 150 ml of an electrolytic solution. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for 1 minute, and a particle size of 50 μm is used with an aperture having a diameter of 50 μm by a Coulter Multisizer II type (manufactured by Beckman-Coulter). The particle size distribution of particles in the range of 1.0 μm to 30 μm is measured. The number of particles to be measured is 50,000. Based on the obtained particle size distribution, a volume cumulative distribution is drawn from the small particle size side with respect to the divided particle size range (channel), and the particle size that becomes 50% cumulative is defined as the volume average particle size D50v.
When measuring powders such as external additives, 2 g of a measurement sample is added to 50 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzene sulfonate, and 2 in an ultrasonic disperser (1,000 Hz). The sample is prepared by dispersing for a minute, and the measurement is performed by the method for the sample in the state of the dispersion described above.

Examples of the toner particle shape factor SF1 include a range of 110 to 140.
Here, the shape factor SF1 is obtained by the following equation.
Formula: SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, ML represents the absolute maximum length of the toner particles, and A represents the projected area of the toner particles.
The SF1 is quantified by, for example, analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer. Specifically, for example, an optical microscope image of the toner dispersed on the surface of the slide glass is taken into a Luzex image analyzer through a video camera, the maximum length and the projected area of 50 or more toner particles are obtained, and calculated by the above formula, It is obtained by obtaining the average value.

Toner Particle Manufacturing Method Next, a toner particle manufacturing method will be described.
The toner particles can be obtained by aggregating and fusing each particle in a raw material dispersion in which at least crystalline resin particles are dispersed in an aqueous medium. Further, amorphous resin particles may be included.

Hereinafter, an example of a method for producing toner particles will be described in detail.
However, in the following description, “resin particles” indicate at least one of polyester resin particles and vinyl resin particles, or resin particles containing at least both polyester resin and vinyl resin.
Further, although a method for obtaining toner particles containing a release agent will be described, the release agent may not be included. Of course, you may use other additives other than a coloring agent and a mold release agent.

~ Resin particle dispersion preparation process ~
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.

  Here, 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 media, 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.).

  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.

  For example, a colorant dispersion or a release agent dispersion is also prepared by applying a dispersion method in the resin particles. 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 particles.

~ Aggregated particle formation process ~
Next, a colorant particle dispersion and a release agent dispersion are mixed together with the resin particle dispersion.
Then, in the mixed dispersion, the resin particles, the colorant particles, and the release agent particles that are the binder resin are hetero-aggregated, and the resin particles and the colorant particles having a diameter close to the diameter of the target toner particles are separated. Aggregated particles containing mold agent 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 optionally a dispersion stabilizer is added, and then resin particles Is heated to a temperature lower than the glass transition temperature (specifically, for example, the glass transition temperature of the resin particles −30 ° C. or more and −10 ° C. or less), and the particles dispersed in the mixed dispersion liquid are aggregated to form aggregated particles. Form.
In the agglomerated particle forming step, for example, the aggregating agent 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, the pH is 2 or more and 5 or less). ) And optionally 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.
Additives that form complexes or similar bonds with the metal ions of the flocculant may optionally be used. As this additive, a chelating agent is preferably used.

Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic substances 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 polyester resin particles as the binder resin, and 0.1 parts by mass or more and 3 parts by mass or less. It may be 0.0 parts by mass or less.

~ Fusion coalescence process ~
Next, with respect to the aggregated particle dispersion in which the aggregated particles are dispersed, for example, a glass transition temperature or higher of the polyester resin particles as the binder resin (for example, a temperature of 10 to 30 ° C. higher than or higher than the glass transition temperature of the resin particles And the aggregated particles are fused and united to form toner particles.
Through the above steps, toner particles are obtained.

Here, after the fusion and coalescence process is completed, the 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 desirable 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, etc. are preferably used from the viewpoint of productivity. Furthermore, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used.

[External additives]
In the toner according to the exemplary embodiment, at least an external additive such as silica particles is externally added to the toner particles.
Examples of the method of externally adding the external additive include a method of mixing with a known mixer such as a V-type blender, a Henschel mixer, and a Redige mixer.

  In addition, other additives other than sol-gel silica may be externally added. Examples of other additives include fluidizing agents, cleaning aids such as polystyrene particles, polymethyl methacrylate particles, and polyvinylidene fluoride particles, and transfer agents. An auxiliary agent etc. are mentioned.

<Electrophotographic developer>
The electrophotographic developer according to the present embodiment includes at least the toner according to the present embodiment.
The electrophotographic developer according to this embodiment may be a one-component developer containing 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, a magnetic dispersion carrier, a resin dispersion carrier, and the like.

  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 and Image Forming Method>
Next, an image forming apparatus and an image forming method according to the present embodiment using the electrophotographic toner (electrophotographic developer) according to the present embodiment will be described.
The image forming apparatus according to the present embodiment includes an image carrier, a charging device that charges the image carrier, an electrostatic charge image forming device that forms an electrostatic image on the surface of the charged image carrier, and the present embodiment. A developing device that accommodates the electrophotographic toner according to the embodiment and develops the electrostatic image formed on the image carrier as a toner image with the electrophotographic toner, and the toner image formed on the image carrier And a transfer device that transfers the image onto the transfer medium.

  According to the image forming apparatus of the present embodiment, a charging step for charging the image carrier, an electrostatic charge image forming step for forming an electrostatic image on the surface of the charged image carrier, and the image carrier on the image carrier. A development step of developing the formed electrostatic charge image as a toner image with the electrophotographic toner according to the present embodiment, and a transfer step of transferring the toner image formed on the image carrier onto the transfer target. An image forming method is carried out.

  Image formation in the image forming apparatus according to the present embodiment is performed, for example, as follows when an electrophotographic photosensitive member is used as an image holding member. First, the surface of the electrophotographic photosensitive member is charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic charge image. Next, the toner is attached to the electrostatic latent image in contact with or in proximity to a developing roll having a developer layer formed on the surface, thereby forming a toner image on the electrophotographic photosensitive member. The formed toner image is transferred onto the surface of a recording medium such as paper using a corotron charger or the like. Further, the toner image transferred to the surface of the recording medium is fixed by a fixing device, and an image is formed on the recording medium.

In the image forming apparatus according to the present embodiment, for example, the part including the developing unit may have a cartridge structure (toner cartridge, process cartridge, etc.) that is detachable from the image forming apparatus.
As the toner cartridge, for example, a toner cartridge that accommodates the electrophotographic toner according to the present embodiment and is detachable from the image forming apparatus is preferably used.
As the process cartridge, for example, the electrostatic charge developing developer according to this embodiment is accommodated, and the electrostatic latent image formed on the surface of the image carrier is developed with the electrostatic charge developing developer to form a toner image. A process cartridge that includes a developing means for forming the image forming unit and is detachable from the image forming apparatus is preferably used.

  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 juxtaposed at a predetermined distance from each other. The units 10Y, 10M, 10C, and 10K may be process cartridges that can be attached to and detached 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. A toner including the four colors of toner 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. Around the photosensitive member 1Y, a charging roller 2Y for charging the surface of the photosensitive member 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on the color-separated image signal to form an electrostatic charge image. An exposure device (electrostatic image forming means) 3 for forming, a developing device (developing means) 4Y for supplying the charged toner to the electrostatic image and developing the electrostatic image, and transferring the developed toner image onto the intermediate transfer belt 20 A primary transfer roller 5Y (primary transfer unit) that performs the transfer and a photoconductor cleaning device (cleaning unit) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer are sequentially arranged.
The primary transfer roller 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described. First, prior to the operation, the surface of the photoreceptor 1Y is charged to a potential of about −600V to −800V by the charging roller 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (a resistance equivalent to that of a general resin), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic 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, the electrophotographic developer according to this embodiment including at least yellow toner and a carrier is stored. 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 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, and the transfer bias is applied to the intermediate transfer belt 20. The toner image is transferred onto the recording paper P. Note that the secondary transfer bias at this time is determined according to the resistance detected by a resistance detecting means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

  Thereafter, the recording paper P is fed to the pressure contact portion (nip portion) of the pair of fixing rolls in the fixing device (roll-type fixing means) 28, the toner image is heated, and the color-superposed toner image is melted to record the recording paper. Fixed onto P.

  Examples of the transfer target to which the toner image is transferred include plain paper and OHP sheet used for electrophotographic copying machines, printers, and the like. For example, coated paper in which the surface of plain paper is coated with resin, art paper for printing, and the like are 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 the present invention is not limited to this configuration, and the toner image is directly transferred from the photoconductor. It may be a structure that is transferred to a recording sheet.

<Process cartridge, toner cartridge>
FIG. 2 is a schematic configuration diagram showing a preferred example embodiment of a process cartridge containing an electrophotographic developer according to this embodiment. The process cartridge 200 is mounted with a charging roller 108, a developing device 111, a photosensitive member cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure together with the photosensitive member 107, and a rail 116 is used. Combined 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. May be combined. In the process cartridge of this 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 stores toner for electrophotography and is detachable from 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 the developing devices (colors). 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 Example and a comparative example are given and this embodiment is described in detail more concretely, this embodiment is not limited to these Examples at all. Further, “part” means “part by mass” unless otherwise specified.

[Example 1]
<Synthesis of crystalline polyester resin containing nitrogen atom (PES-C1)>
The following components were put into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, and after the inside of the reaction vessel was replaced with dry nitrogen gas, titanium tetrabutoxide (reagent) was replaced with the polymerizable monomer. 0.3 part was added to 100 parts of the component. After stirring and reacting at 170 ° C. for 3 hours under a nitrogen gas stream, the temperature was further raised to 210 ° C. over 1.5 hours, the pressure in the reaction vessel was reduced to 3 kPa, and the reaction was performed when the required molecular weight was reached. And a crystalline polyester resin (PES-C1) containing a nitrogen atom in the cyclic structure portion was obtained. The composition is shown in Table 1 (the compositions shown in Tables 1 and 2 below are indicated by “mol%”), and the physical properties of the obtained crystalline polyester resin (PES-C1) are shown in Table 3.
・ 49 mol% of 1,10-decanedicarboxylic acid
・ 2,6-pyridinedicarboxylic acid 1mol%
・ 1,9-nonanediol 50mol%

<Preparation of crystalline polyester resin dispersion (DA-C1)>
In a reactor with a jacket (Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, a thermometer, a water dropping device and an anchor blade, 300 parts of the crystalline polyester resin (PES-C1) and methyl ethyl ketone (solvent) ) 160 parts and 100 parts of isopropyl alcohol (solvent) were added, and the resin was dissolved while stirring and mixing at 100 rpm while maintaining the temperature at 70 ° C. in a water circulating thermostat.
Thereafter, the rotational speed of stirring was set to 150 rpm, the water circulation type thermostatic bath was set to 66 ° C., 15 parts of 10% by mass aqueous ammonia solution was dropped in 5 minutes, mixed for 10 minutes, and then 900 parts of ion-exchanged water kept at 66 ° C. Was added dropwise at a rate of 5 parts per minute to invert the phase to obtain an emulsion.
Immediately thereafter, 800 parts of the obtained emulsion and 700 parts of ion-exchanged water were placed in an eggplant flask and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, the mixture was heated in a hot water bath at 60 ° C., and the solvent was removed by reducing the pressure to 7 kPa while paying attention to bumping. When the solvent recovery amount reached 1100 parts, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a dispersion. There was no solvent odor in the obtained dispersion.
The volume average particle diameter D50v of the resin particles in this dispersion was 130 nm. Then, ion exchange water was added and it adjusted so that solid content concentration might be 20 mass%. This was used as a crystalline polyester resin dispersion (DA-C1).

<Synthesis of Amorphous Polyester Resin (PES-A1)>
Into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, a polymerizable monomer other than dodecenyl succinic acid was charged according to the composition of Table 5, and the inside of the reaction vessel was replaced with dry nitrogen gas. Tin dioctanoate was added in an amount of 0.3% by mass based on the total amount of the polymerizable monomer components. After stirring and reacting at 180 ° C. for 6 hours under a nitrogen gas stream, the temperature was further raised to 235 ° C. over 1 hour, reacted for 3 hours, cooled to 220 ° C., and 10.0 mmHg in the reaction vessel. The pressure was reduced to 1, and the reaction was stirred for 1 hour. After returning to normal pressure, dodecenyl succinic acid in Table 5 was added and reacted, and the reaction was terminated when the required molecular weight was reached. Table 5 shows the physical properties (glass transition temperature, mass average molecular weight (Mw), number average molecular weight (Mn), peak top molecular weight (Mp), acid value, 1/2 drop temperature) of the obtained amorphous polyester resin. It was.

<Synthesis of Amorphous Polyester Resin (PES-A2)>
In accordance with the composition shown in Table 5, a polymerizable monomer other than dodecenyl succinic acid and trimellitic anhydride is charged into a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube, and dry nitrogen gas is contained in the reaction vessel. Then, 0.3% by mass of tin dioctanoate was added to the total amount of the polymerizable monomer components. After stirring and reacting at 180 ° C. for 6 hours under a nitrogen gas stream, the temperature was further raised to 235 ° C. over 1 hour, reacted for 3 hours, cooled to 220 ° C., and 10.0 mmHg in the reaction vessel. The pressure was reduced to 1, and the reaction was stirred for 1 hour. After returning to normal pressure, the dodecenyl succinic acid of Table 5 was added and reacted for 2 hours, then trimellitic anhydride was added and further reacted, and the reaction was terminated when the required molecular weight was reached. Table 5 shows the physical properties (glass transition temperature, mass average molecular weight (Mw), number average molecular weight (Mn), peak top molecular weight (Mp), acid value, 1/2 drop temperature) of the obtained amorphous polyester resin. It was.

<Preparation of Amorphous Polyester Resin Particle Dispersions (DA-A1) and (DA-A2)>
While maintaining a jacketed reactor equipped with a condenser, thermometer, water dropping device and anchor blade (Tokyo Rika Kikai Co., Ltd .: BJ-30N) at 40 ° C. in a water circulating thermostatic chamber, acetic acid was added to the reactor. A mixed solvent of 180 parts of ethyl and 80 parts of isopropyl alcohol is added, and 300 parts of the above amorphous polyester resin (PES-A1) is added thereto, stirred at 150 rpm using a three-one motor, dissolved, and oiled. Got the phase. To this stirred oil phase, a mixed solution of 1 part of 10% by weight aqueous ammonia solution and 47 parts of 5% by weight aqueous sodium hydroxide solution was added dropwise over 5 minutes, mixed for 10 minutes, and then 900 parts of ion-exchanged water was further added. An emulsion was obtained by dripping at a rate of 5 parts per minute to invert the phase.
Immediately, 800 parts of the obtained emulsified liquid and 700 parts of ion-exchanged water were put into an eggplant flask and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, the mixture was heated in a hot water bath at 60 ° C., and the solvent was removed by reducing the pressure to 7 kPa while paying attention to bumping. When the solvent recovery amount reached 1,100 parts, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a dispersion. There was no solvent odor in the obtained dispersion. The volume average particle diameter D50v of the resin particles in this dispersion was 130 nm. Then, alkyldiphenyl oxide disulfonic acid sodium salt (Dowfax 2A-1 manufactured by Dow Chemical Co., Ltd.) was added in an amount of 2.5% by mass based on the resin solid content, and the pH was adjusted to 4.5 with nitric acid, and then ion-exchanged water. To adjust the solid content concentration to 20% by mass. This was designated as an amorphous polyester resin dispersion (DA-A1).

  In addition, in the preparation of the amorphous polyester resin particle dispersion (DA-A1), the amorphous polyester resin (PES-A1) used was changed to an amorphous polyester resin (PES-A2), except that Thus, an amorphous polyester resin dispersion (DA-A2) was obtained.

<Preparation of black colorant dispersion (PDK1)>
Carbon black (Cabot Japan Co., Ltd., REAGAL 330): 200 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC): 33 parts (60% by mass of active ingredient, based on colorant) 10% by mass)
-Ion exchange water: 750 parts When the above components are all charged, the above components are charged into a stainless steel container whose liquid level is 1/3 of the height of the container, and 280 parts of ion exchange water After adding an anionic surfactant and sufficiently dissolving the surfactant, all the pigments are added, and the mixture is stirred using a stirrer until there are no wet pigments, and the remaining ion exchange water is added. The mixture was sufficiently degassed by stirring.
After defoaming, the mixture was dispersed for 10 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then defoamed by stirring for one day with a stirrer. After defoaming, the mixture was dispersed again at 6,000 rpm for 10 minutes using a homogenizer, and then stirred for one day and night with a stirrer to defoam.
After defoaming, dispersion was performed at a pressure of 240 MPa using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). The dispersion was equivalent to 25 passes in terms of the total charge and the processing capacity of the apparatus.
The obtained dispersion was allowed to stand for 72 hours to remove precipitates, and ion exchanged water was added to adjust the solid content concentration to 15% by mass to obtain a black colorant dispersion (PDK1). The volume average particle diameter D50v of the particles in this colorant dispersion was 110 nm. For the volume average particle diameter D50v, an average value of three measurement values excluding a maximum value and a minimum value out of five times measured with a microtrack was used.

<Preparation of magenta colorant dispersion (PDM1)>
In the preparation of the black colorant dispersion (PDK1), magenta coloring was carried out in the same manner except that the colorant was changed from carbon black to magenta pigment (Dainipei Seika Co., Ltd., Pigment Red 122, for electrophotography). An agent dispersion was prepared.

<Preparation of yellow colorant dispersion (PDY1)>
In the preparation of the black colorant dispersion (PDK1), magenta coloring was performed in the same manner except that the colorant was changed from carbon black to yellow pigment (Dainipei Seika Co., Ltd., Pigment Yellow 74, for electrophotography). An agent dispersion was prepared.

<Preparation of Cyan Colorant Dispersion (PDC1)>
In the preparation of the colorant dispersion (PDK1), the same procedure was followed except that the colorant was changed from carbon black to a cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3, for electrophotography). A colorant dispersion was prepared.

<Preparation of release agent dispersion (DW1)>
Hydrocarbon wax (manufactured by Nippon Seiki Co., Ltd., trade name: FNP0090, melting temperature Tw = 90.2 ° C.): 270 parts Anionic surfactant (Taika Power BN2060, manufactured by Teika Co., Ltd.) Active ingredient amount: 60% by mass): 13.5 parts (as active ingredient, 3.0% by mass with respect to the release agent)
-Ion-exchanged water: 700 parts The above components were mixed, and the release agent was dissolved at an internal liquid temperature of 120 ° C with a pressure discharge type homogenizer (Gorin homogenizer manufactured by Gorin), and then at a dispersion pressure of 5 MPa for 120 minutes. The dispersion was treated at 40 MPa for 360 minutes and cooled to obtain a release agent dispersion (DW1). The volume average particle diameter D50v of the particles in this release agent dispersion is 220 nm. Then, ion exchange water was added and it adjusted so that solid content concentration might be 20.0 mass%.

(Production of toner particles)
-Crystalline polyester resin particle dispersion (DA-C1) 100 parts-Amorphous polyester resin particle dispersion (DA-A1) 380 parts-Amorphous polyester resin particle dispersion (DA-A2) 380 parts-Black coloring Agent dispersion (PDK1) 110 parts Release agent dispersion (DW1) 120 parts Aluminum sulfate aqueous solution 150 parts (Asada Chemical Industry Co., Ltd., 1% by weight aqueous solution of aluminum sulfate powder)
The above components were mixed and dispersed in a round stainless steel flask with a homogenizer (manufactured by IKA, Ultra Turrax T50) at 5000 rpm for 10 minutes, and then the contents in the flask were heated and stirred to 50 ° C. while stirring the contents in the flask. Held in. When the particle size reached 5.0 μm, a mixed dispersion of 150 parts by mass of the amorphous polyester resin particle dispersion (DA-A1) and 150 parts by mass of the amorphous polyester resin particle dispersion (DA-A2) was prepared. It was charged and held for 60 minutes. When the obtained contents were observed with an optical microscope, it was confirmed that aggregated particles were generated. After adding 9 parts by mass of ethylenediaminetetraacetic acid (EDTA) tetrasodium salt (manufactured by Kirest Co., Ltd., Kirest 40), an aqueous sodium hydroxide solution was added to adjust the pH to 8, and then the temperature was raised to 92 ° C. After that, the pH is lowered by 0.1 with nitric acid every 15 minutes, and when the shape factor SF1 becomes 130, after cooling, it is filtered, sufficiently washed with ion-exchanged water, and dried to obtain toner particles 1. It was.

  In the above method, the colorant dispersion (PDK1) used was changed to a magenta colorant dispersion (PDM1), a yellow colorant dispersion (PDY1), and a cyan colorant dispersion (PDC1), respectively. M, Y, and C toner particles were obtained by the above method.

  To 100 parts by mass of the toner particles obtained above, 1.5 parts by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed and blended at 13000 rpm for 30 seconds using a sample mill. Thereafter, each color toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

<Preparation of resin-coated carrier (C)>
Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 parts by mass Toluene: 14 parts by mass A cyclohexyl methacrylate / dimethylaminoethyl methacrylate copolymer (weight ratio 99: 1, Mw 80000): 2.0 Mass parts / carbon black (VXC72: manufactured by Cabot): 0.12 mass parts The above components excluding ferrite particles and glass beads (φ1 mm, equivalent to toluene) were stirred at 1200 rpm for 30 minutes using a sand mill manufactured by Kansai Paint Co., Ltd. Thus, a resin coating layer forming solution was obtained. Furthermore, this resin coating layer forming solution and ferrite particles were put into a vacuum degassing type kneader, decompressed, distilled off toluene, and dried to prepare a resin-coated carrier (C).

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

[Examples 2-19, Comparative Examples 1-2]
In the synthesis of the crystalline polyester resin (PES-C1), except that the composition was changed to the materials shown in Table 1 or 2, the crystalline polyester resin (PES-C2) to ( PES-C21) and crystalline polyester resin dispersions (DA-C2) to (DA-C21) were obtained. The physical properties of the obtained crystalline polyester resin are shown in Tables 3 and 4.
Furthermore, each color developer was obtained by the operation described in Example 1 except that the following crystalline polyester resin dispersions (DA-C2) to (DA-C21) were used.

<Evaluation method>
The developer of the DocuColor 1450 GA manufactured by Fuji Xerox Co., Ltd., toner cartridge, and the vicinity of the toner replenishment mechanism in the main body are cleaned in an environment room at a temperature of 25 ° C. and a humidity of 60%. The toner of each color was put in the toner cartridge of each color and set to the original position of the DocuColor 1450 GA main body. Subsequently, in order to charge the developer, 20 sheets of A3 paper were passed without being developed. Next, using an OHP film (Fuji Xerox Co., Ltd.), the development amount of colored toner on paper was adjusted to 4.0 g / m ² .
Next, five linear images having a line width of 5 mm and a length of 50 mm were produced in parallel with the OHP paper feeding direction at intervals of 30 mm and fixed in the OHP mode.
Next, the OHP was folded in a direction perpendicular to the straight line image at a half position in the length direction of the OHP, a load of 1000 g was applied to the entire surface of the folded OHP, and the load was removed after being left for 10 seconds.
Observed the image part of the folded OHP, there is no image defect (A), there is an image defect but the width is less than 0.5 mm (B), there is an image defect, but the width is 0.5 mm to 1.0 mm The evaluation was as follows (C), where there was an image defect and the width was greater than 1.0 mm (D).

1Y, 1M, 1C, 1K, 107 photoconductor (image carrier), 2Y, 2M, 2C, 2K, 108 charging roller, 3Y, 3M, 3C, 3K laser beam, 3 exposure device, 4Y, 4M, 4C, 4K , 111 Developing device (developing unit), 5Y, 5M, 5C, 5K Primary transfer roller, 6Y, 6M, 6C, 6K, 113 Photoconductor cleaning device (cleaning unit), 8Y, 8M, 8C, 8K Developer cartridge, 10Y, 10M, 10C, 10K units, 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 apparatus, 116 mounting rail, 117 opening for static elimination exposure, 118 opening for exposure, 200 process cartridge , P, 300 recording paper (transfer member)

Claims (8)

  An electrophotographic toner containing a crystalline resin obtained by polymerizing a polymerizable monomer (A) having a nitrogen atom and a cyclic structure in a structure which becomes a structural unit of a polymer after being polymerized.   The electrophotographic toner according to claim 1, wherein the polymerizable monomer (A) contains at least the nitrogen atom in the cyclic structure portion.   The crystalline resin is a resin obtained by polymerizing the polymerizable monomer (A) in an amount of 3 mol% or more and 15 mol% or less with respect to 100 mol% of the total polymerizable monomer constituting the crystalline resin. The toner for electrophotography according to claim 1, wherein the toner is an electrophotographic toner.   An electrophotographic developer comprising at least the electrophotographic toner according to claim 1. Containing the toner for electrophotography according to claim 1;
A toner cartridge to be attached to and detached from the image forming apparatus.   A developing device comprising: a developing member that accommodates the electrophotographic toner according to claim 1 and develops the electrostatic image formed on the image carrier as a toner image with the electrophotographic toner. An image carrier,
A charging device for charging the image carrier;
An electrostatic charge image forming apparatus for forming an electrostatic charge image on the surface of the charged image carrier;
A developing device containing the electrophotographic toner according to claim 1 and developing the electrostatic image formed on the image carrier as a toner image with the electrophotographic toner;
A transfer device for transferring a toner image formed on the image carrier onto a transfer target;
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 an electrostatic image formed on the image carrier as a toner image with the electrophotographic toner according to claim 1;
A transfer step of transferring a toner image formed on the image carrier onto a transfer target;
An image forming method comprising: