JP2016051048A - Toner for electrostatic charge image development, 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 that achieves both low-temperature fixability and heat resistance.SOLUTION: There is provided a toner for electrostatic charge image development that includes: a binder resin including an amorphous polyester composite resin having a vinyl resin unit and a polyester resin unit chemically bonded to each other, and a crystalline polyester resin, where the mass ratio of the crystalline polyester resin and the amorphous polyester composite resin (the crystalline polyester resin/the amorphous polyester composite resin) is 14/86 or more 30/70 or less; and at least one selected from the group consisting of vinyl resin particles and urethane resin particles.SELECTED DRAWING: None

Description

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

Various toners for developing an electrostatic image applied to an electrophotographic image forming apparatus have been proposed.
For example, Patent Document 1 states that “a toner containing at least a first polymer and a second polymer, wherein the first polymer is the sea, and the first polymer has crystallinity. A toner having a sea-island structure in which a second polymer is dispersed is disclosed.

JP 2012-068589 A

  An object of the present invention is to provide a toner for developing an electrostatic image that has both low-temperature fixability and heat resistance.

The above problem is solved by the following means.
That is, the invention according to claim 1
A non-crystalline polyester composite resin in which a vinyl resin unit and a polyester resin unit are chemically bonded, and a crystalline polyester resin, and a mass ratio of the crystalline polyester resin and the amorphous polyester composite resin (described above) A binder resin having a crystalline polyester resin / the amorphous polyester composite resin) of 14/86 or more and 30/70 or less;
At least one selected from the group consisting of vinyl resin particles and urethane resin particles;
A toner for developing an electrostatic charge image.

The invention according to claim 2
2. The electrostatic image developing toner according to claim 1, wherein the vinyl resin unit is a styrene (meth) acrylic resin unit.

The invention according to claim 3
Polyester resin in which the polyester resin unit is a polycondensation of a polyhydric alcohol containing an alkylene oxide adduct of bisphenol A in an amount of 50 mol% to 100 mol% with respect to the whole polyhydric alcohol, and a polyvalent carboxylic acid. The electrostatic image developing toner according to claim 1, wherein the toner is a unit.

The invention according to claim 4
4. The mass ratio of the vinyl resin unit and the polyester resin unit (the vinyl resin unit / the polyester resin unit) is 10/90 or more and 30/70 or less. 5. This is a toner for developing an electrostatic image.

The invention according to claim 5
The toner for developing an electrostatic charge image according to claim 1, wherein the vinyl resin particles are styrene (meth) acrylic resin particles.

The invention according to claim 6
6. The electrostatic image developing toner according to claim 1, wherein the vinyl resin particles are contained in an amount of 10% by mass or more and 20% by mass or less based on the whole toner.

The invention according to claim 7 provides:
7. The electrostatic charge image developing toner according to claim 1, wherein the vinyl resin particles have a volume average particle diameter of 80 nm or more and 250 nm or less.

The invention according to claim 8 provides:
The electrostatic charge image according to any one of claims 1 to 7, wherein the crystalline polyester resin is an aliphatic polyester resin obtained by condensation polymerization of an aliphatic polyvalent carboxylic acid and an aliphatic polyhydric alcohol. Development toner.

The invention according to claim 9 is:
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1.

The invention according to claim 10 is:
The toner for developing an electrostatic charge image according to any one of claims 1 to 8 is accommodated,
The toner cartridge is detachable from the image forming apparatus.

The invention according to claim 11 is:
A developing means for containing the electrostatic charge image developer according to claim 9 and developing the electrostatic charge image formed on the surface of the image carrier 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 12
An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic charge image developer according to claim 9 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus.

The invention according to claim 13 is:
A charging step for charging the surface of 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 charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 9;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
Is an image forming method.

  According to the first aspect of the present invention, the toner containing the polyester resin and the vinyl resin particles is fixed at a lower temperature than the case where an amorphous polyester resin that is not combined with the vinyl resin is used as the polyester resin. Provided is a toner for developing an electrostatic charge image that is compatible with heat resistance and heat resistance.

  According to the invention of claim 2, in the toner containing the polyester resin and the vinyl resin particles, the vinyl resin is used in comparison with the case where an amorphous polyester resin not combined with the vinyl resin is used as the polyester resin. Provided is an electrostatic charge image developing toner that includes an amorphous polyester composite resin having a styrene (meth) acrylic resin unit as a unit and has both low-temperature fixability and heat resistance.

  According to the invention of claim 3, the polyester resin unit of the amorphous polyester composite resin comprises a polyhydric alcohol containing an alkylene oxide adduct of bisphenol A in an amount of less than 50 mol% in the polyhydric alcohol component; As compared with the case where the polyester unit is obtained by polycondensation with carboxylic acid, a toner for developing an electrostatic charge image having both low-temperature fixability and heat resistance is provided.

  According to the fourth aspect of the present invention, the low-temperature fixing is performed as compared with the case where the mass ratio of the vinyl resin unit to the polyester resin unit (vinyl resin unit / polyester resin unit) is less than 10/90 or more than 30/70. Provided is a toner for developing an electrostatic charge image that is compatible with heat resistance and heat resistance.

  According to the invention according to claim 5, in the toner including the polyester resin and the vinyl resin particles, the vinyl resin is used as the polyester resin, compared with the case where the amorphous polyester resin not combined with the vinyl resin is used. Provided is a toner for developing an electrostatic charge image that includes styrene (meth) acrylic resin particles as particles and has both low-temperature fixability and heat resistance.

  According to the invention of claim 6, there is provided a toner for developing an electrostatic charge image having both low temperature fixability and heat resistance as compared with the case where the vinyl resin particles are contained in the toner at less than 10% by mass. .

  According to the seventh aspect of the present invention, there is provided an electrostatic image developing toner that achieves both low temperature fixability and heat resistance as compared with the case where the volume average particle size of the vinyl resin particles exceeds 250 nm.

  According to the invention according to claim 8, in the toner containing the polyester resin and the vinyl resin particles, the polyester resin is aliphatic compared to the case where an amorphous polyester resin that is not combined with the vinyl resin is used. Provided is a toner for developing an electrostatic charge image that includes a crystalline polyester resin obtained by polycondensation of an aliphatic polyvalent carboxylic acid and an aliphatic polyhydric alcohol as the polyvalent carboxylic acid, and has both low-temperature fixability and heat resistance. The

  According to the invention according to claim 9, 10, 11, 12, or 13, in the toner containing the polyester resin and the vinyl resin particles, an amorphous polyester resin not compounded with the vinyl resin is used as the polyester resin. An electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming apparatus, or an image forming method that provides both low-temperature fixability and heat resistance as compared with the case where the toner used is applied.

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

  Hereinafter, an embodiment which is an example of the present invention will be described in detail.

<Toner for electrostatic image development>
The toner for developing an electrostatic charge image (hereinafter referred to as “toner”) according to the present embodiment includes an amorphous polyester composite resin (hereinafter referred to as “amorphous”) in which a vinyl resin unit and a polyester resin unit are chemically bonded. A binder resin containing a crystalline polyester resin and at least one selected from the group consisting of vinyl resin particles and urethane resin particles.
And content of crystalline polyester resin and amorphous polyester composite resin is the range of 14/86 or more and 30/70 or less by mass ratio (crystalline polyester resin / amorphous polyester composite resin).

  The toner according to the exemplary embodiment achieves both low-temperature fixability and heat resistance by the above configuration. The reason for this is not clear, but is presumed to be as follows.

  As the binder resin in the toner, for example, means for obtaining low-temperature fixability during image formation by incorporating an amorphous polyester resin and a crystalline polyester resin is employed. By including the crystalline polyester resin, the glass transition temperature of the entire polyester resin is lowered and low-temperature fixability is imparted, but the heat resistance tends to be lowered. When the heat resistance is lowered, for example, in the developing means of the image forming apparatus, toner agglomeration is likely to occur due to the action of an external force such as agitation on the toner, and image defects are likely to occur. Therefore, if a binder resin containing an amorphous polyester resin and a crystalline polyester resin and, for example, vinyl resin particles are contained, it is considered that the vinyl resin particles exhibit a filler effect, thereby achieving low-temperature fixing. However, it is easy to suppress a decrease in heat resistance.

  However, in the toner containing the polyester resin and the vinyl resin particles, the vinyl resin particles have a low dispersion state in the toner and are likely to be unevenly distributed, or the vinyl resin particles themselves tend to aggregate. Seen. For this reason, even when vinyl resin particles are contained, the filler effect may be difficult to be exhibited. This is considered due to the low affinity between the polyester resin and the vinyl resin particles.

On the other hand, since the toner according to the exemplary embodiment includes the above-described amorphous polyester composite resin in the binder resin, the toner has higher affinity with the vinyl resin particles than in the case where the above-described polyester resin is used. As the affinity is increased, the vinyl resin particles are highly dispersed in the toner. Thereby, the filler effect by the vinyl resin particles is easily exhibited, and the heat resistance is considered to be improved. As described above, it is considered that the low-temperature fixability and heat resistance of the toner are compatible.
By using a toner having both low-temperature fixability and heat resistance, for example, in the developing unit of the image forming apparatus, toner agglomerates are hardly generated due to the action of external force such as stirring on the toner. It is considered that it is difficult to cause image defects and the like.
Even when urethane resin particles are used, a toner having both low-temperature fixability and heat resistance can be obtained.

  Hereinafter, details of the toner according to the exemplary embodiment will be described.

  The toner according to the exemplary embodiment includes toner particles and, if necessary, external additives.

[Toner particles]
The toner particles constituting the toner according to the exemplary embodiment include an amorphous polyester composite resin and a crystalline polyester resin, and a mass ratio of the crystalline polyester resin and the amorphous polyester composite resin (crystalline polyester resin / amorphous). Polyester composite resin) includes a binder resin in the range of 14/86 to 30/70, vinyl resin particles, and, if necessary, a colorant, a release agent, and other additives. The

The “crystallinity” of the resin means that it has a clear endothermic peak in differential scanning calorimetry (DSC) rather than a stepwise endothermic amount change. Specifically, the temperature rise rate is 10 (° C. / Min) indicates that the half-value width of the endothermic peak is 10 ° C. or less.
On the other hand, “amorphous” of the resin means that the half width exceeds 10 ° C., shows a stepwise endothermic change, or does not show a clear endothermic peak.

(Binder resin)
The binder resin used for the toner according to the exemplary embodiment contains an amorphous polyester composite resin and a crystalline polyester resin. And content of crystalline polyester resin and amorphous polyester composite resin is 14/86 or more and 30/70 or less by mass ratio (crystalline polyester resin / amorphous polyester composite resin). 16/86 or more and 23/77 or less are preferable, and 18/82 or more and 20/80 or less are more preferable from the viewpoint of making it easier to achieve both low-temperature fixability and heat resistance.

-Amorphous polyester composite resin-
The amorphous polyester composite resin according to the present embodiment is not particularly limited as long as it is amorphous and the vinyl resin unit and the polyester resin unit are chemically bonded. For example, having a block polymer structure in which a vinyl resin unit is bonded to the terminal of a polyester resin unit; having a graft polymer structure in which a side chain of a vinyl resin unit is bonded to the main chain of the polyester resin unit Thing; etc. are mentioned.

  In the amorphous polyester composite resin according to this embodiment, from the viewpoint of making it easier to achieve both low temperature fixability and heat resistance, the mass ratio of the vinyl resin unit and the polyester resin unit (vinyl resin unit / polyester resin unit) is: It is preferably in the range of 5/95 or more and 40/60 or less. More preferably, it is 10/90 or more and 30/70 or less. A range of 10/90 or more and 20/80 or less is particularly preferable.

  A known manufacturing method can be applied to the amorphous polyester composite resin according to the present embodiment. For example, (1) A method in which a polyester resin for forming a polyester resin unit is preliminarily polymerized, and a monomer for forming a vinyl resin unit is reacted in the presence of the polyester resin subjected to the polycondensation (for example, (2) A method of polymerizing a polyester containing a monomer having a radical bonding property which is polycondensed with a vinyl monomer after adding a monomer having a radical bonding property when the polyester is subjected to condensation polymerization, and then polycondensing the polyester); (2 ) A method in which a vinyl resin for forming a vinyl resin unit is polymerized in advance, and in the presence of the polymerized vinyl resin, a polyhydric alcohol and a polyvalent carboxylic acid for forming a polyester resin unit are subjected to polycondensation ( For example, a radically polymerizable compound having a carboxylic acid or alcohol component and a vinyl resin monomer are copolymerized. A method of polycondensing a vinyl resin having a carboxylic acid or an alcohol component together with a polyhydric alcohol and a polyvalent carboxylic acid); (3) pre-polymerizing a vinyl resin for forming a vinyl resin unit to form a polyester resin unit The polyester resin to be condensed is preliminarily polymerized and then a method of reacting the vinyl resin with the polyester resin (for example, a reactive group is added during the polymerization of the vinyl resin and the polycondensation of the polyester resin. And a method of reacting a vinyl resin and a polyester resin).

-Vinyl resin unit As a vinyl resin which comprises a vinyl resin unit, it is good to use the vinyl resin which shows an amorphous property from a viewpoint of making low-temperature fixability and heat resistance compatible. The monomer for synthesizing this vinyl resin is not particularly limited and may be polymerized using a known monomer.
In addition, as a vinyl resin, a commercial item may be used and what was synthesize | combined may be used.

Hereinafter, the vinyl resin constituting the vinyl resin unit will be described.
“(Meth) acryl” is an expression including both “acryl” and “methacryl”.

Examples of the vinyl resin include styrene and alkyl-substituted styrene (for example, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, etc. ), Halogen-substituted styrene (for example, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, etc.), styrenes such as vinylnaphthalene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid Esters having vinyl groups such as n-propyl, n-butyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, trimethylolpropane trimethacrylate (TMPTMA); acrylonitrile, methacrylate Vinyl nitriles such as ronitrile; Vinyl ethers such as methyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; Acids such as (meth) acrylic acid, maleic acid, cinnamic acid, fumaric acid and vinyl sulfonic acid And vinyl resin units obtained by polymerizing monomers such as ethyleneimine, vinylpyridine, vinylamine and the like;
Other monomers include monofunctional monomers such as vinyl acetate, bifunctional monomers such as ethylene glycol dimethacrylate, nonane diacrylate, decanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, etc. These polyfunctional monomers may be used in combination.
The vinyl resin may be a resin using these monomers alone, or may be a resin that is a copolymer using two or more monomers.
Among these, as the vinyl resin, a copolymer containing styrenes, esters having vinyl groups, and acids as monomers is preferable.

Styrenes may be used alone or in combination of two or more.
Among these, styrene is particularly preferably used as the styrenes from the viewpoint of easy reaction, easy control of the reaction, and availability.

  Among esters having a vinyl group and acids, it is preferable to use a monomer having a (meth) acrylic moiety (hereinafter referred to as “(meth) acrylic acid”). (Meth) acrylic acids include (meth) acrylic acid and various (meth) acrylic esters. (Meth) acrylic acids may be used alone or in combination of two or more.

For example, as the (meth) acrylic acid alkyl ester, in addition to the monomers listed above, (meth) acrylic acid n-pentyl, acrylic acid n-hexyl, (meth) acrylic acid n-heptyl, (meta ) N-octyl acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate, n- (meth) acrylate Octadecyl, isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isopentyl (meth) acrylate, amyl (meth) acrylate, neopentyl (meth) acrylate, (meth) acrylic Isohexyl acid, isoheptyl (meth) acrylate, isooctyl (meth) acrylate, (meth) acrylic acid Kurohekishiru include (meth) t-butyl cyclohexyl acrylate.
Examples of (meth) acrylic acid aryl esters include phenyl (meth) acrylate, biphenyl (meth) acrylate, diphenylethyl (meth) acrylate, t-butylphenyl (meth) acrylate, and terphenyl acrylate. Can be mentioned.
Further, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, β-carboxyethyl (meth) acrylate, (meth) Examples include acrylamide.

The vinyl resin unit of the amorphous polyester composite resin according to this embodiment is a monomer of styrenes from the viewpoint of easy synthesis of the resin and the viewpoint of making it easier to achieve both low-temperature fixability and heat resistance. Particularly preferred is a styrene (meth) acrylic resin unit obtained by copolymerizing a monomer of (meth) acrylic acid. Further, from the viewpoint of achieving both low-temperature fixability and heat resistance, it is preferable to exhibit amorphousness.
The mass ratio of styrenes to (meth) acrylic acids (styrenes / (meth) acrylic acids) is preferably in the range of 85/15 to 70/30, for example.

The glass transition temperature (Tg) of the vinyl resin is preferably 40 ° C. or higher and 70 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower.
The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, described in the method for determining the glass transition temperature in JIS K-1987 “Method for Measuring Transition Temperature of Plastics”. It is determined by “extrapolated glass transition start temperature”.

The weight average molecular weight (Mw) of the vinyl resin is preferably 20,000 or more and 200,000 or less, and more preferably 40,000 or more and 100,000 or less.
The molecular weight distribution Mw / Mn of the vinyl resin is preferably 1 or more and 10 or less, and more preferably 2 or more and 6 or less.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed with a THF solvent using a Tosoh GPC / HLC-8120GPC as a measuring device and a Tosoh column / TSKgel SuperHM-M (15 cm). 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 synthesis of the vinyl resin is not particularly limited, and a known polymerization method (radical polymerization method such as emulsion polymerization method, soap-free emulsion polymerization, suspension polymerization, miniemulsion polymerization, microemulsion polymerization) is applied.

-Polyester resin unit As a polyester resin which comprises a polyester resin unit, it is good to show amorphousness from a viewpoint of making low-temperature fixability and heat resistance compatible. In addition, as this polyester resin, a commercial item may be used and what was synthesize | combined may be used.

Hereinafter, the polyester resin constituting the polyester resin unit will be described taking an amorphous polyester resin as an example.
Examples of the amorphous polyester resin include a condensation polymer of a polyvalent carboxylic acid and a polyhydric alcohol.
Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids (eg, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenyl succinic acid, adipic acid, sebacic acid, etc.) Alicyclic dicarboxylic acids (for example, cyclohexanedicarboxylic acid), aromatic dicarboxylic acids (for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc.), their anhydrides, or lower (for example, having 1 or more carbon atoms) 5 or less) alkyl esters. Among these, as polyvalent carboxylic acid, aromatic dicarboxylic acid is preferable, for example.
The polyvalent carboxylic acid may be used in combination with a dicarboxylic acid or a trivalent or higher carboxylic acid having a crosslinked structure or a branched structure. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, anhydrides thereof, and lower (for example, having 1 to 5 carbon atoms) alkyl esters.
Polyvalent carboxylic acid may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyhydric alcohol include aliphatic diols (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (for example, cyclohexanediol, cyclohexanedimethanol, Hydrogenated bisphenol A, etc.) and aromatic diols (for example, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, etc.). Among these, as the polyhydric alcohol, for example, aromatic diols and alicyclic diols are preferable, and aromatic diols are more preferable.
As the polyhydric alcohol, a trihydric or higher polyhydric alcohol having a crosslinked structure or a branched structure may be used together with the diol. Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, and pentaerythritol.
A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

Among these, it is preferable to use an amorphous polyester resin using an aromatic diol as the polyhydric alcohol from the viewpoint of more easily obtaining low-temperature fixability. In particular, it is more preferable to use an alkylene oxide adduct of bisphenol A as the polyhydric alcohol. It is more preferable to use a polyhydric alcohol that the alkylene oxide adduct of bisphenol A contains in an amount of 45 mol% to 100 mol% with respect to the entire polyhydric alcohol. It is more preferable to use a polyhydric alcohol that is contained in an amount of 50 mol% to 100 mol%. 60 mol% or more and 100 mol% or less is particularly preferable.
In addition, when the polyhydric alcohol contains an alkylene oxide adduct of bisphenol A in this range, it is preferable in that the affinity with a crystalline polyester resin described later is increased, and low-temperature fixability is more easily obtained.

The glass transition temperature (Tg) of the amorphous polyester resin is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower.
The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, described in the method for determining the glass transition temperature in JIS K-1987 “Method for Measuring Transition Temperature of Plastics”. It is determined by “extrapolated glass transition start temperature”.

The weight average molecular weight (Mw) of the amorphous polyester resin is preferably from 5,000 to 100,000, more preferably from 7,000 to 50,000.
The number average molecular weight (Mn) of the amorphous polyester resin is preferably 2,000 or more and 100,000 or less.
The molecular weight distribution Mw / Mn of the amorphous polyester resin is preferably 1.5 or more and 100 or less, and more preferably 2 or more and 60 or less.
The weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed with a THF solvent using a Tosoh GPC / HLC-8120GPC as a measuring device and a Tosoh column / TSKgel SuperHM-M (15 cm). 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 amorphous polyester resin can be obtained by a known production method. Specifically, for example, the polymerization temperature is set to 180 ° C. or higher and 230 ° C. or lower, the pressure in the reaction system is reduced as necessary, and the reaction is performed while removing water and alcohol generated during the condensation.
In addition, when the monomer of the raw material is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added and dissolved as a solubilizing agent. In this case, the polycondensation reaction is performed while distilling off the solubilizer. If a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polymerized together with the main component. It is good to condense.

-Crystalline polyester resin-
Examples of the crystalline polyester resin include a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol. In addition, as a crystalline polyester resin, a commercial item may be used and what was synthesize | combined may be used.
Here, since the crystalline polyester resin easily forms a crystal structure, a polycondensate using a polymerizable monomer having a linear aliphatic group is preferable to a polymerizable monomer having an aromatic group.

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids (for example, oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid. Acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc.), aromatic dicarboxylic acid (eg phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid) Dibasic acids such as acids), anhydrides thereof, or lower (for example, having 1 to 5 carbon atoms) alkyl esters.
The polyvalent carboxylic acid may be used in combination with a dicarboxylic acid or a trivalent or higher carboxylic acid having a crosslinked structure or a branched structure. Examples of the trivalent carboxylic acid include aromatic carboxylic acids (for example, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, etc.), these Examples thereof include anhydrides and lower (for example, having 1 to 5 carbon atoms) alkyl esters thereof.
As the polyvalent carboxylic acid, a dicarboxylic acid having a sulfonic acid group or a dicarboxylic acid having an ethylenic double bond may be used in combination with these dicarboxylic acids.
Polyvalent carboxylic acid may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyhydric alcohol include aliphatic diols (for example, linear aliphatic diols having a main chain portion having 7 to 20 carbon atoms). Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18- Examples include octadecanediol and 1,14-eicosandecanediol.
The polyhydric alcohol may be used in combination with a diol and a trivalent or higher alcohol having a crosslinked structure or a branched structure. Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like.
A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

  Here, the polyhydric alcohol may have an aliphatic diol content of 80 mol% or more, and preferably 90 mol% or more.

  Among these, it is preferable to use an aliphatic polyester resin obtained by polycondensation of an aliphatic polyvalent carboxylic acid and an aliphatic polyhydric alcohol as the crystalline polyester resin from the viewpoint of easily obtaining low-temperature fixability. . Further, from the same viewpoint, it is more preferable to use an aliphatic polyvalent carboxylic acid having 4 to 12 carbon atoms including a carbon of a carboxy group and an aliphatic polyhydric alcohol having 4 to 12 carbon atoms.

The melting temperature of the crystalline polyester resin is preferably 50 ° C. or higher and 100 ° C. or lower, more preferably 55 ° C. or higher and 90 ° C. or lower, and further preferably 60 ° C. or higher and 85 ° C. or lower.
The melting temperature is determined from the “melting peak temperature” described in the method for determining the melting temperature of JIS K7121-1987 “Method for measuring the transition temperature of plastic” from the DSC curve obtained by differential scanning calorimetry (DSC).

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

  The crystalline polyester resin can be obtained by, for example, a well-known manufacturing method, similarly to the amorphous polyester resin.

  The content of the binder resin is, for example, preferably 40% by weight to 95% by weight, more preferably 50% by weight to 90% by weight, and more preferably 60% by weight to 85% by weight with respect to the entire toner particles. Further preferred.

(Vinyl resin particles and urethane resin particles)
The vinyl resin particles according to this embodiment may be produced by polymerizing the monomer for forming the vinyl resin unit of the amorphous polyester composite resin described above.
As vinyl resin particles, a styrene (meth) acrylic resin obtained by copolymerizing a styrene monomer and a (meth) acrylic acid monomer from the viewpoint of facilitating both low-temperature fixability and heat resistance. Particularly preferred are resin particles.

Moreover, the vinyl resin particles may be cross-linked. In order to crosslink the vinyl resin particles, a crosslinking agent may be used as at least a part of the monomer component used in the resin constituting the vinyl resin particles.
Examples of the crosslinking agent include aromatic polyvinyl compounds such as divinylbenzene and divinylnaphthalene; divinyl phthalate, divinyl isophthalate, divinyl terephthalate, divinyl homophthalate, divinyl trimesate / trivinyl, divinyl naphthalenedicarboxylate, biphenyl Polyvinyl esters of aromatic polycarboxylic acids such as divinyl carboxylate; divinyl esters of nitrogen-containing aromatic compounds such as divinyl pyridinedicarboxylate; neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Branched polypropylene glycol di (meth) acrylate, 2-hydroxy-1,3-diacryloxypropane, etc., (meth) acrylic acid esters of substituted polyhydric alcohols; divinyl succinate, divinyl fumarate Divinyl maleate, divinyl diglycolate, divinyl itaconate, divinyl acetone dicarboxylate, divinyl glutarate, divinyl 3,3′-thiodipropionate, divinyl trans / aconitate / trivinyl, divinyl adipate, divinyl pimelate, suberin And polyvinyl esters of polyvalent carboxylic acids such as divinyl acid, divinyl azelate, divinyl sebacate, divinyl dodecanedioate, and divinyl brassylate.
When a crosslinking agent is used as at least a part of the monomer component, the proportion of the crosslinking agent in all the monomer components is preferably 0% by mass or more and 20% by mass or less, and particularly preferably 0% by mass or more and 5% by mass or less.

  When the monomer used for the resin constituting the vinyl resin particles contains styrene, the proportion of styrene in all monomer components is preferably 20% by mass or more and 80% by mass or less, and 40% by mass or more and 70% by mass or less. Further preferred.

The volume average particle size of the vinyl resin particles is preferably 80 nm or more and 250 nm or less, and more preferably 100 nm or more and 200 nm or less, from the viewpoint of making it easier to achieve both low-temperature fixability and heat resistance. Especially preferably, it is the range of 110 nm or more and 150 nm or less.
The volume average particle size of the vinyl resin particles contained in the toner particles was divided using the particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring device (for example, LA-700 manufactured by Horiba, Ltd.). With respect to the particle size range (channel), the cumulative distribution is drawn from the small particle size side with respect to the volume, and the particle size that becomes 50% cumulative with respect to all particles is measured as the volume average particle size D50v.

The content of the vinyl resin particles is preferably 5% by mass or more and 30% by mass or less, and more preferably 10% by mass or more and 20% by mass or less, based on the whole toner, from the viewpoint of making it easier to achieve both low-temperature fixability and heat resistance. . Especially preferably, they are 10 mass% or more and 15 mass% or less.
In addition, when vinyl resin particles are contained in this range, it becomes easy to suppress a decrease in transferability.

As the vinyl resin particles, those produced through an emulsion polymerization method, a seed polymerization method, a high temperature high pressure emulsification method, or the like may be used.
For example, when an emulsion polymerization method is applied to the production of vinyl resin particles, monomers such as styrenes and (meth) acrylic acids are dissolved in water in which a water-soluble polymerization initiator such as potassium persulfate or ammonium persulfate is dissolved. In addition, if necessary, a surfactant such as sodium dodecyl sulfate, diphenyl oxide disulfonates and the like is added, and polymerization is carried out by heating while stirring to obtain vinyl resin particles.

Note that whether or not vinyl resin particles are contained in the toner according to the exemplary embodiment is confirmed by the following method.
First, toner particles prepared for scanning transmission electron microscope (STEM) observation are subjected to electron staining with ruthenium tetroxide and STEM observation is performed. As a result, when the concentration of the vinyl resin particles is different from that of the binder resin of the toner particles, since the degree of dyeing is different, the contrast in the STEM image is different, so the presence is confirmed.
Further, since the vinyl resin unit vinyl resin constituting the amorphous polyester composite resin and the vinyl resin particles have different contrasts, they can be distinguished from each other.

  As the urethane resin particles, for example, known urethane resin resin particles obtained by reacting a polyol compound and an isocyanate compound can be used.

-Colorant-
Examples of the colorant include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliant carmine 3B, and brilliant. Carmine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Pigment Red, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Pigment Blue, Phthalocyanine Green, Various pigments such as malachite green oxalate, or acridine, xanthene, , Benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazole, and other dyes Etc.
A colorant may be used individually by 1 type and may use 2 or more types together.

  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.

  The content of the colorant is, for example, preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 15% by mass or less with respect to the entire toner particles.

-Release agent-
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; and ester waxes such as fatty acid esters and montanic acid esters. And so on. The release agent is not limited to this.

The melting temperature of the release agent is preferably 50 ° C. or higher and 110 ° C. or lower, and more preferably 60 ° C. or higher and 100 ° C. or lower.
The melting temperature is determined from the DSC curve obtained by differential scanning calorimetry (DSC) according to the “melting peak temperature” described in JIS K-1987 “Method for measuring the transition temperature of plastics”.

  The content of the release agent is, for example, preferably 1% by mass to 20% by mass and more preferably 5% by mass to 15% by mass with respect to the entire toner particles.

-Other additives-
Examples of other additives include known additives such as a magnetic material, a charge control agent, and inorganic powder. These additives are contained in the toner particles as internal additives.

-Toner particle characteristics-
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be.
Here, the core / shell structure toner particles include, for example, a core portion including a binder resin and, if necessary, other additives such as a colorant and a release agent, and a binder resin. It is good to be comprised with the comprised coating layer.

  The volume average particle diameter (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less.

In addition, various average particle diameters and various particle size distribution indexes of the toner particles are measured using Coulter Multisizer II (manufactured by Beckman-Coulter), and the electrolyte is measured using ISOTON-II (manufactured by Beckman-Coulter). The
In the measurement, 0.5 mg to 50 mg of a measurement sample is added as a dispersant to 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzenesulfonate). This is added to 100 ml or more and 150 ml or less of the electrolytic solution.
The electrolyte in which the sample is suspended is dispersed for 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle size in the range of 2 μm to 60 μm is measured using a 100 μm aperture with a Coulter Multisizer II. taking measurement. The number of particles to be sampled is 50,000.
For the particle size range (channel) divided based on the measured particle size distribution, the cumulative distribution is drawn from the smaller diameter side to the volume and number, respectively, and the particle size to be 16% is the volume particle size D16v, the number particle size D16p, a particle size that is 50% cumulative is defined as a volume average particle size D50v, a cumulative number average particle size D50p, and a particle size that is 84% cumulative is defined as a volume particle size D84v and a number particle size D84p.
Using these, the volume average particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D84p / D16p) ^1/2 .

  The shape factor SF1 of the toner particles is preferably 110 or more and 150 or less, and more preferably 120 or more and 140 or less.

The shape factor SF1 is obtained by the following formula.
Formula: SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, ML represents the absolute maximum length of the toner, and A represents the projected area of the toner.
Specifically, the shape factor SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and is calculated as follows. That is, by capturing an optical microscope image of particles dispersed on the surface of a slide glass into a Luzex image analyzer using a video camera, obtaining the maximum length and projected area of 100 particles, calculating by the above formula, and obtaining the average value can get.

(External additive)
Examples of the external additive include inorganic particles. As the inorganic particles, SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, 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 inorganic particles as an external additive is preferably subjected to a hydrophobic treatment. 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 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic particles, for example.

  Examples of external additives include resin particles (resin particles such as polystyrene, polymethyl methacrylate (PMMA), and melamine resin), cleaning activators (for example, metal salts of higher fatty acids typified by zinc stearate, fluorine-based high molecular weight substances). Particle) and the like.

  The external addition amount of the external additive is, for example, preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.01% by mass or more and 2.0% by mass or less with respect to the toner particles.

(Toner production method)
Next, a toner manufacturing method according to this embodiment will be described.
The toner according to the exemplary embodiment can be obtained by externally adding an external additive to the toner particles after the toner particles are manufactured.

The toner particles may be produced by any of a dry production method (for example, a kneading and pulverizing method) and a wet production method (for example, an aggregation coalescence method, a suspension polymerization method, a dissolution suspension method, etc.). The production method of the toner particles is not particularly limited, and a known production method is adopted.
Among these, it is preferable to obtain toner particles by an aggregation and coalescence method.

Specifically, for example, in the case of producing toner particles by an aggregation and coalescence method, a step of preparing a resin particle dispersion in which resin particles serving as a binder resin are dispersed (resin particle dispersion preparation step), and a vinyl resin A step of preparing a vinyl resin particle dispersion (or urethane resin particle dispersion) in which particles are dispersed (a step of preparing a vinyl resin particle dispersion (or urethane resin particle dispersion)), and a resin particle dispersion (necessary) In accordance with the dispersion after mixing other particle dispersions), the resin particles (other particles if necessary) are aggregated to form aggregated particles (aggregated particle formation step); The dispersed aggregated particle dispersion is heated to fuse and coalesce the agglomerated particles to form toner particles (fused and coalesced step) to produce toner particles.
In the following steps, a resin particle dispersion in which resin particles serving as a binder resin are dispersed is referred to as a “resin particle dispersion”, and a vinyl resin particle dispersion in which vinyl resin particles are dispersed is referred to as “vinyl resin particles”. Dispersed as “dispersion”. Hereinafter, the vinyl resin particles will be described as a representative.

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.

-Preparation step of resin particle dispersion-
First, a resin particle dispersion in which resin particles to be a binder resin are dispersed and a vinyl resin particle dispersion in which vinyl resin particles are dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed, a mold release A release agent particle dispersion liquid in which agent particles are dispersed is 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.

Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. 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 a general dispersion method such as a rotary shear homogenizer, a ball mill having media, a sand mill, and a dyno mill. Depending on the type of resin particles, 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.

The volume average particle size of the resin particles dispersed in the resin particle dispersion is, for example, preferably 0.01 μm to 1 μm, more preferably 0.08 μm to 0.8 μm, and further preferably 0.1 μm to 0.6 μm. preferable.
In addition, the volume average particle diameter of the resin particles is based on the particle size range (channel) divided by using the particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring device (for example, LA-700 manufactured by Horiba, Ltd.). The cumulative distribution is subtracted from the small particle diameter side with respect to the volume, and the particle diameter that becomes 50% cumulative with respect to all the particles is measured as the volume average particle diameter D50v. The volume average particle size of particles in other dispersions is also measured in the same manner.

  As content of the resin particle contained in a resin particle dispersion liquid, 5 to 50 mass% is preferable, for example, and 10 to 40 mass% is more preferable.

For example, a colorant particle dispersion, a release agent particle dispersion, and a vinyl resin particle dispersion are also prepared in the same manner as the resin particle dispersion. In other words, regarding the volume average particle diameter 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 particle dispersion and the release agent particle dispersion The same applies to the release agent particles to be dispersed and the vinyl resin particles to be dispersed in the vinyl resin particle dispersion.
The vinyl resin particle dispersion may be prepared by an emulsion polymerization method.

-Aggregated particle formation process-
Next, the vinyl resin particle dispersion, the colorant particle dispersion, and the release agent particle dispersion are mixed together with the resin particle dispersion.
In the mixed dispersion, resin particles, vinyl resin particles, colorant particles, and release agent particles are hetero-aggregated to have resin particles, vinyl resin particles, and colorants having a diameter close to that of the intended toner particles. Aggregated particles including particles and release agent particles are formed.

Specifically, for example, the flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, the pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. The resin particles are heated to a glass transition temperature (specifically, for example, the glass transition temperature of the resin particles −30 ° C. or more and the glass transition temperature −10 ° C. or less), and the particles dispersed in the mixed dispersion liquid are aggregated. , Forming aggregated particles.
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 after adding a dispersion stabilizer as necessary, the heating may be performed.

Examples of the flocculant include a surfactant having a polarity opposite to that of the surfactant used as the dispersant added to the mixed dispersion, an inorganic metal salt, and a divalent or higher-valent metal complex. 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 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.
As addition amount of a chelating agent, 0.01 mass part or more and 5.0 mass part or less are preferable with respect to 100 mass parts of resin particles, for example, and 0.1 mass part or more and less than 3.0 mass parts are more preferable.

-Fusion / unification process-
Next, the aggregated particle dispersion in which the aggregated particles are dispersed is heated to, for example, a glass transition temperature or higher of the resin particles (for example, a temperature of 10 to 30 ° C. higher than the glass transition temperature of the resin particles). Are fused and united to form toner particles.

Through the above steps, toner particles are obtained.
In addition, after obtaining the aggregated particle dispersion liquid in which the aggregated particles are dispersed, the aggregated particle dispersion liquid and the resin particle dispersion liquid in which the resin particles are dispersed are further mixed, and the resin particles are further added to the surface of the aggregated particles. A process of aggregating to adhere to form second aggregated particles, and heating the second aggregated particle dispersion in which the second aggregated particles are dispersed to fuse and coalesce the second aggregated particles. The toner particles may be manufactured through a step of forming toner particles having a core / shell structure.

Here, after completion of the coalescence / union 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 carry out 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 performed from the viewpoint of productivity. Also, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, or the like is preferably performed.

  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 may be performed, for example, with a V blender, a Henschel mixer, a Ladyge mixer, or the like. Furthermore, 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.
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. As a carrier, for example, a coated carrier in which the surface of a core made of magnetic powder is coated with a coating resin; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and mixed in a matrix resin; a porous magnetic powder is impregnated with a resin Resin impregnated type carriers; and the like.
Note that the magnetic powder-dispersed carrier and the resin-impregnated carrier may be a carrier in which the constituent particles of the carrier are used as a core material and coated with a coating resin.

  Examples of the magnetic powder include magnetic metals such as iron, nickel, and cobalt, and magnetic oxides such as ferrite and magnetite.

  Examples of the conductive particles include particles of metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

Examples of the coating resin and matrix resin include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid copolymer. Examples thereof include a polymer, a straight silicone resin containing an organosiloxane bond or a modified product thereof, a fluororesin, a polyester, a polycarbonate, a phenol resin, and an epoxy resin.
Note that the coating resin and the matrix resin may contain other additives such as a conductive material.

Here, in order to coat the surface of the core material with the coating resin, a method of coating with a coating layer forming solution obtained by dissolving the coating resin and, if necessary, various additives in an appropriate solvent may be mentioned. The solvent is not particularly limited, and may be selected in consideration of the coating resin to be used, coating suitability, and the like.
Specific resin coating methods include a dipping method in which the core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed on the surface of the core material, and a state in which the core material is suspended by flowing air. Examples thereof include a fluidized bed method in which a coating layer forming solution is sprayed, a kneader coater method in which a carrier core material and a coating layer forming solution are mixed in a kneader coater, and the solvent is removed.

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

<Image Forming Apparatus / Image Forming Method>
The image forming apparatus / image forming method according to the present embodiment will be described.
The image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the charged image carrier, and an electrostatic charge. Development means for containing an image developer and developing the electrostatic image formed on the surface of the image carrier as a toner image with the electrostatic image developer, and the toner image formed on the surface of the image carrier as a recording medium Transfer means for transferring to the surface of the recording medium, and fixing means for fixing the toner image transferred to the surface of the recording medium. The electrostatic charge image developer according to this embodiment is applied as the electrostatic charge image developer.

  In the image forming apparatus according to this embodiment, a charging process for charging the surface of the image carrier, an electrostatic charge image forming process for forming an electrostatic image on the surface of the charged image carrier, and an electrostatic charge according to this embodiment. A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with an image developer; a transfer step of transferring the toner image formed on the surface of the image carrier to the surface of the recording medium; An image forming method (an image forming method according to the present embodiment) including a fixing step of fixing the toner image transferred onto the surface of the recording medium is performed.

The image forming apparatus according to the present embodiment is a direct transfer type apparatus that directly transfers a toner image formed on the surface of an image carrier to a recording medium; the toner image formed on the surface of the image carrier is transferred to an intermediate transfer member An intermediate transfer type apparatus that primarily transfers the toner image transferred to the surface of the intermediate transfer body and then secondary transfer the toner image to the surface of the recording medium; after the toner image is transferred, the surface of the image carrier before charging is cleaned. An apparatus provided with a cleaning unit; a known image forming apparatus such as an apparatus provided with a charge removing unit that discharges the surface of an image holding member by irradiating a discharge light after charging a toner image and before charging is applied.
In the case of an intermediate transfer type apparatus, the transfer means includes, for example, an intermediate transfer body on which a toner image is transferred to the surface, and a primary transfer that primarily transfers the toner image formed on the surface of the image holding body to the surface of the intermediate transfer body. And a secondary transfer unit that secondarily transfers the toner image transferred onto the surface of the intermediate transfer member onto the surface of 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 (process cartridge) that is detachable from the image forming apparatus. As the process cartridge, for example, a process cartridge including a developing unit containing the electrostatic charge image developer according to the present embodiment 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. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

FIG. 1 is a schematic configuration diagram illustrating an image forming apparatus according to the present embodiment.
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 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 drive roll 22 and a support roll 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other in the left to right direction in the drawing. The vehicle travels in the direction toward the unit 10K. The support roll 24 is applied with a force in a direction away from the drive roll 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the support roll 24. 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 drive roll 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 is supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K have the same configuration, here, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction. 10Y will be described as a representative. It should be noted that reference numerals with magenta (M), cyan (C), and black (K) are attached to the same parts as those of the first unit 10Y instead of yellow (Y). 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 photoreceptor 1Y, a charging roll (an example of a charging unit) 2Y that charges 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. Then, an exposure device (an example of an electrostatic image forming unit) 3 that forms an electrostatic image, and a developing device (an example of a developing unit) 4Y that develops the electrostatic image by supplying toner charged to the electrostatic image, developed A primary transfer roll 5Y (an example of a primary transfer unit) that transfers a toner image onto the intermediate transfer belt 20, and a photoconductor cleaning device (an example of a cleaning unit) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer. Are arranged in order.
The primary transfer roll 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 rolls 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roll 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 operation, the surface of the photoreceptor 1Y is charged to a potential of −600V to −800V by the charging roll 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (for example, volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (general resin resistance), 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 having a yellow image 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 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) as a toner image by the developing device 4Y.

  In the developing device 4Y, for example, an electrostatic charge image developer containing 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 electric charge on the photoreceptor 1Y, and has a developer roll (a developer holding member). Example) 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 roll 5Y, and an electrostatic force from the photoreceptor 1Y toward the primary transfer roll 5Y is applied to the toner image, so that the photoreceptor is exposed. The toner image on 1Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time has a (+) polarity opposite to the polarity (−) of the toner, and is controlled to +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 photoreceptor cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rolls 5M, 5C, and 5K after the second unit 10M is also controlled in accordance with 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 on which the four color toner images are transferred in multiple ways through the first to fourth units is disposed on the image transfer surface side of the intermediate transfer belt 20, the support roll 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roll (an example of a secondary transfer unit) 26 is formed to a secondary transfer portion configured. On the other hand, recording paper (an example of a recording medium) P is fed at a predetermined timing into a gap where the secondary transfer roll 26 and the intermediate transfer belt 20 are in contact with each other via a supply mechanism, and the secondary transfer bias is supplied to the support roll. 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, so The toner image is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to the resistance detected by a resistance detection means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

  Thereafter, the recording paper P is fed into the pressure contact portions (nip portions) of a pair of fixing rolls in a fixing device (an example of a fixing unit) 28, and the toner image is fixed on the recording paper P to form a fixed image.

Examples of the recording paper P to which the toner image is transferred include plain paper used in electrophotographic copying machines, printers, and the like. In addition to the recording paper P, the recording medium may be an OHP sheet.
In order to further improve the smoothness of the image surface after fixing, the surface of the recording paper P is also preferably smooth. For example, coated paper with the surface of plain paper coated with resin, art paper for printing, etc. are preferably used. Is done.

  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.

<Process cartridge / toner cartridge>
The process cartridge according to this embodiment will be described.
The process cartridge according to the present embodiment accommodates the electrostatic image developer according to the present embodiment, and develops the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic image developer. And a process cartridge that can be attached to and detached from the image forming apparatus.

  Note that the process cartridge according to the present embodiment is not limited to the above-described configuration, and other means such as a developing device and other units such as an image carrier, a charging unit, an electrostatic charge image forming unit, and a transfer unit, if necessary. And at least one selected from the above.

  Hereinafter, an example of the process cartridge according to the present embodiment will be shown, but the present invention is not limited to this. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

FIG. 2 is a schematic configuration diagram showing a process cartridge according to the present embodiment.
The process cartridge 200 shown in FIG. 2 is provided around the photoconductor 107 and the photoconductor 107 by, for example, a housing 117 provided with an attachment rail 116 and an opening 118 for exposure. A charging roller 108 (an example of a charging unit), a developing device 111 (an example of a developing unit), and a photoconductor cleaning device 113 (an example of a cleaning unit) are integrally combined and held to form a cartridge. Yes.
In FIG. 2, 109 is an exposure device (an example of an electrostatic charge image forming unit), 112 is a transfer device (an example of a transfer unit), 115 is a fixing device (an example of a fixing unit), and 300 is a recording paper (a recording medium). An example).

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 accommodates the toner according to the present exemplary embodiment and is detachable from the image forming apparatus. The toner cartridge contains toner for replenishment to be supplied to the developing means provided in the image forming apparatus.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which toner cartridges 8Y, 8M, 8C, and 8K are attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are each 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 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.

[Synthesis of amorphous polyester composite resin]
(Synthesis of vinyl resin unit)
-Synthesis of styrene (meth) acrylic resin (V1)-
Each component of 306 parts by mass of styrene, 94 parts by mass of n-butyl acrylate, 6 parts by mass of acrylic acid, and 0.2 parts by mass of β-carboxyethyl acrylate was put into a reaction vessel with a cooling tube, and 100 parts by mass of toluene. Then, 0.75 parts by mass of a radical initiator azoisobutyronitrile (AIBN) was added and reacted at 70 ° C. for 16 hours under a nitrogen stream. Then, it reprecipitated in 1 liter of methanol and dried to obtain an amorphous styrene (meth) acrylic resin (V1).

(Synthesis of polyester resin unit)
-Synthesis of amorphous polyester resin (A1)-
In a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, 45 mol% of bisphenol A propylene oxide 2 mol adduct (BPA-PO) and 30 mol% of ethylene glycol (EG) are used as polyhydric alcohol components. , 25 mol% of neopentyl alcohol (NPG), 90 mol% of terephthalic acid (TPA) and 10 mol% of dodecenyl succinic anhydride (DSA) are added as polyvalent carboxylic acid components, and the inside of the reaction vessel is replaced with dry nitrogen gas did. Thereafter, 1.0 part by mass of dibutyltin oxide is added as a catalyst to 100 parts by mass of the total amount of the monomer components, and the mixture is stirred and reacted at about 190 ° C. for about 5 hours under a nitrogen gas stream. After raising the temperature to 0 ° C. and causing the reaction to stir for about 6 hours, the pressure in the reaction vessel was reduced to 10.0 mmHg, and the reaction was allowed to stir for about 0.5 hours under reduced pressure to obtain an amorphous polyester resin (A1).

-Synthesis of Amorphous Polyester Resins (A2) to (A7)-
Amorphous polyester resins (A2) to (A) are prepared in the same manner as in the preparation of the amorphous polyester resin (A1) except that the types and amounts of the polyvalent carboxylic acid and the polyhydric alcohol are changed as shown in Table 1. A7) was prepared.
In addition, “BPA-EO” in Table 1 is a bisphenol A ethylene oxide 2-mol adduct.

(Synthesis of amorphous polyester composite resin (HB1))
After weighing 20% by mass of the styrene (meth) acrylic resin (V1) obtained above and 80% by mass of the amorphous polyester resin (A1) obtained above, and dissolving in 70 parts of toluene. Then, the mixture was charged into a reaction vessel with a cooling tube and polymerized by heating and mixing at 120 ° C. for 5 hours under a nitrogen stream to obtain an amorphous polyester composite resin (HB1).

(Synthesis of amorphous polyester composite resin (HB2) to (HB9))
The same as the synthesis of the amorphous polyester composite resin (HB1), except that the type of the amorphous polyester resin and the mass ratio of the styrene (meth) acrylic resin and the amorphous polyester resin were changed as shown in Table 2. Thus, amorphous polyester composite resins (HB2) to (HB9) were synthesized.
In addition, the resin number (HB7) in Table 2 is an amorphous polyester resin not including a vinyl resin unit.

[Preparation of Amorphous Polyester Composite Resin Particle Dispersion]
(Preparation of amorphous polyester composite resin particle dispersion (HB1))
3000 parts by mass of the amorphous polyester composite resin (HB1) obtained above, 10000 parts by mass of ion-exchanged water, and 90 parts by mass of sodium dodecylbenzenesulfonate were charged into an emulsification tank of a high-temperature, high-pressure emulsifier (Cabitron CD1010). Then, after heating and melting to 130 ° C., 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 amorphous polyester composite resin particles having a volume average particle diameter D50v of 115 nm A dispersion (HB1) was obtained.

(Preparation of amorphous polyester composite resin particle dispersions (HB2) to (HB9))
Preparation of the amorphous polyester composite resin particle dispersion (HB1), except that the amorphous polyester composite resin (HB1) was changed to the amorphous polyester composite resins (HB2) to (HB9) obtained above. Similarly, amorphous polyester composite resin particle dispersions (HB2) to (HB9) were obtained.

[Synthesis of crystalline polyester resin]
(Synthesis of crystalline polyester resin (Cr1))
In a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, 1 mol% of 1,6-hexanediol as a polyhydric alcohol component and 1 mol% of dodecanedioic acid as a polycarboxylic acid component And the inside of the reaction vessel was replaced with dry nitrogen gas. Thereafter, 0.25 parts by mass of titanium tetrabutoxide was added as a catalyst to 100 parts by mass of the monomer 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 hour, the pressure inside the reaction vessel was reduced to 3 kPa, and the stirring reaction was performed for 13 hours under reduced pressure to produce crystals. -Soluble polyester resin (Cr1) was obtained.

[Preparation of crystalline polyester resin particle dispersion]
(Preparation of crystalline polyester resin particle dispersion (Cr1))
Next, in a jacketed 3 liter reactor (manufactured by Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, a thermometer, a water dropping device and an anchor blade, 300 parts by mass of polyester resin (Cr1) and 160 parts by mass of methyl ethyl ketone And 100 parts by mass of isopropyl alcohol 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 circulating thermostat was set to 66 ° C., 17 parts of 10% ammonia water (reagent) was added over 10 minutes, and then 7 parts by mass of ion-exchanged water kept at 66 ° C. A total of 900 parts by mass was dropped at a rate of / min to cause phase inversion to obtain an emulsion. 800 parts of the obtained emulsified liquid and 700 parts by mass of ion-exchanged water were placed in a 2 liter eggplant flask and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, 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. Ion exchange water was added to obtain a crystalline polyester resin particle dispersion (Cr1) having a solid content concentration of 20% by mass.

[Preparation of vinyl resin particle dispersion and urethane resin particle dispersion]
(Preparation of styrene (meth) acrylic resin particle dispersion (F1))
Styrene (Wako Pure Chemical Industries, Ltd.): 480 parts by mass Methyl methacrylate (Wako Pure Chemical Industries, Ltd.): 120 parts by mass β-carboxyethyl acrylate (Solvay Nikka Co., Ltd.): 6 parts by mass 6 parts by mass of a surfactant (sodium diphenyl oxide disulfonate) was added to a dispersion medium dissolved in 250 parts by mass of ion-exchanged water, and 5 times at a rotation speed of 5000 rpm with a homogenizer (IKA Ultra Tarrax). By dispersing for a minute, a monomer emulsion was obtained.
Next, 50 parts by mass of the monomer emulsion, 550 parts of ion-exchanged water, and 1 part by mass of a surfactant (sodium diphenyl oxide disulfonate) are added to a container equipped with a stirrer that has been warmed to 80 ° C., and further added as a polymerization initiator. 10 parts by mass of ammonium sulfate (manufactured by Mitsubishi Gas Chemical Company) was added, and stirring at 200 rpm and a warm bath were maintained for 1 hour and 10 minutes.
Further, the remaining monomer emulsion was charged into the container at a rate of 3 parts by mass per minute, and after completion of the addition, the styrene (meth) acrylic resin particle dispersion (F1) was further stirred for 5 hours and kept in a warm bath. Obtained.
The resulting styrene (meth) acrylic resin particle dispersion (F1) had a solid content concentration of 40% by mass, and the volume average particle size of the particles was 200 nm.

(Preparation of polyurethane resin particle dispersion (F2))
In a simple pressure reactor equipped with a stirrer and a heater, a polycarbonate diol having an Mn of 2,000 “Asahi Kasei PCDL-T4672” [Asahi Kasei Chemicals Co., Ltd.] 183.8 parts, DMPA 21.8 parts, hydrogenated MDI 100. 0 parts and 204.1 parts of acetone were charged while introducing nitrogen. Thereafter, the mixture was heated to 85 ° C. and subjected to urethanization reaction for 10 hours to produce a prepolymer. The isocyanate content of the resin solid content at the end of the urethanization reaction was 0.83 mmol / g. After cooling the reaction mixture to 40 ° C., 16.4 parts of triethylamine (neutralizing agent) and 683.6 parts of water were added while stirring in a simple pressure reactor. Subsequently, acetone was removed under reduced pressure at 65 ° C. over 8 hours to obtain 1,000 parts of a polyurethane resin aqueous dispersion.
The resulting polyurethane resin particle dispersion (F2) had a solid content concentration of 40% by mass, and the volume average particle size of the particles was 200 nm.

[Preparation of colorant particle dispersion]
Cyan pigment: 50 parts by mass (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine))
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R): 5 parts by mass-Ion-exchanged water: 200 parts by mass The above components are mixed and dispersed for 10 minutes by a homogenizer (IKA Ultra Tarrax), and then an optimizer. (Opposite collision type wet pulverizer: manufactured by Sugino Machine) was subjected to a dispersion treatment at a pressure of 245 Mpa for 15 minutes to obtain a colorant particle dispersion having a volume average particle diameter of 182 nm and a solid content of 20% by mass. .

[Preparation of release agent particle dispersion]
-Paraffin wax: HNP-9 (Nippon Seiki): 20 parts by mass-Anionic surfactant: Neogen SC (Daiichi Kogyo Seiyaku): 1 part by mass-Ion exchange water: 80 parts by mass The above is mixed in a heat-resistant container. The mixture was heated to 90 ° C. and stirred for 30 minutes. Next, the molten liquid is circulated from the bottom of the container to the gorin homogenizer, and under a pressure condition of 5 MPa, a circulation operation corresponding to 3 passes is performed. Then, the pressure is increased to 35 MPa, and further a circulation operation corresponding to 3 passes is performed. It was. The emulsion thus prepared was cooled in the heat-resistant solution to 40 ° C. or lower to obtain a release agent particle dispersion having a volume average particle size of 182 nm and a solid content of 20% by mass.

<Example 1>
[Production of toner]
(Production of toner particles (1))
Amorphous polyester composite resin particle dispersion (HB1): 100 parts by mass Crystalline polyester resin particle dispersion (Cr1): 37.5 parts by mass Styrene (meth) acrylic resin particle dispersion (F1): 10 parts by mass Part / Colorant particle dispersion: 10 parts by weight Release agent particle dispersion: 9 parts by weight Surfactant aqueous solution: 0.1 part by weight 0.3 M nitric acid aqueous solution: 0.4 part by weight ion exchange water: 200 parts by mass

The above components are housed in a round stainless steel flask, dispersed using a homogenizer (IKA, Ultra Tarrax T50), heated to 42 ° C. in a heating oil bath, held for 30 minutes, and then aggregated At the stage where it was confirmed that the particles were formed, 50 parts by mass of an additional amorphous polyester composite resin particle dispersion (HB1) was added, and the mixture was further held for 30 minutes.
Subsequently, nitrilotriacetic acid Na salt (manufactured by Chubu Kirest Co., Ltd., Kirest 70) was added so as to be 3% by mass of the total liquid. Thereafter, a 1N aqueous sodium hydroxide solution was gently added until pH 7.2 was reached, and then the mixture was heated to 85 ° C. while continuing stirring and maintained for 3.0 hours. Thereafter, the reaction product was filtered, washed with ion exchange water, and then dried using a vacuum dryer to obtain toner particles (1).

(Production of Toner (1))
To 100 parts by mass of toner particles (1), 3 parts by mass of silica particles (silica particles obtained by a sol-gel method and having a surface treatment amount of 5% by mass with hexamethyldisilazane and an average primary particle size of 120 nm) and silica particles ( R972 (manufactured by Nippon Aerosil Co., Ltd.) and adding 1 part by mass, using a 5 liter Henschel mixer, mixing for 15 minutes at a peripheral speed of 30 m / s, then removing coarse particles using a 45 μm mesh sieve, Toner (1) was produced.

<Examples 2-15 and Comparative Examples 1-2>
The same as Example 1 except that the kind of the amorphous polyester composite resin in the toner particles was changed as shown in Table 3, and the amount of the vinyl resin particles in the toner particles was changed as shown in Table 3. Thus, toners (2) to (15) and toners (C1) to (C2) were produced.

[Production of developer]
A developer was prepared as follows using each toner obtained in each example.
100 parts of ferrite particles (manufactured by Powdertech Co., Ltd., average particle size 50 μm) and 1.5 parts of methyl methacrylate resin (manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight 95,000) are placed in a pressure kneader together with 500 parts of toluene, and mixed with stirring for 15 minutes. Then, the temperature was raised to 70 ° C. while mixing under reduced pressure to distill off the toluene, and then the mixture was cooled and classified using a 105 μm sieve to obtain a resin-coated ferrite carrier.
Each developer was prepared by mixing this resin-coated ferrite carrier and the toner obtained in each example in a V blender at a ratio of 8 parts of toner and 92 parts of carrier.

[Evaluation of bending strength]
Each developer was mounted on a DocuCentreColor 500 remodeling machine manufactured by Fuji Xerox Co., Ltd. (remodeled so as to be fixed by an external fixing machine having a variable fixing temperature).
A solid image was formed on a color paper (J paper) manufactured by Fuji Xerox Co., Ltd. by adjusting the toner applied amount to 13.5 g / m 2. After the toner image was produced, the image was fixed using an external fixing machine at a fixing speed of 180 mm / sec with a nip width of 6.5 mm.
However, the fixing temperature is fixed at 130 ° C., the toner image is fixed, a crease is made at the center of the solid portion of the fixed image on the paper, and the portion where the fixed image is destroyed is wiped with a tissue paper and white The missing line width was measured. The evaluation criteria are as follows.
5:30 or less 4:30 to 60 μm or less 3:60 to 80 μm or less 2:80 to 100 μm or less 1: 100 μm or more

[Evaluation of toner cohesion]
Evaluation was carried out by mounting each developer using DocuPrint 1100CF manufactured by Fuji Xerox Co., Ltd. modified so that the peripheral speed of the developing roll was variable. The peripheral speed of the developing roll was 1000 mm / s. In an environment of 30 ° C. and 80% RH, the above-mentioned modified machine outputs 500,000 images with an image density of 1% in A4 conversion, and then outputs 100 full-color images for A4 conversion. The presence or absence of image quality defects was evaluated. Specifically, the ratio of the number of image quality defects such as white spots and white streaks out of 100 sheets of output was evaluated. The paper used was a recycled NIP paper manufactured by Kobayashi Create. The evaluation criteria are as follows.
5: 10% or less 4: 10% over 20% or less 3: 20% over 40% or less 2: 40% over 50% or less 1: 50% over

[Evaluation of transferability]
The obtained developer was mounted on DocuCentre-III 3000 (direct transfer system) manufactured by Fuji Xerox Co., Ltd.
Then, a solid patch of 5 cm × 2 cm is developed in an environment of a temperature of 30 ° C. and a humidity of 70%, and the developed toner image on the surface of the photosensitive member is taped (manufactured by Sumitomo 3M, trade name: transparent beautiful color, 18 mm width) The toner was transferred using the adhesiveness of the surface, and the mass (W1) of the transferred toner was measured repeatedly until the toner could not be visually confirmed on the surface of the photoreceptor.

Next, the toner image developed on the surface of the photoreceptor under the same conditions as described above is transferred to the surface of paper (Fuji Xerox Office Supply, J paper), and the toner is blown off with air before fixing. The mass (W2) of the transferred image was measured from the difference in the weights.
The initial transfer efficiency was determined by the following equation. The transfer current was 13 μA.
Formula: Transfer efficiency (%) = (W2 / W1) × 100

Thereafter, 100,000 sheets of 5 cm × 2 cm solid patches were formed in an environment of a temperature of 30 ° C. and a humidity of 70%, and then the transfer efficiency after operation was determined in the same manner as the initial transfer efficiency. The evaluation criteria are as follows.
A (◯): No change.
B (Δ): Changes by about 10%.
C (x): Almost no toner is transferred.

  In Table 3, “HB-PES” is an amorphous polyester composite resin, “Cr-PES” is a crystalline polyester resin, and “Cr / HB” is a crystalline polyester resin and an amorphous polyester composite resin. Ratio (crystalline polyester resin / amorphous polyester composite resin), “BPA-AO” is an alkylene oxide adduct of bisphenol A, “mol%” is a molar amount relative to the whole polyhydric alcohol, “Vn” / PES ”is the mass ratio of the vinyl resin unit to the polyester resin unit in the amorphous polyester composite resin (the vinyl resin unit / the polyester resin unit),“ Vn unit ”is the vinyl resin unit, and the vinyl resin particle “Particle size” represents the volume average particle size.

  From the above results, it can be seen that in this example, toner aggregates are less likely to occur than in the comparative example. Thereby, it turns out that a present Example is compatible with low temperature fixability and heat resistance compared with a comparative example.

1Y, 1M, 1C, 1K photoconductor (an example of an image carrier)
2Y, 2M, 2C, 2K charging roll (an example of charging means)
3. Exposure device (an example of electrostatic charge image forming means)
3Y, 3M, 3C, 3K Laser beams 4Y, 4M, 4C, 4K Developing device (an example of developing means)
5Y, 5M, 5C, 5K primary transfer roll (an example of primary transfer means)
6Y, 6M, 6C, 6K Photoconductor cleaning device (an example of cleaning means)
8Y, 8M, 8C, 8K Toner cartridge 10Y, 10M, 10C, 10K Image forming unit 20 Intermediate transfer belt (an example of an intermediate transfer member)
22 Drive roll 24 Support roll 26 Secondary transfer roll (an example of secondary transfer means)
30 Intermediate transfer member cleaning device 107 Photosensitive member (an example of an image holding member)
108 Charging roll (an example of charging means)
109 Exposure apparatus (an example of electrostatic charge image forming means)
111 Developing device (an example of developing means)
112 Transfer device (an example of transfer means)
113 photoconductor cleaning device (an example of cleaning means)
115 Fixing device (an example of fixing means)
116 Mounting rail 117 Housing 118 Opening 200 for exposure Process cartridge 300 Recording paper (an example of a recording medium)
P Recording paper (an example of a recording medium)

Claims (13)

A non-crystalline polyester composite resin in which a vinyl resin unit and a polyester resin unit are chemically bonded, and a crystalline polyester resin, and a mass ratio of the crystalline polyester resin and the amorphous polyester composite resin (described above) A binder resin having a crystalline polyester resin / the amorphous polyester composite resin) of 14/86 or more and 30/70 or less;
At least one selected from the group consisting of vinyl resin particles and urethane resin particles;
A toner for developing an electrostatic charge image.   The electrostatic charge image developing toner according to claim 1, wherein the vinyl resin unit is a styrene (meth) acrylic resin unit.   Polyester resin in which the polyester resin unit is a polycondensation of a polyhydric alcohol containing an alkylene oxide adduct of bisphenol A in an amount of 50 mol% to 100 mol% with respect to the whole polyhydric alcohol, and a polycarboxylic acid. The electrostatic image developing toner according to claim 1, wherein the toner is a unit.   4. The mass ratio of the vinyl resin unit and the polyester resin unit (the vinyl resin unit / the polyester resin unit) is 10/90 or more and 30/70 or less. 5. Toner for developing electrostatic images.   The electrostatic charge image developing toner according to claim 1, wherein the vinyl resin particles are styrene (meth) acrylic resin particles.   6. The electrostatic image developing toner according to claim 1, wherein the vinyl resin particles are contained in an amount of 10% by mass or more and 20% by mass or less based on the whole toner.   7. The electrostatic image developing toner according to claim 1, wherein the vinyl resin particles have a volume average particle size of 80 nm or more and 250 nm or less.   The electrostatic charge image according to any one of claims 1 to 7, wherein the crystalline polyester resin is an aliphatic polyester resin obtained by condensation polymerization of an aliphatic polyvalent carboxylic acid and an aliphatic polyhydric alcohol. Development toner. An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1. The toner for developing an electrostatic charge image according to any one of claims 1 to 8 is accommodated,
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for containing the electrostatic charge image developer according to claim 9 and developing the electrostatic charge image formed on the surface of the image carrier 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 surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic charge image developer according to claim 9 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising: A charging step for charging the surface of 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 charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 9;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising: