JP2016060838A - Vinyl/polyester resin composite particle, 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 new vinyl/polyester resin composite particle having a small diameter and containing a large amount of a vinyl resin.SOLUTION: The vinyl/polyester resin composite particle has a structure composed of a core containing a vinyl resin and a coating layer coating the core and containing a polyester resin. The vinyl resin is included by 40 mass% or more and 95 mass% or less with respect to the whole solid content of the core and the coating layer. The particle has a volume average particle diameter (D50v) of 100 nm or more and 500 nm or less.SELECTED DRAWING: None

Description

  The present invention relates to vinyl / polyester resin composite particles, 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.

Resin particles having a structure composed of a core part (core part) and a coating layer (shell layer) covering the core layer, that is, resin composite particles having a so-called core-shell structure have been produced. Various types of core-shell structure resin composite particles have been proposed.
For example, Patent Document 1 states that “encapsulated particles whose surfaces are coated with finely dispersed polyester resin fine particles in an aqueous medium, wherein the encapsulated particles are polyvalent carboxylic acids having a composition of the polyester resin fine particles. Among them, phthalic acids are contained in an amount of 80 mol% or more, the average particle diameter of the polyester resin fine particles is 1 μm or less, and the film thickness of the capsule layer containing the encapsulated particles is the average of the core particles having the polyester resin fine particles "Encapsulated particle | grains characterized by being 0.5 to 7.5% of a particle size" are disclosed.

  In Patent Document 2, “in a capsule for thermal pressure fixing composed of a heat-meltable core material containing at least a thermoplastic resin and a colorant and an outer shell provided so as to cover the surface of the core material, A hydrophilic outer shell material is coated on the surface of the core material to form precursor particles, and then at least a vinyl polymerizable monomer and a vinyl polymerization initiator are added to the aqueous suspension of the precursor particles to add the precursor particles to the precursor particles. A capsule toner for heat and pressure fixing characterized by being obtained by polymerizing the monomer component in the precursor particles after absorption is disclosed.

  Patent Document 3 states that, in producing a non-film-forming polymer emulsion, a monomer mixture having an α, β-ethylenically unsaturated group is emulsion-polymerized in the presence of a film-forming aid and / or a plasticizer. A method for producing a non-film-forming polymer emulsion characterized by the above is disclosed.

  In Patent Document 4, "(I) (II) (a) (meth) acrylic acid alkyl ester 5 to 99% by weight in the presence of 1 to 95 parts by weight of water-dispersible polyester, (b) aromatic vinyl compound" 0 to 60% by weight, (c) 1 to 30% by weight of polyalkylene glycol (meth) acrylate, and (d) 0 to 94% by weight of other copolymerizable ethylenically unsaturated monomers [where (a) + (B) + (c) + (d) = 100% by weight] The monomer component 99 to 5 parts by weight (where (I) + (II) = 100 parts by weight) is obtained by emulsion polymerization. A "polymer latex" is disclosed.

  Patent Document 5 states that “a dicarboxylic acid component (A) containing a dicarboxylic acid having a sulfonic acid metal base (A1) and a dicarboxylic acid compound having a reactive double bond (A2) and a diol component (B) are polycondensed. An emulsion obtained by emulsion polymerization of an ethylenically unsaturated compound (C) in an aqueous medium in the presence of a polyester having 1 to 5 meq / g of reactive double bonds in the molecular chain. A “composition” is disclosed.

  Patent Document 6 states that “polycarboxylic acid anhydride (C) is added to a polyester polyol obtained by reacting a dicarboxylic acid component (A) containing a dicarboxylic acid compound (A1) having a reactive double bond and a diol component (B)”. An emulsion composition characterized in that it is obtained by emulsion polymerization of an ethylenically unsaturated compound in an aqueous medium in the presence of an added polyester is disclosed.

  Patent Document 7 discloses “an aqueous primer for a lamp reflector characterized by containing an aqueous solution or aqueous dispersion of a water-soluble or water-dispersible aqueous polyester resin as an essential component”.

JP 2006-002109 A Japanese Patent Application Laid-Open No. 06-317925 JP-A-63-186703 Japanese Patent Laid-Open No. 05-301933 JP 2003-292548 A JP 2003-292549 A JP 2009-249573 A

  The subject of this invention is the structure (henceforth a core part and a coating layer which coat | covers a core part) comprised by the core part containing a vinyl resin, and the coating layer containing a polyester resin as a coating layer which coat | covers the said core part. And a vinyl / polyester resin composite particle having a small diameter and containing a large amount of vinyl resin. It is to provide composite particles.

The above problem is solved by the following means.
That is, the invention according to claim 1
A core portion including a vinyl resin, and a coating layer covering the core portion, the coating layer including a polyester resin,
The vinyl resin is contained in an amount of 40% by mass or more and 95% by mass or less based on the total solid content of the core and the coating layer,
These are vinyl / polyester resin composite particles having a volume average particle size (D50v) of 100 nm or more and 500 nm or less.

The invention according to claim 2
The vinyl / polyester resin composite particles according to claim 1, wherein the vinyl / polyester resin composite particles are resin composite particles obtained by polymerizing a vinyl monomer inside the polyester resin particles.

The invention according to claim 3
A phase inversion emulsification step in which a polyester resin particle dispersion is obtained by phase inversion emulsification of the chlorinated polyester resin;
A polymerization step of polymerizing a vinyl monomer inside the polyester resin particles of the polyester resin particle dispersion,
It is a manufacturing method of the vinyl / polyester resin composite particle of any one of Claim 1 or 2.

The invention according to claim 4
An electrostatic charge image developing toner comprising toner particles containing a binder resin containing a polyester resin and the vinyl / polyester resin composite particles according to claim 1.

The invention according to claim 5
5. The electrostatic image developing toner according to claim 4, wherein the vinyl / polyester resin composite particles are contained in an amount of 20% by mass or more and 50% by mass or less based on the entire toner particles.

The invention according to claim 6
The binder resin includes a crystalline polyester resin and an amorphous polyester resin, and the crystalline polyester resin is contained in an amount of 10% by mass or more and 50% by mass or less based on the whole toner particles. Or the toner for developing an electrostatic charge image according to any one of 5;

The invention according to claim 7 provides:
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 4.

The invention according to claim 8 provides:
Containing the toner for developing an electrostatic charge image according to any one of claims 4 to 6,
The toner cartridge is detachable from the image forming apparatus.

The invention according to claim 9 is:
A developing means for containing the electrostatic charge image developer according to claim 7 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 10 is:
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 image developer according to claim 7 and developing the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic 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 11 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 7;
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 and second aspects of the invention, novel vinyl / polyester resin composite particles having a small diameter and a core / shell structure containing a large amount of vinyl resin are provided.

  According to the invention which concerns on Claim 3, compared with the case where the polyester resin which is not chlorinated is used, the manufacturing method of the vinyl / polyester resin composite particle by which the exposure of the vinyl resin was suppressed is provided.

  According to the fourth aspect of the present invention, there is provided an electrostatic image developing toner in which the occurrence of toner aggregation is suppressed as compared with the case where vinyl resin particles not formed with a coating layer containing a polyester resin are applied. Is done.

  According to the invention of claim 5, for electrostatic image development in which toner aggregation is suppressed compared to the case where the content of vinyl / polyester resin composite particles in the toner particles is less than 20% by mass. Toner is provided.

  According to the sixth aspect of the present invention, the content of the crystalline polyester resin in the toner particles is 10% by mass or more compared to the case where the vinyl resin particles not formed with the coating layer containing the polyester resin are applied. Even if it exists, the toner for electrostatic image development in which aggregation of the toner was suppressed is provided.

  According to the invention according to claim 7, 8, 9, 10 or 11, the occurrence of toner aggregation is suppressed as compared with the case of using vinyl resin particles on which a coating layer containing a polyester resin is not formed. An electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming apparatus, or an image forming method is provided.

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.

<Vinyl / polyester resin composite particles>
The vinyl / polyester resin composite particles according to the present embodiment (hereinafter, the vinyl / polyester resin composite particles may be referred to as “resin composite particles”) include a core containing vinyl resin and a coating layer covering the core. And it has the structure comprised with the coating layer containing a polyester resin. And vinyl resin is contained by 40 to 95 mass% with respect to the total solid of a core part and a coating layer. Furthermore, the volume average particle diameter (D50v) is 100 nm or more and 500 nm or less.

Vinyl resins are generally cheaper and easier to adjust physical properties than polyester resins. Therefore, in the resin composite particles having a core / shell structure, the vinyl / polyester resin composite particles including the vinyl resin in the core and the polyester resin in the coating layer have an affinity with, for example, various base materials and fibers. Useful.
Here, since the vinyl resin is inexpensive and the physical properties can be easily adjusted, the novel resin composite particles according to this embodiment containing a large amount of the vinyl resin are, for example, a toner for developing an electrostatic image (hereinafter referred to as “toner”). It can be applied to various uses such as adhesives and paints, and is considered to be highly useful.

For example, in the toner technology, toner particles containing a binder resin including a polyester resin and vinyl resin particles are used.
However, since a simple vinyl resin particle does not have a core / shell structure and there is no coating layer covering the surface of the vinyl resin particle, for example, when the glass transition temperature of the vinyl resin particle is low, The toner containing resin particles may agglomerate. For this reason, it has been difficult to obtain toner particles containing a large amount of vinyl resin component.

  On the other hand, when the new resin composite particles having the above-described configuration of the present embodiment are applied to, for example, toner particles contained in the toner, occurrence of toner aggregation is suppressed. Since toner aggregation is suppressed, a large amount of vinyl resin component can be contained in the toner particles. These reasons are not clear, but are presumed to be due to the following reasons.

Since the vinyl / polyester resin composite particles according to this embodiment have a structure in which the core portion containing the vinyl resin is covered with the coating layer containing the polyester resin, the vinyl resin is exposed to the toner particle surfaces. It is suppressed. By having this structure, it is considered that toner aggregation is suppressed even when the glass transition temperature of the vinyl resin is low.
As a result of suppressing the occurrence of toner aggregation, it is considered that a large amount of the resin composite particles having the above configuration can be contained in the toner particles, and toner particles containing a large amount of vinyl resin component can be obtained. That is, by applying the vinyl / polyester resin composite particles according to the present embodiment to toner, toner particles containing a large amount of vinyl resin component can be obtained, and a toner in which toner aggregation is suppressed can be obtained.

In addition, as a binder resin in the toner particles, for example, a means for obtaining a low temperature fixability at the time of image formation by incorporating an amorphous polyester resin and a crystalline polyester resin is employed. By including the crystalline polyester resin, the toner particles tend to have low mechanical strength and the like. Therefore, for example, in the developing unit of the image forming apparatus, when an external force such as agitation acts on the toner exhibiting low-temperature fixability, a phenomenon such as deformation of the toner is likely to occur. Therefore, by including vinyl resin particles together with a binder resin including an amorphous polyester resin and a crystalline polyester resin, a means for suppressing the occurrence of toner deformation or the like while maintaining low-temperature fixability is performed. It has been broken. This is considered to be due to the vinyl resin particles exhibiting a filler effect in the toner particles.
However, since the affinity between the polyester resin and the vinyl resin particles is low, when both are mixed, the dispersion state of the vinyl resin particles tends to be low in the toner particles. Therefore, the vinyl resin may be unevenly distributed, and the filler effect may be difficult to be exhibited.

On the other hand, when the vinyl / polyester resin composite particles of the present embodiment are applied to toner particles having a binder resin containing an amorphous polyester resin and a crystalline polyester resin, for example, deformation of the toner Occurrence is suppressed.
Since the resin composite particles of this embodiment have the above-described configuration, the dispersion state of the resin composite particles is improved in the toner particles by increasing the affinity with the polyester resin. Therefore, it is considered that the filler effect is easily exhibited and the occurrence of toner deformation and the like is suppressed. As a result, it is considered that a large amount of the resin composite particles having the above-described configuration can be contained in the toner particles, and toner particles containing a large amount of vinyl resin can be obtained while having low-temperature fixability.

For example, in an example of Japanese Patent Application Laid-Open No. 2006-002109, an encapsulated particle in which the surface of a vinyl resin is coated with a polyester resin and the volume average particle size is about 120 nm is described. However, in this encapsulated particle, although the vinyl resin is present inside the polyester resin, the content of the vinyl resin in the entire capsule particle is about 33% by mass at the maximum, and those containing 40% by mass or more It was not obtained.
Japanese Patent Application Laid-Open No. 06-317925 discloses a capsule toner for heat and pressure fixing in which the surface of a vinyl resin is coated with a polyester resin. However, the average particle diameter of the heat-pressure fixing capsule toner was 8 μm, and no toner having a small diameter of 500 nm or less was obtained.

  Hereinafter, the vinyl / polyester resin composite particles according to this embodiment will be described in detail.

In the vinyl / polyester resin composite particles according to the present embodiment, “a structure including a core portion including a vinyl resin and a coating layer covering the core portion and including a polyester resin” is X It indicates that the ratio of the polyester resin present on the surface of the resin composite particles measured by a line photoelectron spectrometer (XPS) is 80% or more.
That is, the resin composite particles having a polyester resin ratio of 80% or more measured by an X-ray photoelectron spectrometer (XPS) indicate that the exposure of the vinyl resin to the surface of the resin composite particles is suppressed. Yes.

In addition, the method of measuring the ratio of the polyester resin which exists in the surface of a vinyl / polyester resin composite particle is as follows.
JPS-9000MX (manufactured by JEOL Ltd.) is used as the X-ray photoelectron spectrometer (XPS), MgKα ray is used as the X-ray source, the acceleration voltage is set to 10 kV, and the emission current is set to 30 mA.
The amount of the polyester resin component on the surface of the resin composite particles is quantified by peak-separating the component resulting from the polyester resin component on the surface of the vinyl / polyester resin composite particles from the C1S spectrum obtained under the above conditions. A peak is separated into each component of the measured C1S spectrum using curve fitting by a least square method. As a component spectrum serving as a base for separation, a C1S spectrum obtained by independently measuring the vinyl resin and the polyester resin used for producing the vinyl / polyester resin composite particles is used. Based on the quantitative determination result of the resin component separated in peak, the ratio of the polyester resin in the resin component on the surface of the resin composite particle is calculated.

  In the vinyl / polyester resin composite particles according to this embodiment, the content of the vinyl resin is 40% by mass or more and 95% by mass or less with respect to the total solid content of the core and the coating layer. From the viewpoint of further suppressing the exposure of the vinyl resin, the content is preferably 45% by mass or more and 90% by mass or less. More preferably, it is 50 mass% or more and 80 mass% or less.

The volume average particle diameter of the vinyl / polyester resin composite particles is 100 nm or more and 500 nm or less. It is preferable that it is 100 nm or more and 400 nm or less. More preferably, it is 100 nm or more and 300 nm or less.
In addition, the volume average particle diameter of the vinyl / polyester resin composite particles is determined by using a particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring apparatus (for example, LA-700, manufactured by Horiba, Ltd.). With respect to the channel), the cumulative distribution is drawn from the small particle diameter side with respect to the volume, and the particle diameter that becomes 50% cumulative with respect to all 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.

The volume average particle size distribution index GSDv) of the vinyl / polyester resin composite particles is preferably 1.30 or less. More preferably, it is 1.25 or less.
The volume average particle size distribution index of the vinyl / polyester resin composite particles is determined based on the particle size distribution obtained by the measurement of the volume average particle size described above to obtain a volume by converting spheroids from r1 to r100 from the small diameter side. A cumulative distribution is drawn, and the particle size that is 16% cumulative is defined as the volume particle size D16v, and the particle size that is 84% cumulative is defined as the volume particle size D84v.
The volume average particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 .
[Core containing vinyl resin]
(Vinyl resin)
The core part which comprises the vinyl / polyester resin composite particle which concerns on this embodiment contains vinyl resin as above-mentioned.

Examples of the vinyl monomer for obtaining the vinyl resin include styrene and alkyl-substituted styrene (for example, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, Ethyl styrene, 4-ethyl styrene, etc.), halogen-substituted styrene (for example, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, etc.), styrenes having a styrene moiety such as vinylnaphthalene; methyl (meth) acrylate, (Meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate n-butyl, (meth) acrylate lauryl, (meth) acrylate 2-ethylhexyl, trimethylolpropane trimethacrylate (TMPTMA) Esters having a vinyl group such as acrylonitrile, Vinyl nitriles such as tacrylonitrile; Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; (Meth) acrylic acid, maleic acid and cinnamic acid And monomers having vinyl groups such as fumaric acid and vinylsulfonic acid; bases having vinyl groups such as ethyleneimine, vinylpyridine and vinylamine;
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. May be used in combination.

  The vinyl resin may be a polymer polymerized using these monomers alone or a copolymer polymerized using two or more kinds. Among these, the vinyl monomer is preferably a copolymer containing styrenes having a styrene moiety, esters having a vinyl group, and acids having a vinyl group as monomers.

  Styrenes having a styrene moiety may be used alone or in combination of two or more. It is particularly preferable to use styrene from the viewpoint of easy reaction, easy control of reaction, and availability.

Of the esters having a vinyl group and the acids having a vinyl group, it is preferable to use a monomer having a (meth) acrylic moiety (hereinafter referred to as “(meth) acrylic acid”).
“(Meth) acryl” is an expression including both “acryl” and “methacryl”.
(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.

Examples of the (meth) acrylic acid alkyl ester include, 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.
Also, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, β-carboxyethyl (meth) acrylate, (meth) Examples include acrylamide.

The glass transition temperature (Tg) of the vinyl resin is preferably 40 ° C. or higher and 110 ° C. or lower, and more preferably 50 ° C. or higher and 70 ° 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 from 20,000 to 500,000, more preferably from 40,000 to 200,000.
The molecular weight distribution Mw / Mn of the vinyl resin is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 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.

  A polymerization initiator may be used when polymerizing the vinyl monomer. Examples of the polymerization initiator include hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, Lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid tert-butyl hydroperoxide, formic acid tert -Butyl, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl permethoxyacetate, tert-butyl per-N- (3-toluyl) carbamate, ammonium bisulfate Peroxides such as sodium bisulfate; azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), etc. Can be mentioned.

  Moreover, you may use a chain transfer agent from a viewpoint of adjusting the molecular weight of a resin particle. Examples of the chain transfer agent include compounds having a thiol moiety such as hexylthiol, heptanethiol, octanethiol, nonanethiol, decanethiol, dodecanethiol, tetradecanethiol, hexadecanethiol, and the like.

[Coating layer containing polyester resin]
(Polyester resin)
The coating layer that covers the core part of the vinyl / polyester resin composite particles according to the present embodiment contains a polyester resin.

Examples of the polyester resin include known polyester resins. For example, a condensation polymer of a polyvalent carboxylic acid and a polyhydric alcohol can be mentioned.
In addition, as a polyester resin, a commercial item may be used and what was synthesize | combined may be used.
The polyester resin may be either an amorphous polyester resin or a crystalline polyester resin, or both may be used in combination.

  When the vinyl / polyester resin composite particles according to this embodiment are applied to a toner, the polyester resin contained in the coating layer is amorphous from the viewpoint of suppressing the occurrence of toner aggregation and toner deformation. A polyester resin is preferably used.

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.

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, or lower (eg, having 1 to 5 carbon atoms) alkyl ester.
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.

The glass transition temperature (Tg) of the 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 polyester resin is preferably from 5,000 to 1,000,000, and more preferably from 7,000 to 500,000.
The number average molecular weight (Mn) of the polyester resin is preferably from 2,000 to 100,000.
The molecular weight distribution Mw / Mn of the 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.

From the viewpoint of phase inversion emulsification, the acid value of the polyester resin (the number of mg of KOH required to neutralize 1 g of resin) is preferably in the range of 3 mgKOH / g to 30 mgKOH / g. Furthermore, it is preferably in the range of 5 mgKOH / g to 25 mgKOH / g, particularly preferably in the range of 6 mgKOH / g to 20 mgKOH / g. The acid value of the polyester resin is adjusted by controlling the carboxy group of the polyester resin according to the blending ratio of the polyvalent carboxylic acid and the polyhydric alcohol and the reaction rate.
In the present embodiment, the acid value is measured according to JIS K0070, and is measured by a neutralization titration method. That is, an appropriate amount of a sample is taken, 100 ml of a solvent (diethyl ether / ethanol mixed solution) and a few drops of an indicator (phenolphthalein solution) are added, and shaken sufficiently until the sample is completely dissolved in a water bath. This is titrated with a 0.1 mol / l potassium hydroxide ethanol solution, and the end point is when a light red color of the indicator lasts for 30 seconds. When the acid value is A, the sample amount is S (g), the 0.1 mol / l potassium hydroxide ethanol solution used for the titration is B (ml), and f is the factor of the 0.1 mol / l potassium hydroxide ethanol solution. , A = (B × f × 5.611) / S.

The polyester resin is obtained by a well-known manufacturing 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.

<Method for producing vinyl / polyester resin composite particles>
In the above-mentioned JP-A-2006-002109 and JP-A-06-317925, the polymerization methods described in the respective examples contain vinyl resin in an amount of 40% by mass or more and a volume average particle size of 1 μm or less. No vinyl / polyester resin composite particles having a core / shell structure as described above were obtained. Although this reason is not certain, it is guessed that it is due to the following reasons, for example.

  Since the polyester resin and the vinyl resin have low affinity, it is considered difficult to simply mix the components constituting both and to polymerize the vinyl resin to increase inside the polyester resin. For example, when a component constituting a polyester resin and a component constituting a vinyl resin are mixed together to obtain a vinyl / polyester resin composite particle having a core / shell structure, vinyl inside the polyester resin is obtained. Even if a part of the monomer is polymerized, the vinyl monomer may be polymerized outside the polyester resin. Therefore, it is considered that it is difficult to obtain the core / shell structure vinyl / polyester resin composite particles in which the coating layer containing the polyester resin is formed without suppressing the exposure of the vinyl resin.

As described above, the vinyl / polyester resin composite particles of the present embodiment include a vinyl resin in an amount of 40% by mass to 95% by mass and a volume average particle size of 100 nm to 500 nm. As a production method for obtaining the resin composite particles, it is preferable to polymerize the vinyl monomer inside the polyester resin particles from the viewpoint of increasing the vinyl resin inside the polyester resin. For example, a phase inversion emulsification step in which a polyester resin particle dispersion is obtained by phase inversion emulsification of a chlorinated polyester resin, and a polymerization step in which a vinyl monomer is polymerized inside the polyester resin particles of the polyester resin particle dispersion. A preferred example is a production method comprising
The “inside of the polyester resin particle” is a region inside the surface of the polyester resin particle.

  Hereinafter, although the preferable example given above is demonstrated in detail as a method of manufacturing the vinyl / polyester resin composite particle concerning this embodiment, it is not limited to this method.

The following points can be considered as the reason why the production method mentioned as an example is preferable.
Polyester resin particles obtained by phase inversion emulsification of a chlorinated polyester resin have self-emulsifying properties, and hydrophilic groups face outward. For this reason, when a vinyl monomer is added to the polyester resin particles, the vinyl monomer easily enters the polyester resin particles. It is considered that the content of the vinyl resin can be increased to 40% by mass or more by polymerizing the vinyl monomer inside the polyester resin particles. The vinyl / polyester resin composite particles obtained by polymerizing the vinyl monomer inside the polyester resin particles have a small diameter and are considered to contain a large amount of vinyl resin. Further, in the resin composite particles obtained as described above, the exposure of the vinyl resin is suppressed on the surface of the resin composite particles.

As a production method mentioned as a preferable example, there are a phase inversion emulsification step in which a chlorinated polyester resin is phase-inverted and emulsified to obtain a polyester resin particle dispersion, and vinyl is added inside the polyester resin particles in the polyester resin particle dispersion And a polymerization step for polymerizing the monomer.
Furthermore, in the phase inversion emulsification process, for example, a polyester resin is dissolved in an organic solvent to prepare a polyester resin solution; a polyester resin solution prepared in the dissolution process and a base are mixed. A chlorinated polyester resin is prepared, and further mixed with water to undergo phase inversion emulsification to obtain a polyester resin particle dispersion; the organic solvent is removed from the polyester resin particle dispersion obtained in the phase inversion process. Each step of the organic solvent removal step.

[Phase inversion emulsification process]
(Dissolution process)
The dissolution step is a step of dissolving the polyester resin in an organic solvent. Examples of the organic solvent that dissolves the polyester resin include organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; organic solvents such as tetrahydrofuran, 1,4-dioxane, and 1,3-dioxane; chloroform, Examples include halogen-containing organic solvents such as methylene chloride; organic solvents such as n-butanol and isopropanol; and organic solvents such as esters such as ethyl acetate. These organic solvents may be used individually by 1 type, and may use 2 or more types together. Among these organic solvents, an organic solvent having a boiling point lower than that of water is preferable from the viewpoint of removing the organic solvent in a later step. For example, an organic solvent using a combination of an organic solvent of ketones and an organic solvent of alcohols is used. More preferably, it is used.
In addition, the organic solvent is 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyester resin from the viewpoint of the efficiency of obtaining a polyester resin particle dispersion, the particle size distribution of the polyester resin particles, the dispersibility, etc. It is good to use in. It is preferably used in an amount of 20 parts by mass or more and 150 parts by mass or less, and more preferably 25 parts by mass or more and 100 parts by mass or less.

(Phase inversion process)
The phase inversion emulsification step is a step in which a polyester resin solution prepared in the dissolution step and a base are mixed to prepare a chlorinated polyester resin, which is mixed with water for phase inversion emulsification to obtain a polyester resin particle dispersion. It is.

  Here, the chlorinated polyester resin is a polyester resin having a structure in which a carboxy group contained in the polyester resin is salified with a base. The chlorinated polyester resin can be obtained, for example, by a step of dissolving a polyester resin in an organic solvent to prepare an organic solvent solution of the polyester resin and adding a base.

  Examples of the base for obtaining a chlorinated polyester resin include amine compounds such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and triethylamine; inorganic bases such as aqueous ammonia, sodium hydroxide, and potassium hydroxide. can give.

  The amount of the base to be mixed is determined according to the amount of the carboxy group of the polyester resin. From the viewpoint of phase inversion emulsification, for example, it is preferable to use an amount of base that is 0.4 equivalents or more and 2.0 equivalents or less with respect to all carboxy groups of the polyester resin. It is more preferable to use an amount of the base that is 0.5 equivalent or more and 1.0 equivalent or less. Specifically, the acid value of the chlorinated polyester resin is preferably in the range of 5 mgKOH / g to 30 mgKOH / g, and more preferably in the range of 5 mgKOH / g to 20 mgKOH / g.

  Next, the chlorinated polyester resin and water are mixed to effect phase inversion emulsification. Although the liquid containing the chlorinated polyester resin and water can be mixed at one time, it is preferable to gradually mix the liquid containing the chlorinated polyester resin and water. For example, specifically, a method in which a liquid containing a chlorinated polyester resin is gradually added by dropping water while stirring at room temperature (for example, 25 ° C.).

(Organic solvent removal step)
The organic solvent removal step is a step of removing the organic solvent from the polyester resin particle dispersion obtained in the phase inversion emulsification step. The removal of the organic solvent may be performed under any conditions under reduced pressure or normal pressure. Moreover, you may carry out under any conditions of heating or non-heating.

The volume average particle size of the polyester resin particles dispersed in the polyester resin particle dispersion obtained through the organic solvent removal step is preferably, for example, from 30 nm to 400 nm, from the viewpoint of obtaining small-diameter resin composite particles, and 40 μm or more. 300 μm or less is more preferable, and 50 nm or more and 200 nm or less is particularly preferable.
In addition, the volume average particle size is about the volume with respect to the divided particle size range (channel) using the particle size distribution obtained by measurement of a laser diffraction type particle size distribution measuring device (for example, LA-700 manufactured by Horiba, Ltd.). The cumulative distribution is subtracted from the small particle size side, and the particle size that becomes 50% cumulative with respect to all particles is measured as the volume average particle size (D50v).

  Moreover, as content of the polyester resin particle contained in this polyester resin particle dispersion liquid, 1 to 50 mass% is preferable, for example, and 2 to 40 mass% is more preferable.

[Polymerization process]
The polymerization step is a step in which the polyester resin particle dispersion obtained in the phase inversion emulsification step and the vinyl monomer are mixed and the vinyl monomer is polymerized inside the polyester resin particles.
As a specific method of the polymerization step, for example, for example, a vinyl monomer and a chain transfer agent are mixed and emulsified with water and a surfactant to produce an emulsion of the vinyl monomer. To do. Next, the polyester resin particle dispersion obtained in the organic solvent removal step and the polymerization initiator are mixed, and further the emulsion of the vinyl monomer is gradually mixed. Thereafter, the vinyl monomer is polymerized inside the polyester resin particles by heating or the like.
In addition, a chain transfer agent and a polymerization initiator are components added as needed. Moreover, although the emulsion liquid of the vinyl monomer was produced, what is necessary is just to perform it as an emulsion liquid as needed.

  It is preferable to gradually mix (for example, drop) the vinyl monomer from the viewpoint of increasing the vinyl resin content by entering the polyester resin particles. Moreover, as temperature which polymerizes a vinyl monomer inside a polyester resin particle, it is preferable that it is the range of 40 to 85 degreeC, for example.

  In addition, although the preferable example was given and demonstrated as a manufacturing method of the vinyl / polyester resin composite particle concerning this embodiment, it is not limited to said example. Any method can be used as long as the resin composite particles containing 40% by mass or more and 95% by mass or less of the vinyl resin with respect to the total solid content of the core and the coating layer can be obtained. Any one of the methods may be used.

<Toner for electrostatic image development>
Next, as an example of the use of the vinyl / polyester resin composite particles according to this embodiment, an example applied to toner will be described.
The application of the resin composite particles is not limited to toner.

  The toner according to the exemplary embodiment includes toner particles containing a binder resin including a polyester resin and the vinyl / polyester resin composite particles.

  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 include, for example, a binder resin including a polyester resin and the vinyl / polyester resin composite particles according to the present embodiment, and if necessary, a colorant, a release agent, and other additives. Consists of.

(Vinyl / polyester resin composite particles)
When the above-mentioned vinyl / polyester resin composite particles are applied to toner particles, the resin composite particles are contained in an amount of 20% by mass or more and 50% by mass or less based on the whole toner particles from the viewpoint of suppressing toner aggregation and the like. It is preferable. Moreover, 20 mass% or more and 45 mass% or less are more preferable. More preferably, it is 25 mass% or more and 40 mass% or less.

The volume average particle size of the resin composite particles is 100 nm or more and 500 nm or less. From the viewpoint of further suppressing toner aggregation and the like, 100 nm or more and 400 nm or less is more preferable. The thickness is particularly preferably from 100 nm to 300 nm.
The volume average particle size of the vinyl / polyester resin composite particles in the toner particles is measured by the following method.
First, put a few drops of a surfactant such as Contaminone (manufactured by Wako Pure Chemical Industries, Ltd.) into ion-exchanged water, add toner to it, wet and mix and disperse, and then perform ultrasonic treatment for 1 to 5 minutes. To remove the external additive. Thereafter, the dispersion liquid mixed and dispersed is passed through a filter paper, rinsed, and then the toner particles on the filter paper are dried.
Next, the toner particles are mixed and embedded in an epoxy resin to solidify the epoxy resin. Thereafter, the obtained solidified product is cut by an ultramicrotome apparatus (Ultracut UCT, manufactured by Leica) to produce a thin piece sample having a thickness of 80 nm to 130 nm. Next, the obtained flake sample is dyed with osmium tetroxide in a desiccator at 30 ° C. for 3 hours. And the STEM image of the dyed thin piece sample is obtained with SEM (scanning electron microscope: S-4800, manufactured by Hitachi High-Technologies Corporation). If it is difficult to distinguish the shade due to the condition of the sample, adjust the staining time.
Then, the stained vinyl / polyester resin composite particles (its domains) are observed in the cross section of the toner particles in the STEM image. 100 resin composite particles are selected, and the diameter (longest portion) r1 of the resin composite particles is measured for each resin composite particle to be measured by image analysis. This is measured for 100 particles, a particle size distribution is obtained, the volume is obtained by converting the spheres from r1 to r100 into a spherical shape, and the value when the accumulation from the first to the 100th becomes 50% is the volume average particle diameter ( D50v).

(Binder resin)
The polyester resin used for the binder resin is not particularly limited. For example, the amorphous polyester resin alone may be used, or the amorphous polyester resin and the crystalline polyester resin may be used in combination. From the viewpoint of imparting low-temperature fixability, a binder resin containing an amorphous polyester resin and a crystalline polyester resin is preferable.
The “crystallinity” of the resin is as described above.

When the binder resin contains a crystalline polyester resin, it is preferably used at a content of 10% by mass or more and 50% by mass or less with respect to the whole toner particles. Furthermore, it is preferable to use with content of 12 mass% or more and 40 mass% or less. In particular, it is preferably used in an amount of 15% by mass to 30% by mass.
Hereinafter, the polyester resin used for the binder resin will be described.

-Amorphous polyester resin-
As an amorphous polyester resin, the condensation polymer of polyhydric carboxylic acid and polyhydric alcohol is mentioned, for example. In addition, as an amorphous polyester resin, a commercial item may be used and what was synthesize | combined may be used.

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, or lower (eg, having 1 to 5 carbon atoms) alkyl ester.
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.

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 5,000 or more and 100,000 or less, and more preferably 7,000 or more and 50,000 or less.
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.

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 50,000 or less.

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

  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.

-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 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, when toner particles are produced by an aggregation coalescence method,
A step of preparing a resin particle dispersion in which resin particles to be a binder resin are dispersed (resin particle dispersion preparation step) and a step of preparing a vinyl / polyester resin composite particle dispersion (vinyl / polyester resin composite particle dispersion) Preparatory step), in the resin particle dispersion (in the dispersion after mixing other particle dispersion if necessary), agglomerate the resin particles (other particles as necessary), A step of forming (aggregated particle forming step) and a step of heating the aggregated particle dispersion in which the aggregated particles are dispersed to fuse and coalesce the aggregated particles to form toner particles (fusion and coalescence step) Then, toner particles are manufactured.

Details of each step will be described below.
In the following description, a method for obtaining toner particles containing vinyl / polyester resin composite particles, a colorant, and a release agent will be described. 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, together with a resin particle dispersion in which resin particles serving as a binder resin are dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed and a release agent particle dispersion in which release agent particles are dispersed are prepared. To do. Further, a vinyl / polyester resin composite particle dispersion 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 a particle size range (channel) divided by using a particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring apparatus (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.

  Note that, for example, a colorant particle dispersion and a release agent 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.

-Aggregated particle formation process-
Next, the colorant particle dispersion and the release agent particle dispersion are mixed together with the resin particle dispersion. Further, a vinyl / polyester resin composite particle dispersion is mixed.
In the mixed dispersion, resin particles and colorant particles having a diameter close to the diameter of the target toner particles are obtained by heteroaggregating resin particles, colorant particles, release agent particles, and vinyl / polyester resin composite particles. And agglomerated particles containing release agent particles.

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

Examples of 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.
The addition amount of the chelating agent is, for example, preferably 0.01 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass with respect to 100 parts by mass of the resin particles.

-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 fusion / unification 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 a coating resin is coated on the surface of a core made of magnetic powder; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and blended 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 that accommodates the electrostatic charge image developer according to this embodiment and includes a developing unit 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.

(Preparation of polyester resin particle dispersion for vinyl / polyester resin composite particles)
-Synthesis of Amorphous Polyester Resin (1)-
In a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube, 50 mol parts of bisphenol A ethylene oxide 2 mol adduct (BPA-EO) and 2 mol of bisphenol A propylene oxide adduct as a polyhydric alcohol component (BPA-PO) 50 mol parts, polyhydric carboxylic acid component, terephthalic acid (TPA) 60 mol parts, dodecenyl succinic anhydride (DSA) 30 mol parts, trimellitic anhydride (TMA) 10 mol parts The inside of the reaction vessel was replaced with dry nitrogen gas. 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 produce an amorphous polyester resin (1) for resin composite particles. Got. The amorphous polyester resin (1) had an acid value of 16.0, a weight average molecular weight (Mw) of 86,000, and a glass transition temperature of 58 ° C.

-Preparation of Amorphous Polyester Resin Particle Dispersion (1A)-
After dissolving 100 parts by mass of amorphous polyester resin (1) for resin composite particles in 80 parts by mass of methyl ethyl ketone (MEK) and 20 parts by mass of isopropyl alcohol (IPA), 4.0 parts by mass of 10% ammonia water was added. . Thereafter, 200 parts by mass of ion-exchanged water was added dropwise over 2 hours while stirring at room temperature (25 ° C.). Next, after the solvent was distilled off under reduced pressure, water was added to adjust the solid content concentration to 30% to obtain an amorphous polyester resin particle dispersion (1A) for resin composite particles. The volume average particle diameter (D50v) of the amorphous polyester resin particles in this amorphous polyester resin particle dispersion (1A) was 78 nm.

-Preparation of Amorphous Polyester Resin Particle Dispersion (1B)-
Amorphous polyester resin for resin composite particles (1) Amorphous polyester resin except that 100 parts by mass of MEK is dissolved in 50 parts by mass of MEK and 10 parts by mass of IPA, and then 3.5 parts by mass of 10% ammonia water is added. An amorphous polyester resin particle dispersion (1B) for resin composite particles was obtained in the same procedure as the preparation of the particle dispersion (1A). The volume average particle diameter of the amorphous polyester resin particles in the amorphous polyester resin particle dispersion (1B) was 175 nm.

-Preparation of Amorphous Polyester Resin Particle Dispersion (1C)-
100 parts by mass of the amorphous polyester resin (1) for resin composite particles was dissolved in 300 parts by mass of ethyl acetate. 4.0 parts by mass of sodium dodecylbenzenesulfonate was dissolved in 250 parts by mass of ion-exchanged water, and added to the ethyl acetate solution in which the amorphous polyester resin (1) for resin composite particles was dissolved. Using a TK homomixer, the mixture was stirred and emulsified at 10,000 rpm for 10 minutes. After the solvent was distilled off under reduced pressure, water was added to adjust the solid content concentration to 30% to obtain an amorphous polyester resin particle dispersion (1C) for resin composite particles. The volume average particle diameter of the amorphous polyester resin particles in this amorphous polyester resin particle dispersion (1C) was 210 nm.

<Example 1>
[Preparation of vinyl / polyester resin composite particle dispersion (CS-1)]
616 parts by mass of styrene, 184 parts by mass of butyl acrylate, 12.6 parts by mass of dodecanethiol, 10 parts by mass of surfactant Dowfax2A1 (47% solution), 320 parts by mass of ion-exchanged water were mixed, and 1,500 rpm, Stirring and emulsification were performed for 30 minutes to prepare a monomer emulsion.
Separately, 666.7 parts by mass of an amorphous polyester resin particle dispersion (1A) for resin composite particles and 1093.3 parts by mass of ion-exchanged water were charged into a reaction vessel. Subsequently, after heating to 75 degreeC under nitrogen stream, the polymerization initiator solution which melt | dissolved 7.5 parts of ammonium persulfate in 120 mass parts of ion-exchange water was added. Thereafter, the monomer emulsion prepared above was added dropwise over 150 minutes. After a further 180 minutes of reaction at 75 ° C. under a nitrogen stream, 11.3 parts by weight of surfactant Dowfax2A1 (47% solution) was added, the solid content concentration was adjusted to 30% after cooling, and vinyl / A polyester resin composite particle dispersion (CS-1) was obtained.
The resin composite particles had a volume average particle size (D50v) of 133 nm and a volume average particle size distribution index (GSDv) of 1.18. Further, the ratio of the polyester resin present on the surface of the resin composite particles (hereinafter referred to as “PES presence ratio”) was measured by an X-ray photoelectron spectrometer (XPS) and found to be 84%. The proportion of vinyl resin was 16%.

<Example 2>
[Preparation of vinyl / polyester resin composite particle dispersion (CS-2)]
Styrene is changed to 385 parts by mass, butyl acrylate is changed to 115 parts by mass, dodecanethiol is changed to 7.9 parts by mass, and amorphous polyester resin particle dispersion (1A) for resin composite particles is further added to 1666.7 parts by mass. A vinyl / polyester resin composite particle dispersion (CS-2) was obtained in the same manner as in Example 1 except that the ion-exchanged water was changed to 393.3 parts by mass.
Table 1 shows the measurement results of the volume average particle diameter, the volume average particle size distribution index, and the PES presence ratio by XPS of the resin composite particles.

<Example 3>
[Preparation of vinyl / polyester resin composite particle dispersion (CS-3)]
693 parts by mass of styrene, 207 parts by mass of butyl acrylate, and 14.1 parts by mass of dodecanethiol, and 333.3 parts by mass of an amorphous polyester resin particle dispersion (1A) for resin composite particles A vinyl / polyester resin composite particle dispersion (CS-3) was obtained in the same manner as in Example 1 except that the ion-exchanged water was changed to 1326.7 parts by mass.
Table 1 shows the measurement results of the volume average particle diameter, the volume average particle size distribution index, and the PES presence ratio by XPS of the resin composite particles.

<Example 4>
[Preparation of vinyl / polyester resin composite particle dispersion (CS-4)]
The composition was changed to 385 parts by mass of styrene, 115 parts by mass of butyl acrylate and 7.9 parts by mass of dodecanethiol. Polyester resin particle dispersion (1B) 1666.7 parts by mass, ion / exchange water was changed to 393.3 parts by mass in the same manner as in Example 1, vinyl / polyester resin composite particle dispersion (CS-4) Got.
Table 1 shows the measurement results of the volume average particle diameter, the volume average particle size distribution index, and the PES presence ratio by XPS of the resin composite particles.

<Example 5>
[Preparation of vinyl / polyester resin composite particle dispersion (CS-5)]
Vinyl / polyester in the same manner as in Example 1 except that the amorphous polyester resin particle dispersion (1A) for resin composite particles was changed to the amorphous polyester resin particle dispersion (1B) for resin composite particles. A resin composite particle dispersion (CS-5) was obtained.
Table 1 shows the measurement results of the volume average particle diameter, the volume average particle size distribution index, and the PES presence ratio by XPS of the resin composite particles.

<Example 6>
[Preparation of vinyl / polyester resin composite particle dispersion (CS-6)]
The composition was changed to 693 parts by mass of styrene, 207 parts by mass of butyl acrylate, and 14.1 parts by mass of dodecanethiol, and the amorphous polyester resin particle dispersion (1A) for resin composite particles was further converted to amorphous for resin composite particles. Vinyl / polyester resin composite particle dispersion (CS-6) in the same manner as in Example 1 except that 320.5 parts by mass of the polyester resin particle dispersion (1B) and ion exchange water were changed to 1299.5 parts by mass. Got.
Table 1 shows the measurement results of the volume average particle diameter, the volume average particle size distribution index, and the PES presence ratio by XPS of the resin composite particles.

<Comparative Example 1>
[Preparation of vinyl / polyester resin composite particle dispersion (CS-1c)]
Vinyl / polyester in the same manner as in Example 1 except that the amorphous polyester resin particle dispersion (1A) for resin composite particles was changed to the amorphous polyester resin particle dispersion (1C) for resin composite particles. A resin composite particle dispersion (CS-1c) was obtained.
Table 1 shows the measurement results of the volume average particle diameter, the volume average particle size distribution index, and the PES presence ratio by XPS of the resin composite particles.

<Comparative Example 2>
[Preparation of vinyl / polyester resin composite particle dispersion (CS-2c)]
Amorphous polyester resin particle dispersion (1A) 666.7 parts by mass for resin composite particles, 616 parts by mass of styrene, 184 parts by mass of butyl acrylate, 12.6 parts by mass of dodecanethiol, surfactant Dowfax 2A1 (47% solution) ) 10 parts by mass and 1413.3 parts by mass of ion-exchanged water were mixed and stirred and emulsified with a dissolver under conditions of 1,500 rpm and 30 minutes.
After heating to 75 ° C. under a nitrogen stream, a polymerization initiator solution in which 7.5 parts of ammonium persulfate was dissolved in 120 parts of ion-exchanged water was added dropwise over 150 minutes. After further reaction for 180 minutes at 75 ° C. under a nitrogen stream, 11.3 parts by mass of surfactant Dowfax2A1 (47% solution) was added, and after cooling, the solid content concentration was adjusted to 30%, and the resin composite A particle dispersion (CS-2c) was obtained.
Table 1 shows the measurement results of the volume average particle diameter, the volume average particle size distribution index, and the PES presence ratio by XPS of the resin composite particles.

  In Table 1 below, “particle size” indicates a volume average particle size.

  From the above results, it can be seen that in this example, novel vinyl / polyester resin composite particles having a small diameter and containing a large amount of vinyl resin were obtained. And the resin composite particle | grains in which the polyester resin measured by the X ray photoelectron spectrometer (XPS) in the surface of a vinyl / polyester resin composite particle shows 80% or more were obtained. This shows that the exposure of the vinyl resin to the surface is suppressed.

<Application to toner>
[Preparation of crystalline polyester resin particle dispersion]
-Preparation of crystalline polyester resin particle dispersion (Cr1)-
In a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, 50 mol% of 1,6-hexanediol as a polyhydric alcohol component and 50 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. The obtained crystalline polyester resin (Cr1) had a melting temperature by DSC of 74 ° C.
Next, in a jacketed 3 liter reaction tank (Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, thermometer, water dropping device, anchor blade, 300 parts of crystalline polyester resin (Cr1) and 160 parts of methyl ethyl ketone And 100 parts 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 stirring speed 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 / ion of ion-exchanged water kept at 66 ° C. A total of 900 parts was dropped at a rate of minutes to invert the phase to obtain an emulsion. 800 parts of the obtained emulsified liquid and 700 parts 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. Thereafter, ion-exchanged water was added to obtain a crystalline polyester resin particle dispersion (Cr1) having a solid content concentration of 20% by mass.

[Preparation of Amorphous Polyester Resin Particle Dispersion]
-Preparation of Amorphous Polyester Resin Particle Dispersion (A1)-
In the same manner as the amorphous polyester resin particle dispersion (1A) for resin composite particles, an amorphous polyester resin particle dispersion (A1) was obtained.

[Preparation of colorant particle dispersion]
Carbon black (Cabot Co., Regal 330): 45 parts by mass Ionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R): 5 parts by mass Ion-exchanged water: 200 parts by mass Mixing and dissolving the above, homogenizer Dispersion was carried out for 10 minutes using (IKA, Ultra Turrax T50), and then dispersion treatment was performed using an optimizer to obtain a colorant particle dispersion having a solid content concentration of 20% and a volume average particle size of 245 nm.

[Preparation of release agent particle dispersion]
-Paraffin wax (Nippon Seiki Co., Ltd., HNP0190): 45 parts by mass-Ionic surfactant (Daiichi Kogyo Seiyaku, Neogen R): 5 parts by mass-Ion-exchanged water: 200 parts by mass The mixture was heated and dispersed with a pressure discharge type gorin homogenizer to obtain a release agent particle dispersion having a solid content of 20% and a volume average particle size of 219 nm.

[Preparation of vinyl resin particle dispersion]
-Preparation of styrene / (meth) acrylic resin particle dispersion (Vn1)-
770 parts by mass of styrene, 230 parts by mass of butyl acrylate, 15.7 parts by mass of dodecanethiol, 19.8 parts by mass of surfactant Dowfax2A1 (47% solution), 576 parts by mass of ion-exchanged water, and 1, The mixture was stirred and emulsified at 500 rpm for 30 minutes to prepare a monomer emulsion. 1.49 parts by mass of Dowfax 2A1 (47% solution) and 1270 parts by mass of ion-exchanged water were charged into the reaction vessel. After heating to 75 ° C. under a nitrogen stream, 75 parts by mass of the monomer emulsion is added, and then a polymerization initiator solution in which 15 parts by mass of ammonium persulfate is dissolved in 98 parts by mass of ion-exchanged water is added dropwise over 10 minutes. did. After reacting for 50 minutes after the dropwise addition, the remaining monomer emulsion was added dropwise over 220 minutes and allowed to react for an additional 180 minutes. After cooling, the solid content concentration was adjusted to 30% to obtain a styrene / (meth) acrylic resin particle dispersion (Vn1). The volume average particle diameter was 181 nm.

[Production of toner]
(Production of Toner (1))
Amorphous polyester resin particle dispersion (A1): 69.5 parts by mass Crystalline polyester resin particle dispersion (Cr1): 202.9 parts by mass Vinyl / polyester resin composite particle dispersion (CS-1): 262.6 parts by mass-Colorant particle dispersion: 127.5 parts by weight-Release agent particle dispersion: 133.3 parts by mass-0.3M aqueous nitric acid solution: 12.7 parts by mass-Ion exchange water: 439.7 Parts by mass

The above components are housed in a round stainless steel flask and dispersed using a homogenizer (IKA, Ultra Turrax T50). After confirming the formation of particles, an additional mixture of 249.2 parts by mass of the amorphous polyester resin particle dispersion (1A) and 25.2 parts of 0.3M aqueous nitric acid was added, and another 30 minutes. Retained.
Subsequently, EDTANa salt (manufactured by Chubu Kirest Co., Ltd., Kirest 40) was added so as to be 2.5% by mass of the total liquid. Thereafter, a 1N aqueous sodium hydroxide solution was gently added until pH 8.5 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).
The volume average particle diameter of the toner particles (1) is 3.85 μm.

  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 ( Nippon Aerosil Co., Ltd., R972) 1 part by mass was added, mixed for 5 minutes at a peripheral speed of 30 m / s using a 5 liter Henschel mixer, then coarse particles were removed using a 45 μm sieve and toner was removed. (1) was produced.

(Production of Toner (2))
Toner (2) was prepared in the same manner as toner (1) except that vinyl / polyester resin composite particle dispersion (CS-1) was changed to vinyl / polyester resin composite particle dispersion (CS-2). did.
The volume average particle size of the toner particles (2) is 3.90 μm.

(Production of Toner (3))
Toner (3) was prepared in the same manner as toner (1), except that vinyl / polyester resin composite particle dispersion (CS-1) was changed to vinyl / polyester resin composite particle dispersion (CS-6). did.
The volume average particle diameter of the toner particles (3) is 3.94 μm.

(Production of Toner (4))
Amorphous polyester resin particle dispersion (A1): 6.2 parts by mass Crystalline polyester resin particle dispersion (Cr1): 163.1 parts by mass Vinyl / polyester resin composite particle dispersion (CS-1): 356.4 parts by mass-Colorant particle dispersion: 127.5 parts by mass-Release agent particle dispersion: 133.3 parts by mass-0.3M aqueous nitric acid solution: 12.7 parts by mass-Ion exchange water: 439.7 Part by mass A toner (4) was produced in the same manner as in the production of the toner (1) except that the composition was changed.
The volume average particle diameter of the toner particles (4) is 3.73 μm.

(Production of Toner (5))
Amorphous polyester resin particle dispersion (A1): 23.2 parts by mass Crystalline polyester resin particle dispersion (Cr1): 270.5 parts by mass Vinyl / polyester resin composite particle dispersion (CS-1): 267.3 parts by mass-Colorant particle dispersion: 127.5 parts by weight-Release agent particle dispersion: 133.3 parts by mass-0.3M aqueous nitric acid solution: 12.7 parts by mass-Ion exchange water: 439.7 Part by mass A toner (5) was produced in the same manner as in the production of the toner (1) except that the composition was changed.
The volume average particle size of the toner particles (5) is 3.80 μm.

(Production of Toner (1c))
First, 65.5 parts by mass of the amorphous polyester resin particle dispersion (1A) contained in the flask is 255.5 parts by mass, and 202.9 parts by mass of the crystalline polyester resin particle dispersion (Cr1) is 322.2 parts by mass. The toner (1c) was prepared in the same manner as in the preparation of the toner (1) except that the vinyl / polyester resin composite particle dispersion (SC-1) was not used.
The volume average particle size of the toner particles (1c) was 3.81 μm.

(Production of Toner (2c))
Toner (2c) was prepared in the same manner as toner (1), except that the vinyl / polyester resin composite particle dispersion (CS-1) was changed to styrene / (meth) acrylic resin particle dispersion (Vn1). did.
The volume average particle diameter of the toner particles (2c) is 3.94 μm.

(Production of Toner (3c))
Toner (3c) was prepared in the same manner as toner (1) except that vinyl / polyester resin composite particle dispersion (CS-1) was changed to vinyl / polyester resin composite particle dispersion (CS-1c). did.
The volume average particle diameter of the toner particles (3c) is 3.95 μm.

(Production of Toner (4c))
Toner (4c) was prepared in the same manner as toner (1) except that vinyl / polyester resin composite particle dispersion (CS-1) was changed to vinyl / polyester resin composite particle dispersion (CS-2c). did.
The volume average particle diameter of the toner particles (4c) is 4.01 μm.

[Evaluation]
Developers were prepared using the toners obtained in toner preparation, and the following evaluations were performed. The evaluation results are shown in Table 2.

The developer was produced as follows.
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.
This resin-coated ferrite carrier and each toner obtained by the preparation of the toner were mixed in a V blender at a ratio of 92 parts by mass of the carrier: 8 parts by mass of the toner to prepare each developer.

(Toner aggregation)
Each developer was filled in the developing device of an electrophotographic copying machine (trade name: A-color, manufactured by Fuji Xerox Co., Ltd.), and 10,000 images with an image density of 1% were output using this electrophotographic copying machine. The state of the toner in the later developing unit was visually observed.
-Evaluation criteria-
A (◯): Almost no toner aggregated in the developing device is observed.
B (Δ): Slightly aggregated toner is observed in the developing device.
C (x): Aggregated toner is observed in the developing device.

(Evaluation of image defects)
As image defects, evaluation of missing images was performed as follows.
A halftone image having an image density of 50% was output on A4 paper (manufactured by Fuji Xerox Co., Ltd.) using a copy machine DocuCenter Color C400 manufactured by Fuji Xerox Co., Ltd.
The image was output in an environment of 25 ° C. and 50% RH.
-Evaluation criteria-
A (◯): A4 The number of missing white spots per sheet is less than one.
B (Δ): A4 The number of white spots of missing images per sheet is 1 or more and less than 5.
C (x): A4 There are 5 or more white spots that are missing in one image.

  In Table 2 below, “PES” indicates a polyester resin.

  It can be seen that toners 1 to 5 have better results for both toner aggregation and image defects than toners 1c to 4c.

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 Attachment rail 118 Opening 117 for exposure 117 Case 200 Process cartridge 300 Recording paper (an example of recording medium)
P Recording paper (an example of a recording medium)

Claims (11)

A core portion including a vinyl resin, and a coating layer covering the core portion, the coating layer including a polyester resin,
The vinyl resin is contained in an amount of 40% by mass or more and 95% by mass or less based on the total solid content of the core and the coating layer,
Vinyl / polyester resin composite particles having a volume average particle size (D50v) of 100 nm to 500 nm.   The vinyl / polyester resin composite particles according to claim 1, wherein the vinyl / polyester resin composite particles are resin composite particles obtained by polymerizing a vinyl monomer inside the polyester resin particles. A phase inversion emulsification step in which a polyester resin particle dispersion is obtained by phase inversion emulsification of the chlorinated polyester resin;
A polymerization step of polymerizing a vinyl monomer inside the polyester resin particles of the polyester resin particle dispersion,
The manufacturing method of the vinyl / polyester resin composite particle of any one of Claim 1 or 2 which has these.   An electrostatic image developing toner comprising toner particles containing a binder resin containing a polyester resin and the vinyl / polyester resin composite particles according to claim 1.   The electrostatic charge image developing toner according to claim 4, wherein the vinyl / polyester resin composite particles are contained in an amount of 20% by mass or more and 50% by mass or less based on the entire toner particles.   The binder resin includes a crystalline polyester resin and an amorphous polyester resin, and the crystalline polyester resin is contained in an amount of 10% by mass or more and 50% by mass or less based on the whole toner particles. Or the toner for developing an electrostatic charge image according to any one of 5;   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 4. Containing the toner for developing an electrostatic charge image according to any one of claims 4 to 6,
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 7 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 image developer according to claim 7 and developing the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic 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 7;
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: