JP2018025723A - Toner for electrostatic charge image development and method for manufacturing the same, method for manufacturing mold release agent particle fluid dispersion, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development excellent in releasability of a fixed image from a fixing member.SOLUTION: A toner for electrostatic charge image development includes toner particles each containing a binder resin and a mold release agent, where when the cross section of the toner particle is analyzed with an energy dispersive X-ray analyzer (EDX), the value of B being the amount of sulfur element in a domain part of the mold release agent is 0.2 atom% or more and 1.5 atom% or less.SELECTED DRAWING: None

Description

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

  In electrophotographic image formation, toner is used as an image forming material.For example, toner particles containing a binder resin, a release agent, and a colorant, and an external additive externally added to the toner particles; Many toners containing toner are used.

Examples of conventional toners include toners described in Patent Documents 1 to 7.
Patent Document 1 has toner particles containing a binder resin including a polyester resin that forms a sea part of a sea-island structure and a vinyl resin that forms an island part of a sea-island structure, and a domain-shaped release agent. In the cut surface of the toner particles observed by a scanning electron microscope (TEM), the peripheral length of the cross section of the domain of the release agent is L, and the portion of the peripheral length L of the cross section that contacts the vinyl resin Describes a toner for developing an electrostatic image satisfying a relationship of 0.60 ≦ Ls / L ≦ 0.90, where Ls is Ls.
Patent Document 2 includes a binder resin, a colorant, and a release agent. In the cross-sectional observation of the toner before fixing, the release agent has a flat domain, and the domain diameter of the release agent is The long diameter (DL1) is 0.6 μm or more, and the ratio (DL1 / DS1) of the long diameter (DL1) to the short diameter (DS1) of the domain diameter of the release agent is 2.0 or more. In the cross-sectional observation, an electrostatic charge image developing toner in which a domain diameter (D2) of the release agent is 0.5 μm or less is described.
Patent Document 3 discloses a toner containing at least a non-crystalline resin and a crystalline resin as a binder resin, and a release agent, which is detected from a transmission electron microscope (TEM) photograph of a broken section of the toner. The maximum length Lmax of the release agent in the toner particles is 1.1 times or more of the maximum value Feret diameter Df of the toner particles containing the release agent, and the crystalline resin is dispersed in the amorphous resin. The electrophotographic toner is characterized in that the maximum ferret diameter Cf of the domain made of the crystalline resin is 0.20 μm or less.

In Patent Document 4, at least a step of forming a clear toner particle layer using a clear toner on an image support, and heating and pressurizing in a state where the surface of the image support on which the clear toner particle layer is formed are in close contact with a belt. And a step of cooling to form a clear toner layer, wherein the clear toner contains at least a binder resin and a release agent and is measured by a differential scanning calorimeter of the clear toner. The DSC curve has a heat of fusion of 3.0 J / g or more and 9.5 J / g or less, and the total area of the release agent domains in the clear toner particle cross section is S1, from the particle surface toward the center of gravity. A glossy image forming method, wherein S2 / S1 is 0.5 or more and 1.0 or less, where S2 is the total area of the release agent domains existing within a range of 2 μm or less. It has been.
Patent Document 5 discloses a resin particle dispersion in which at least resin particles are dispersed, a colorant particle dispersion in which at least colorant particles are dispersed, and a release agent particle dispersion in which at least release agent particles are dispersed. In the method for producing a toner for developing an electrostatic charge image, the step of aggregating the particles, the step of aggregating the particles, and the step of fusing the agglomerates to fuse the particles, the release agent particles of the release agent particle dispersion However, there is described a method for producing a toner for developing an electrostatic image, wherein the volume average particle size is less than 0.5 μm and the particle size of 1.0 μm or more is 5% or less.

Patent Document 6 discloses a toner including a plurality of toner particles each having a core and a shell layer formed on the surface of the core, and the ratio of the intensity INc to the intensity INs when the cross section of the toner particle is analyzed by EELS. A shell layer having a thickness of 5 nm or more satisfying the condition of 0.0 or more and 0.2 or less contains toner particles present in 80% or more of the circumference of the cross section at a ratio of 80% by number or more, and the strength ISs A shell layer having a thickness of 5 nm or more satisfying a condition that the ratio of the strength ISc is 0.0 or more and 0.2 or less contains toner particles present in 80% or more of the circumference of the cross section at a ratio of 80% by number or more; The strength INs indicates the strength of the NK shell absorption edge derived from the nitrogen element contained in the shell layer, and the strength INc indicates the strength of the NK shell absorption edge derived from the nitrogen element contained in the core. The above The degree ISs indicates the strength of the SK shell absorption edge derived from the sulfur element contained in the shell layer, and the strength ISc indicates the strength of the SK shell absorption edge derived from the sulfur element contained in the core. Toner is described.
Patent Document 7 includes a binder resin containing a crystalline resin and a colorant, wherein the content of the crystalline resin is in the range of 3 to 15% by mass, and the acid value of the toner is in the range of 10 to 30 mgKOH / g. And, the presence ratio of the sulfur element in the total existing element intensity by XPS (X-ray photoelectron spectroscopy) is A, the sulfur element in the total existing element intensity by XRF (fluorescence X-ray analysis) after the treatment with the alcohol solvent. An electrostatic charge image developing toner is described in which A / B is in a range of 0.01 to 0.3, where B is an existing ratio.

Japanese Patent Laying-Open No. 2015-090487 JP2015-169899A JP, 2006-004150, A JP2012-078382A JP-A-11-002922 Japanese Patent Laying-Open No. 2015-075557 JP 2008-233175 A

  The problem to be solved by the present invention is that the amount of sulfur element in the domain part of the release agent of the toner is less than 0.2 atomic% or more than 1.5 atomic%, compared with the fixing to the fixing member. An object of the present invention is to provide a toner for developing an electrostatic image having excellent image releasability.

  The above problem is solved by the following means.

The invention according to claim 1
Having toner particles containing a binder resin and a release agent, the amount of sulfur element in the domain part of the release agent obtained by analyzing the cross section of the toner particles with an energy dispersive X-ray analyzer (EDX) is B In this case, the electrostatic charge image developing toner has a B value of 0.2 atomic% to 1.5 atomic%.

The invention according to claim 2
The value of B / A is 1.1 or more and 2.6 or less, where A is the amount of sulfur element in the binder resin portion obtained by analyzing the cross section of the toner particles with an energy dispersive X-ray analyzer (EDX). The toner for developing an electrostatic image according to claim 1.

The invention according to claim 3
A step of heating the release agent to a melting temperature or higher, a step of dispersing the release agent in an aqueous medium using a disperser, and a step of cooling the release agent particle dispersion, the release agent and the aqueous system Surface activity added to the medium, a mixture containing them, or the step of adding a surfactant to the release agent particle dispersion at least once before and after the dispersing step and before the dispersing step agent and amount M _b, the value of the ratio M _{a /} M _b of the amount M _a of the surfactant added after the dispersing step, the releasing agent particle dispersion is 0.2 to 2.3 It is a manufacturing method.

The invention according to claim 4
A release agent particle dispersion prepared by the method for manufacturing a release agent particle dispersion according to claim 3 and a resin particle dispersion are mixed at least to aggregate the release agent particles and the resin particles to aggregate particles. And a method for producing a toner for developing an electrostatic image, comprising: heating the aggregated particle dispersion in which the aggregated particles are dispersed to fuse and coalesce the aggregated particles to form toner particles It is.

The invention according to claim 5
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1.

The invention according to claim 6
A toner cartridge that accommodates the electrostatic image developing toner according to claim 1 and is detachable from an image forming apparatus.

The invention according to claim 7 provides:
An image forming apparatus, comprising: a developing unit that contains the electrostatic image developer according to claim 5 and that develops the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic image developer. A process cartridge to be attached and detached.

The invention according to claim 8 provides:
6. The electrostatic image development according to claim 5, wherein the 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 charged surface of the image carrier, and A developer that contains an agent and develops the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic image developer; and records the toner image formed on the surface of the image carrier. An image forming apparatus includes: a transfer unit that transfers to a surface of a medium; and a fixing unit that fixes a toner image transferred to the surface of the recording medium.

  The invention according to claim 9 comprises a charging step for charging the surface of the image carrier, an electrostatic charge image forming step for forming an electrostatic charge image on the surface of the charged image carrier, and the electrostatic charge according to claim 5. A development step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image by an image developer, and a transfer step of transferring the toner image formed on the surface of the image carrier to the surface of a recording medium And a fixing step of fixing the toner image transferred to the surface of the recording medium.

According to the first or second aspect of the invention, the amount of sulfur element in the domain part of the toner release agent is less than 0.2 atomic% or more than 1.5 atomic%. An electrostatic charge image developing toner excellent in releasability of a fixed image from a fixing member is provided.
According to the invention of claim 3, the ratio M _a / M of the amount M _b of the surfactant added before the dispersing step and the amount M _a of the surfactant added after the dispersing step. Release agent particle dispersion for producing a toner for developing an electrostatic charge image, which is excellent in peelability of a fixed image from a fixing member as compared with a case where the value of _b is less than 0.2 or exceeds 2.3 A manufacturing method is provided.
According to the invention of claim 4, the ratio M _a / M of the amount M _b of the surfactant added before the dispersing step and the amount M _a of the surfactant added after the dispersing step. Compared to the case where the value of _b is less than 0.2 or the release agent particle dispersion liquid produced by the production method exceeding 2.3 is not used, the static image is excellent in the peelability of the fixed image from the fixing member. A method for producing a toner for developing a charge image is provided.
According to the invention of claim 5, 6, 7, 8, or 9, the amount of sulfur element in the domain part of the release agent of the toner is less than 0.2 atomic% or exceeds 1.5 atomic%. As compared with the case, an electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming apparatus, or an image forming method, which are excellent in peelability of a fixed image from a fixing member, are 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 which concerns on this embodiment.

Hereinafter, the present embodiment will be described.
In addition, description with "mass part" and "mass%" is synonymous with "weight part" and "weight%", respectively.

<Toner for electrostatic image development>
An electrostatic charge image developing toner according to the present embodiment (also simply referred to as “toner”) has toner particles containing a binder resin and a release agent, and an energy dispersive X-ray analyzer is used for the cross section of the toner particles. When the amount of sulfur element in the domain part of the release agent analyzed by (EDX) is B, the value of B is 0.2 atomic% or more and 1.5 atomic% or less.

  The electrostatic charge image developing toner according to the exemplary embodiment is excellent in the releasability of the fixed image from the fixing member due to the above configuration. The reason for this is not clear, but is presumed to be as follows.

  In a fixing process in which heat and pressure are applied to a toner fixed image (also simply referred to as “image”) and fixed on a recording medium (hereinafter also referred to as “paper”), heat from the fixing member is difficult to be transmitted to the deep part of the image. In some cases, the amount of the release agent oozing out on the image surface is reduced, and the peelability between the fixing member and the fixed image is deteriorated. The deterioration of the peelability is noticeable when fixing a high toner density image with a high speed machine. For this reason, in order to ensure appropriate peelability (also referred to as “release property”), more release agents may be required. However, when the content of the release agent is increased, the release agent may ooze out on the toner surface over time in a high-temperature and high-humidity environment, resulting in a problem that charge reduction and powder characteristics deteriorate.

Further, the domain part of the release agent in the toner particles is a region of the release agent that forms an island part of a sea-island structure in the toner particles. The sea part of the sea-island structure is mainly formed of a binder resin.
The sulfur element in the domain part of the release agent is basically a sulfur element derived from a surfactant. Usually, the release agent itself does not have a sulfur atom, and most of the compounds other than the release agent incorporated into the domain part of the release agent when the toner is manufactured are surfactants. Examples of the surfactant having a sulfur atom include sulfonate compounds and sulfate ester compounds. Examples of the sulfur element in the binder resin portion of the toner particles include a sulfur element derived from a surfactant and a sulfur element derived from a chain transfer agent. When a vinyl resin such as an acrylic resin is used as a binder resin, it may contain a chain transfer agent, but its content is small, and the sulfur element in the binder resin part is a sulfur element derived from a surfactant. The Lord.

By increasing the amount of surfactant component in the domain part of the release agent and reducing the compatibility between the binder resin and the release agent, the ease of seepage of the release agent during fixing is improved, and the image forming apparatus In particular, sufficient releasability is ensured even when an image having a high toner density is fixed by a high-speed machine.
As described above, in the toner for developing an electrostatic charge image according to the present embodiment, the sulfur element amount in the domain part of the release agent obtained by analyzing the cross section of the toner particle with an energy dispersive X-ray analyzer (EDX) is B. In this case, the value of B is 0.2 atomic% or more and 1.5 atomic% or less. When the value of B is less than 0.2 atomic%, the binder resin and the release agent are easily compatible with each other, and it is difficult to exude the release agent at the time of fixing due to an increase in compatible parts. Will not be obtained. On the other hand, when the value of B exceeds 1.5 atomic%, the electrostatic repulsion force of the release agent particles becomes too strong, and the release agent particles are not taken in when the toner particles are granulated, and the release agent is contained. In some cases, toner (release agent-less toner) that is not removed may be generated, and appropriate releasability may not be obtained.

  Details of the electrostatic image developing toner according to this embodiment will be described below.

The electrostatic charge image developing toner according to this embodiment has a value of B, where B is the amount of sulfur element in the domain part of the release agent obtained by analyzing the cross section of the toner particles with an energy dispersive X-ray analyzer (EDX). However, it is 0.2 atomic% or more and 1.5 atomic% or less.
The value B is preferably 0.2 atomic% or more and 1.5 atomic% or less, and preferably 0.4 atomic% or more and 1.3 atomic% or less from the viewpoint of the peelability of the fixed image on the fixing member. It is more preferable that it is 0.6 atomic% or more and 1.1 atomic% or less.

Further, the toner for developing an electrostatic charge image according to the present embodiment is B / A, where A is the amount of sulfur element in the binder resin portion obtained by analyzing the cross section of the toner particles with an energy dispersive X-ray analyzer (EDX). Is preferably 1.1 or more, 2.6 or less, more preferably 1.3 or more and 2.3 or less, and particularly preferably 1.5 or more and 2.1 or less. When the value of B / A is in the above range, the binder resin particles and the release agent particles are difficult to be compatible, and the release agent is likely to ooze out at the time of fixing due to a small amount of compatible parts. The mold effect is obtained, the electrostatic repulsion force of the release agent particles is small, and when the toner is granulated, the generation of the release agent-less toner in which the release agent particles are not taken in is suppressed, and an appropriate A mold release effect is obtained.
Furthermore, the value of A is preferably 0.08 atomic% or more and 1.36 atomic% or less, and preferably 0.17 atomic% or more and 1.00 atomic% or less from the viewpoint of the peelability of the fixed image on the fixing member. It is more preferable that it is 0.29 atomic% or more and 0.73 atomic% or less.

In this embodiment, the amount of sulfur element in the domain part of the release agent and the binder resin part in the cross section of the toner particle is confirmed by the following method.
First, the toner particles are embedded using a bisphenol A type liquid epoxy resin and a curing agent, and then a cutting sample is prepared. Next, the cutting sample is cut at −100 ° C. using a cutting machine using a diamond knife, for example, LEICA ultramicrotome (manufactured by Hitachi High-Technologies Corporation) to prepare an observation sample. Further, this observation sample is left in a desiccator under a ruthenium tetroxide atmosphere for dyeing. Dyeing is continued until the naistack double-sided tape (Nichiban Co., Ltd.) left at the same time turns light brown.
The observation sample dyed in this manner is observed with a transmission electron microscope (TEM) at a magnification of 10,000 times. Since the toner sample is dyed with ruthenium tetroxide, the binder resin portion (region other than the release agent domain and colorant) and the release agent domain portion (release agent domain region) are stained. It is discriminated from the difference in density and shape. The gray portion inside the toner is present as a binder resin portion, a rod shape, and a lump shape, and the white portion is determined as the domain of the release agent.
Next, for the amount of sulfur element in the domain part of the release agent and the amount of sulfur element in the binder resin part, an energy dispersive X-ray analyzer EMAX model 6923H (manufactured by Horiba, Ltd.) is used as an observation sample. And observing at an acceleration voltage of 20 kV and a magnification of 10,000 times, and measuring the sulfur element amount A in the binder resin portion. The release agent is mapped so as not to protrude from the domain part, and the sulfur element amount B in the domain part of the release agent is measured.

  The electrostatic image developing toner according to the exemplary embodiment includes toner particles and, if necessary, an external additive.

(Toner particles)
The toner particles include a binder resin, a release agent, and, if necessary, a colorant and other additives.

-Binder resin-
Examples of the binder resin include styrenes (eg, styrene, parachlorostyrene, α-methylstyrene, etc.), (meth) acrylic acid esters (eg, methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic acid). n-butyl, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc.), ethylenically unsaturated nitriles (for example, acrylonitrile, Methacrylonitrile, etc.), vinyl ethers (eg, vinyl methyl ether, vinyl isobutyl ether, etc.), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), olefins (eg, ethylene, propylene, etc.) Emissions, a homopolymer of a monomer such as butadiene) and the like, or a vinyl-based resin composed of these monomers with two or more combinations copolymer.
As the binder resin, for example, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, non-vinyl resin such as modified rosin, a mixture of these with the vinyl resin, or these Examples also include a graft polymer obtained by polymerizing a vinyl monomer in the coexistence.
These binder resins may be used alone or in combination of two or more.

A polyester resin is suitable as the binder resin.
Examples of the polyester resin include known amorphous polyester resins. A polyester resin may use a crystalline polyester resin together with an amorphous polyester resin. However, the crystalline polyester resin is preferably used in the range of 2 mass% to 40 mass% (preferably 2 mass% to 20 mass%) with respect to the total binder resin.

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.

-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, and lower (for example, having 1 to 5 carbon atoms) alkyl esters.
Polyvalent carboxylic acid may be used individually by 1 type, and may use 2 or more types together.

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

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 7121-1987 “Method for Measuring Plastic Transition Temperature”. Of “extrapolated glass transition start temperature”.

The weight average molecular weight (Mw) of the amorphous polyester resin is preferably from 5,000 to 1,000,000, more preferably from 7,000 to 500,000.
The number average molecular weight (Mn) of the amorphous polyester resin is preferably 2,000 or more and 100,000 or less.
The molecular weight distribution Mw / Mn of the amorphous polyester resin is preferably 1.5 or more and 100 or less, and more preferably 2 or more and 60 or less.
The weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed with a THF solvent using a Tosoh GPC / HLC-8120GPC as a measuring device and a Tosoh column / TSKgel SuperHM-M (15 cm). The weight average molecular weight and the number average molecular weight are calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from this measurement result.

The amorphous polyester resin can be obtained by a known production method. Specifically, for example, the polymerization temperature is set to 180 ° C. or higher and 230 ° C. or lower, the pressure in the reaction system is reduced as necessary, and the reaction is performed while removing water and alcohol generated during the condensation.
In addition, when the monomer of the raw material is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added and dissolved as a solubilizing agent. In this case, the polycondensation reaction is performed while distilling off the solubilizer. If there is a monomer with poor compatibility, it is recommended to condense the monomer with poor compatibility with the monomer and the acid or alcohol to be polycondensed in advance before polycondensing with the main component. .

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. Among these, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferable as the aliphatic diol.
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 35,000 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.

-Release agent-
Examples of the release agent include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum waxes such as polyethylene wax and montan wax; fatty acid esters and montanic acid esters. And ester waxes. The release agent is not limited to this.
Among these, a release agent selected from the group consisting of hydrocarbon wax, carnauba wax, rice wax, candelilla wax, and montan wax is preferable from the viewpoint of peelability of the fixed image on the fixing member. And a mold release agent selected from the group consisting of carnauba wax.

The melting temperature of the release agent is preferably 50 ° C. or higher and 140 ° C. or lower, and more preferably 60 ° C. or higher and 130 ° C. or lower.
Note that the melting temperature is obtained from the DSC curve obtained by differential scanning calorimetry (DSC) according to “melting peak temperature” described in JIS K 7121-1987 “Method for measuring the melting 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.

-Surfactant-
The toner particles in the toner for developing an electrostatic charge image according to the exemplary embodiment preferably include a surfactant from the viewpoint of releasability of the fixed image from the fixing member, and include at least a surfactant in the release agent domain. It is more preferable.
As the surfactant, a surfactant having a sulfur element is preferable from the viewpoint of peelability of a fixed image on a fixing member, and a surfactant selected from the group consisting of a sulfate ester compound and a sulfonate compound is used. More preferred are sulfonate compounds, and alkylbenzene sulfonate compounds are particularly preferred.

As the surfactant used in the present embodiment, other surfactants may be used in combination with the surfactant having sulfur element.
Examples of other surfactants include anionic surfactants such as phosphate esters and soaps; cationic surfactants such as amine salt types and quaternary ammonium salt types; polyethylene glycols and alkylphenol ethylene oxide adducts And nonionic surfactants such as polyhydric alcohols and polyhydric alcohols. 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.
The content of the surfactant, particularly the sulfate ester salt compound and the sulfonate compound is not particularly limited as long as it is an amount satisfying the range of the value B.

-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.

-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 toner particles are measured using Coulter Multisizer II (manufactured by Beckman Coulter, Inc.), and an electrolytic solution is measured using ISOTON-II (manufactured by Beckman Coulter, Inc.). 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 particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 and the number 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. Examples include 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, and aluminum coupling agents. 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.

<Method for producing release agent particle dispersion>
The method for producing a release agent particle dispersion according to this embodiment includes a step of heating the release agent to a melting temperature or higher, a step of dispersing the release agent in an aqueous medium using a disperser, and a release agent particle. A step of cooling the dispersion, and a step of adding a surfactant to the release agent, the aqueous medium, a mixture containing these, or the release agent particle dispersion before and after the dispersion step, respectively. The value of the ratio M _a / M _b of the amount M _b of the surfactant added at least once and added before the dispersing step and the amount M _a of the surfactant added after the dispersing step is It is 0.2 or more and 2.3 or less.
Further, the release agent particle dispersion produced by the method for producing the release agent particle dispersion according to the present embodiment is suitably used for producing the electrostatic image developing toner according to the present embodiment.

  In the method for producing a release agent particle dispersion according to the present embodiment, a release agent particle dispersion for producing an electrostatic charge image developing toner having excellent releasability of a fixed image from a fixing member by having the above-described steps. Manufacturing is realized. The reason is estimated as follows.

Generally, a method for producing a release agent particle dispersion includes a mixing step in which a release agent and a surfactant are mixed, a melting step in which the release agent is melted, and the melted release agent in the target particles. A release agent particle dispersion is obtained through a dispersion step of dispersing to a diameter and a cooling step for solidifying the dispersed release agent particles.
As a means of increasing the amount of the surfactant component on the surface of the release agent particles, simply increasing the amount of the surfactant in the general production method reduces the dispersed particle size by increasing the amount of surfactant per unit area. . As a result, the domain diameter of the release agent inside the toner particles is also reduced, and the peelability of the fixed image from the fixing member is lowered. In addition, it is possible to adjust the dispersed particle size by changing the conditions such as dispersion pressure and temperature of the disperser, but if a large amount of surfactant is added before the dispersion step, it is also kneaded inside the release agent particles. As a result, the compatibility between the binder resin and the release agent is improved, so that the ease of seepage of the release agent at the time of fixing is reduced, and the releasability at the time of fixing is reduced. A secondary failure such as a decrease in transfer efficiency due to loss deterioration may occur.

Therefore, the step of adding the surfactant is included at least once before and after the step of dispersing the release agent in the aqueous medium using a disperser, so that the dispersed particle size of the release agent particles is appropriately large. Thus, a release agent particle dispersion having a large amount of the surfactant component on the surface of the release agent particles can be obtained while the amount of the entire surfactant is moderate.
By producing a toner for developing an electrostatic image using this release agent particle dispersion, the compatibility between the binder resin and the release agent in the toner particles is low, and the surfactant in the domain part of the release agent Therefore, a toner having excellent releasability of the fixed image from the fixing member can be obtained.

  Hereinafter, the detail of the manufacturing method of the mold release agent particle dispersion which concerns on this embodiment is demonstrated.

The heating step, the dispersing step, and the cooling step may be performed using known means and methods.
The heating temperature in the heating step may be equal to or higher than the melting temperature of the release agent, but is preferably equal to or higher than the melting temperature (melting temperature + 50 ° C.) and is equal to or higher than the melting temperature (melting temperature + 35 ° C.). It is more preferable.
In the heating step, it is preferable to heat the release agent while stirring. There is no restriction | limiting in particular as a stirring means, A well-known stirring means is used. Moreover, about the stirring means, it is the same also in processes other than the process of heating.
There is no restriction | limiting in particular as a heating means, A well-known means is used.

As the disperser used in the dispersing step, a high-pressure disperser such as a homogenizer, a wet jet mill, or a wet cavitation mill is preferably used.
The temperature during dispersion in the dispersing step is preferably not less than the melting temperature of the release agent, more preferably not less than the melting temperature (melting temperature + 50 ° C.), and more preferably not less than the melting temperature (melting temperature + 35 ° C.). It is particularly preferred that
As an aqueous medium used for this embodiment, water, such as distilled water and ion-exchange water, alcohol, etc. are mentioned, for example. These may be used individually by 1 type and may use 2 or more types together.
The amount of the aqueous medium used is not particularly limited, but the solid content of the release agent particle dispersion to be produced is preferably 5% by mass or more and 40% by mass or less, and preferably 10% by mass or more and 35% by mass. It is more preferable that the amount is not more than%.

The cooling in the cooling step may be rapid cooling or slow cooling, but is preferably rapid cooling. The cooling rate in the cooling step is preferably 1 ° C./min or more and 10 ° C./min or less.
There is no restriction | limiting in particular as a cooling means, A well-known means is used.
In the cooling step, it is preferable to cool the dispersion while stirring.

The method for producing a release agent particle dispersion according to this embodiment includes the step of adding the surfactant at least once before the step of dispersing, and at least once after the step of dispersing. From the viewpoints of operability and simplicity, it is preferable that the step of adding the surfactant is included once before the dispersing step and once after the dispersing step.
Moreover, it is preferable that the process of adding the said surfactant performed after the said process of dispersion | distribution is before the said process of cooling from a viewpoint of the adhesiveness to the mold release agent particle surface.
The kind of surfactant used in the step of adding the surfactant is the same as the preferred kind of surfactant described above in the toner.
The addition method in the step of adding the surfactant is not particularly limited, and the addition amount in each step may be added all at once, gradually, or intermittently.
In addition, in the step of adding the surfactant, the surfactant may be added to the mixture, either to the mold release agent or to the aqueous medium, before the step of dispersing. May be. Moreover, if it is after the said process to disperse | distribute, it is preferable to add surfactant to the said mold release agent particle dispersion.
In the ratio of the amount M _b of the surfactant added before the dispersing step and the amount M _a of the surfactant added after the dispersing step, the value of M _a / M _b is 0.2. From the viewpoint of producing a toner that is 2.3 or less and excellent in releasability of a fixed image from a fixing member, it is preferably 0.3 or more and 2.1 or less, and 0.8 or more and 1.9 or less. More preferably, it is 1.2 or more and 1.8 or less.

The volume average particle diameter of the release agent particles in the release agent particle dispersion produced by the production method of the release agent particle dispersion according to the present embodiment is preferably 50 nm or more and 400 nm or less, and 80 nm or more and 300 nm or less. It is more preferable that
The volume average particle size of the release agent particles is determined by using a particle size distribution obtained by measurement with a laser diffraction particle size distribution analyzer (for example, LA-700, manufactured by Horiba, Ltd.). ), The cumulative distribution is drawn from the small particle size side with respect to the volume, and the particle size that is 50% cumulative with respect to all particles is measured as the volume average particle size D50v.
In addition, the content of the surfactant in the release agent particle dispersion is such that the release agent particle dispersion has a compatibility with the binder resin and the release agent and the transferability of the obtained toner. It is preferably 1% by mass or more and 25% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less with respect to 100 parts by mass of the release agent. Is particularly preferred.

<Method for producing toner for developing electrostatic image>
The method for producing an electrostatic charge image developing toner according to the present embodiment is not particularly limited as long as it is a method for producing the toner according to the present embodiment, but the method for producing a release agent particle dispersion according to the present embodiment. A step of mixing at least the release agent particle dispersion and the resin particle dispersion produced by the step of agglomerating to form aggregated particles, and heating the aggregated particle dispersion in which the aggregated particles are dispersed to form the aggregate It is preferable to include a step of fusing and coalescing the particles to form toner particles.
Further, the electrostatic image developing toner according to the exemplary embodiment is preferably obtained by externally adding an external additive to the toner particles after the toner particles are manufactured. That is, it is preferable that the method for producing an electrostatic charge image developing toner according to the exemplary embodiment further includes a step of externally adding an external additive to the toner particles.

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 serving as a binder resin are dispersed (resin particle dispersion preparation step), and a release agent manufactured by the method of manufacturing a release agent particle dispersion according to the present embodiment In a dispersion in which at least a particle dispersion and a resin particle dispersion are mixed (in a dispersion after mixing other particle dispersion if necessary), release agent particles and resin particles (as necessary) Toner particles are formed by aggregating other particles) to form aggregated particles (aggregated particle forming step) and the aggregated particle dispersion in which the aggregated particles are dispersed to fuse and coalesce the aggregated particles. It is preferable to produce toner particles through a step of forming the toner (fusion and coalescence step).

Details of each step will be described below.
In the following description, a method for obtaining toner particles containing a colorant will be described. The colorant is used as necessary. Of course, other additives other than the colorant may be used.

-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.

  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 preferably 0.01 μm or more and 1 μm or less, more preferably 0.08 μm or more and 0.8 μm or less, further 0.1 μm or more and 0.6 μm or less. preferable.
In addition, the volume average particle diameter of the resin particles is based on the particle size range (channel) divided by using the particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring 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 particles is measured as the volume average particle diameter D50v. The volume average particle size of particles in other dispersions is also measured in the same manner.

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

  For example, a colorant particle dispersion is also prepared in the same manner as the resin particle dispersion. That is, the same applies to the colorant particles dispersed in the colorant particle dispersion with respect to 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.

-Aggregated particle formation process-
Next, together with the resin particle dispersion, the colorant particle dispersion and the release agent particle dispersion produced by the method for producing the release agent particle dispersion according to the present embodiment are mixed.
Then, in the mixed dispersion, resin particles, colorant particles, and release agent particles are hetero-aggregated to have resin particles, colorant particles, and release agent particles having a diameter close to the diameter of the target toner particles. Aggregated particles are formed.

Specifically, for example, the flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, the pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. The resin particles are heated to a glass transition temperature (specifically, for example, the glass transition temperature of the resin particles −30 ° C. or more and the glass transition temperature −10 ° C. or less), and the particles dispersed in the mixed dispersion liquid are aggregated. , Forming aggregated particles.
In the agglomerated particle forming step, for example, the aggregating agent is added at room temperature (for example, 25 ° C.) while stirring the mixed dispersion with a rotary shearing homogenizer, and the pH of the mixed dispersion is acidic (for example, the pH is 2 or more and 5 or less). ), And after adding a dispersion stabilizer as necessary, the heating may be performed.

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

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

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

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

Here, after completion of the 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. In addition, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, airflow 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 by, for example, a V blender, a Henschel mixer, a Laedige mixer, or the like. Further, if necessary, coarse toner particles may be removed using a vibration sieving machine, a wind sieving machine, or the like.

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

There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. As a carrier, for example, a coated carrier in which the surface of a core made of magnetic powder is coated with a coating resin; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and mixed in a matrix resin; a porous magnetic powder is impregnated with a resin Resin impregnated type carriers; and the like.
Note that the magnetic powder-dispersed carrier and the resin-impregnated carrier may be a carrier in which the constituent particles of the carrier are used as a core material and coated with a coating resin.

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

Examples of the conductive particles include particles of metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.
Examples of the coating resin and the 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 ester. Examples thereof include a straight silicone resin comprising a copolymer, an organosiloxane bond, or a modified product thereof, a fluororesin, a polyester, a polycarbonate, a phenol resin, and an epoxy resin.
The coating resin and matrix resin may contain other additives such as conductive particles.
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.

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

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

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

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

The image forming apparatus according to the present embodiment is a direct transfer type apparatus that directly transfers a toner image formed on the surface of an image carrier to a recording medium; the toner image formed on the surface of the image carrier is transferred to an intermediate transfer member An intermediate transfer type apparatus that primarily transfers the toner image transferred to the surface of the intermediate transfer body and then secondary transfer the toner image to the surface of the recording medium; after the toner image is transferred, the surface of the image carrier before charging is cleaned. An apparatus provided with a cleaning unit; a known image forming apparatus such as an apparatus provided with a charge removing unit that discharges the surface of an image holding member by irradiating a discharge light after charging a toner image and before charging is applied.
In the case of an intermediate transfer type apparatus, the transfer means includes, for example, an intermediate transfer body on which a toner image is transferred to the surface, and a primary transfer that primarily transfers the toner image formed on the surface of the image holding body to the surface of the intermediate transfer body. And a secondary transfer unit that secondarily transfers the toner image transferred onto the surface of the intermediate transfer member onto the surface of the recording medium.

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

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

FIG. 1 is a schematic configuration diagram illustrating an image forming apparatus according to the present embodiment.
The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter sometimes simply referred to as “units”) 10Y, 10M, 10C, and 10K are arranged in parallel at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a drive roll 22 and a support roll 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other in the left to right direction in the drawing. The vehicle travels in the direction toward the unit 10K. The support roll 24 is applied with a force in a direction away from the drive roll 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the support roll 24. An intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the drive roll 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K has yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The toner including the four color toners is supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K have the same configuration, here, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction. 10Y will be described as a representative. It should be noted that reference numerals with magenta (M), cyan (C), and black (K) are attached to the same parts as those of the first unit 10Y instead of yellow (Y). Description of the units 10M, 10C, and 10K will be omitted.

The first unit 10Y includes a photoreceptor 1Y that functions as an image holding member. Around the photoreceptor 1Y, a charging roll (an example of a charging unit) 2Y that charges the surface of the photoreceptor 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on the color-separated image signal. Then, an exposure device (an example of an electrostatic image forming unit) 3 that forms an electrostatic image, and a developing device (an example of a developing unit) 4Y that develops the electrostatic image by supplying toner charged to the electrostatic image, developed A primary transfer roll 5Y (an example of a primary transfer unit) that transfers a toner image onto the intermediate transfer belt 20, and a photoconductor cleaning device (an example of a cleaning unit) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer. Are arranged in order.
The primary transfer roll 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rolls 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roll under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described.
First, prior to operation, the surface of the photoreceptor 1Y is charged to a potential of −600V to −800V by the charging roll 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive (for example, volume resistivity at 20 ° C .: 1 × 10 −6 Ωcm or less) substrate. 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, a 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 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 whose surface of plain paper is 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 charge image developer according to the present embodiment, and develops the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge 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 Example and a comparative example are given and this embodiment is described in detail in detail, this embodiment is not limited to the following examples. Unless otherwise specified, “parts” and “%” represent “parts by mass” and “mass%”.

(Preparation of resin particle dispersion 1)
Polyester resin: 160 parts by mass Ethyl acetate: 230 parts by mass Sodium hydroxide aqueous solution (0.3N): 0.1 part by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 3.0 parts by mass

  The above components were put into a separable flask, heated at 70 ° C., and stirred by a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 373 parts by mass of ion-exchanged water was gradually added for phase inversion emulsification, and the solvent was removed to prepare resin particle dispersion 1.

(Preparation of resin particle dispersion 2)
Resin particle dispersion 2 was prepared by transfer emulsification in the same procedure as resin particle dispersion 1, except that the anionic surfactant added to the resin mixture was changed to 3.6 parts by mass.

(Preparation of resin particle dispersion 3)
The resin particle dispersion 3 was prepared by transferring and emulsifying in the same procedure as the resin particle dispersion 1, except that the anionic surfactant added to the resin mixture was changed to 2.5 parts by mass.

(Preparation of resin particle dispersion 4)
The resin particle dispersion 4 was prepared by transferring and emulsifying in the same procedure as the resin particle dispersion 1, except that the anionic surfactant added to the resin mixture was changed to 1.5 parts by mass.

(Preparation of resin particle dispersion 5)
-Styrene: 280 parts by mass-n-butyl acrylate: 120 parts by mass-Acrylic acid: 8 parts by mass-Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 12 parts by mass-Ion-exchanged water: 550 g
A solution in which the above components are dissolved is placed in a separable flask and dispersed and emulsified. A solution in which 3 g of ammonium persulfate is dissolved in 50 g of ion-exchanged water is gradually added, and the mixture is heated to 70 ° C. and polymerized for 5 hours. 6 was prepared.

(Preparation of release agent particle dispersion 1)
Carnauba wax (Toa Kasei Co., Ltd., RC-160): 100 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 2.0 parts by mass Ion exchange water: 400 Part by mass The above material is put into a pressurized container and heated to 110 ° C. while stirring, and dispersion treatment corresponding to 10 passes is performed with a high-pressure homogenizer, and then 3.0 parts by mass of an anionic surfactant is further added for 30 minutes. Hold with stirring. After the holding, a cooling treatment was performed promptly to prepare a release agent particle dispersion 1.

(Preparation of release agent particle dispersion 2)
A release agent particle dispersion 2 was prepared by performing a dispersion treatment in the same procedure as the release agent particle dispersion 1, except that the anionic surfactant added after the dispersion treatment was changed to 2.5 parts by mass.

(Preparation of release agent particle dispersion 3)
A release agent particle dispersion 3 was prepared by performing a dispersion treatment in the same procedure as the release agent particle dispersion 1 except that the anionic surfactant added after the dispersion treatment was changed to 3.5 parts by mass.

(Preparation of release agent particle dispersion 4)
A release agent particle dispersion 4 was prepared by performing a dispersion treatment in the same procedure as the release agent particle dispersion 1 except that the anionic surfactant added after the dispersion treatment was changed to 4.5 parts by mass.

(Preparation of release agent particle dispersion 5)
A release agent particle dispersion 5 was prepared by performing a dispersion treatment in the same procedure as the release agent particle dispersion 1 except that the anionic surfactant added after the dispersion treatment was changed to 2.0 parts by mass.

(Preparation of release agent particle dispersion 6)
A release agent particle dispersion 6 was prepared by carrying out a dispersion treatment in the same procedure as the release agent particle dispersion 1, except that the anionic surfactant added after the dispersion treatment was changed to 1.3 parts by mass.

(Preparation of release agent particle dispersion 7)
A release agent particle dispersion 7 was prepared by performing a dispersion treatment in the same procedure as the release agent particle dispersion 1 except that the anionic surfactant added after the dispersion treatment was changed to 1.6 parts by mass.

(Preparation of release agent particle dispersion 8)
Release agent particle dispersion 1 except that the anionic surfactant added before the dispersion treatment was changed to 3.5 parts by mass and the anionic surfactant added after the dispersion treatment was changed to 2.0 parts by mass. The release agent particle dispersion liquid 8 was prepared by performing a dispersion treatment in the same procedure as described above.

(Preparation of release agent particle dispersion 9)
A release agent particle dispersion 9 was prepared by performing a dispersion treatment in the same procedure as the release agent particle dispersion 1 except that the anionic surfactant added after the dispersion treatment was changed to 1.0 part by mass.

(Preparation of release agent particle dispersion 10)
Release agent particle dispersion 1 except that the anionic surfactant added before the dispersion treatment was changed to 1.5 parts by weight and the anionic surfactant added after the dispersion treatment was changed to 4.0 parts by weight. The release agent particle dispersion liquid 10 was prepared by performing a dispersion treatment in the same procedure as described above.

(Preparation of release agent particle dispersion 11)
Release agent particle dispersion 1 except that the anionic surfactant added before the dispersion treatment is changed to 1.5 parts by mass and the anionic surfactant added after the dispersion treatment is changed to 4.5 parts by mass. The release agent particle dispersion liquid 11 was prepared by performing a dispersion treatment in the same procedure as described above.

(Preparation of release agent particle dispersion 12)
Release agent particle dispersion 1 except that the anionic surfactant added before the dispersion treatment was changed to 2.0 parts by weight and the anionic surfactant added after the dispersion treatment was changed to 5.0 parts by weight. The release agent particle dispersion liquid 12 was prepared by performing a dispersion treatment in the same procedure as described above.

(Preparation of release agent particle dispersion 13)
Carnauba wax (manufactured by Toa Kasei Co., Ltd., RC-160): 100 parts by mass Ion-exchanged water: 400 parts by mass The above materials are put into a pressure vessel and heated to 110 ° C. with stirring, and 10 with a high-pressure homogenizer. Dispersion treatment corresponding to the pass was performed, and then 2.0 parts by mass of an anionic surfactant was further added and held for 30 minutes with stirring. After the holding, a cooling treatment was performed promptly to prepare a release agent particle dispersion 13.

(Preparation of release agent particle dispersion 14)
Paraffin wax (Nippon Seiwa Wax Co., Ltd., HNP0190): 100 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 3.0 parts by mass Ion-exchanged water: 400 parts by mass Pressurization Charge the above materials into a container and heat to 95 ° C. with stirring, disperse for 10 passes with a high-pressure homogenizer, then add 4.0 parts by weight of an anionic surfactant and hold for 30 minutes with stirring. did. After the holding, a cooling treatment was performed promptly to prepare a release agent particle dispersion 14.

(Preparation of release agent particle dispersion 15)
Polyester wax (Mitsui Petrochemical Industries, 100P): 100 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 2.5 parts by mass Ion-exchanged water: 400 parts by mass The above materials are put into a pressure vessel and heated to 130 ° C. while stirring, and dispersion treatment corresponding to 10 passes is performed with a high-pressure homogenizer, and then 4.0 parts by weight of an anionic surfactant is further added and stirred for 30 minutes. Retained. After the holding, a cooling treatment was promptly performed to prepare a release agent particle dispersion 15.

(Preparation of release agent particle dispersion 16)
Carnauba wax (Toa Kasei Co., Ltd., RC-160): 100 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC): 2.2 parts by mass Ion exchange water: 400 Part by mass The above material is put into a pressure vessel and heated to 110 ° C. with stirring, and subjected to a dispersion treatment corresponding to 10 passes with a high-pressure homogenizer, and then 3.4 parts by mass of an anionic surfactant is further added for 30 minutes. Hold with stirring. After the holding, a cooling treatment was performed promptly to prepare a release agent particle dispersion liquid 16.

(Preparation of release agent particle dispersion 17)
Carnauba wax (manufactured by Toa Kasei Co., Ltd., RC-160): 100 parts by mass Anionic surfactant (manufactured by NOF Corporation, Newlex R): 2.3 parts by mass Ion-exchanged water: 400 parts by mass Part The above material is put into a pressurized container and heated to 110 ° C. while stirring, and dispersion treatment corresponding to 10 passes is performed with a high-pressure homogenizer, and then 4.2 parts by weight of an anionic surfactant is further added, followed by stirring for 30 minutes. While holding. After the holding, a cooling treatment was performed promptly to prepare a release agent particle dispersion liquid 17.

<Example 1>
(Preparation of Toner 1)
-Ion-exchanged water: 340 parts by mass-Release agent particle dispersion 1: 20 parts by mass-Resin particle dispersion 1: 180 parts by mass After adding the above components to a cylindrical stainless steel container and stirring, a homogenizer (manufactured by IKA, Dispersion was carried out for 1 minute using an ultra turrax T50). Next, 1.5 parts by mass of a 1% by mass aqueous solution of aluminum sulfate as a flocculant was dropped and further dispersed and mixed for 5 minutes to obtain an agglomerated slurry. Next, a stirrer and a thermometer were installed in the container, and gradually heated with a mantle heater while maintaining proper stirring, and kept at 45 ° C. for 1 hour. Next, 60 parts by mass of the resin particle dispersion was added and the temperature was raised to 50 ° C., and the resin particles were adhered to the surface of the aggregated particles. It was confirmed with an optical microscope that the thickness of the resin coating layer was increased. Thereafter, the pH of the aggregated particle slurry was adjusted to 8.0, the temperature was raised to 80 ° C., and the mixture was cooled by holding for an appropriate time while checking the degree of coalescence with an optical microscope.
The obtained toner slurry was coarsely removed with a nylon mesh, filtered, cake washed with ion-exchanged water, and then dried with a vacuum dryer for 12 hours to obtain toner particles 1.

To 100 parts by mass of toner particles 1, 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 parts by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) Was mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain toner 1 (toner for developing an electrostatic image).
The obtained toner had a volume average particle diameter D _50v of 6.5 μm.

<Example 2>
(Preparation of Toner 2)
Toner 2 was obtained by granulation in the same procedure as toner 1 except that release agent particle dispersion 2 was used instead of release agent particle dispersion 1.

<Example 3>
(Preparation of Toner 3)
Toner 3 was obtained by granulation in the same procedure as toner 1 except that release agent particle dispersion 3 was used instead of release agent particle dispersion 1.

<Example 4>
(Preparation of Toner 4)
Toner 4 was obtained by granulation in the same procedure as toner 1 except that resin particle dispersion 2 was used in place of resin particle dispersion 1.

<Example 5>
(Preparation of Toner 5)
Granulation in the same procedure as toner 1 except that the release agent particle dispersion 2 was used instead of the release agent particle dispersion 1, and the resin particle dispersion 2 was used instead of the resin particle dispersion 1. Toner 5 was obtained.

<Example 6>
(Production of Toner 6)
Granulation in the same procedure as toner 1 except that the release agent particle dispersion 3 is used instead of the release agent particle dispersion 1, and the resin particle dispersion 2 is used instead of the resin particle dispersion 1. Toner 6 was obtained.

<Example 7>
(Preparation of Toner 7)
Granulation in the same procedure as toner 1 except that the release agent particle dispersion 4 is used instead of the release agent particle dispersion 1, and the resin particle dispersion 2 is used instead of the resin particle dispersion 1. Toner 7 was obtained.

<Example 8>
(Production of Toner 8)
Toner 8 was obtained by granulation in the same procedure as toner 1 except that resin particle dispersion 3 was used instead of resin particle dispersion 1.

<Example 9>
(Preparation of Toner 9)
Granulation in the same procedure as toner 1 except that the release agent particle dispersion 3 is used instead of the release agent particle dispersion 1, and the resin particle dispersion 2 is used instead of the resin particle dispersion 1. Toner 9 was obtained.

<Example 10>
(Production of Toner 10)
Granulation in the same procedure as toner 1 except that the release agent particle dispersion 3 is used instead of the release agent particle dispersion 1 and the resin particle dispersion 3 is used instead of the resin particle dispersion 1. Toner 10 was obtained.

<Example 11>
(Production of Toner 11)
Granulation in the same procedure as toner 1 except that the release agent particle dispersion 5 is used instead of the release agent particle dispersion 1, and the resin particle dispersion 3 is used instead of the resin particle dispersion 1. Toner 11 was obtained.

<Example 12>
(Preparation of Toner 12)
Granulation in the same procedure as toner 1 except that the release agent particle dispersion 5 is used instead of the release agent particle dispersion 1, and the resin particle dispersion 4 is used instead of the resin particle dispersion 1. Toner 12 was obtained.

<Example 13>
(Preparation of Toner 13)
Granulation is performed in the same manner as in the toner 1 except that the release agent particle dispersion 6 is used instead of the release agent particle dispersion 1, and the resin particle dispersion 4 is used instead of the resin particle dispersion 1. Toner 13 was obtained.

<Example 14>
(Preparation of Toner 14)
Granulation in the same procedure as toner 1 except that the release agent particle dispersion 7 is used instead of the release agent particle dispersion 1, and the resin particle dispersion 4 is used instead of the resin particle dispersion 1. Toner 14 was obtained.

<Example 15>
(Preparation of Toner 15)
Toner 15 was obtained by granulation in the same procedure as toner 1 except that resin particle dispersion 14 was used instead of resin particle dispersion 1.

<Example 16>
(Production of Toner 16)
Toner 16 was obtained by granulation in the same procedure as toner 1 except that resin particle dispersion 15 was used instead of resin particle dispersion 1.

<Example 17>
(Preparation of Toner 17)
Granulation was performed in the same manner as in the toner 1 except that the resin particle dispersion 16 was used in place of the resin particle dispersion 1, whereby a toner 17 was obtained.

<Example 18>
(Production of Toner 18)
Toner 17 was obtained by granulation in the same procedure as for toner 1 except that resin particle dispersion 17 was used instead of resin particle dispersion 1.

<Example 19>
(Production of Toner 19)
-Ion exchange water: 300 parts by mass-Release agent particle dispersion 1: 20 parts by mass-Resin particle dispersion 5: 180 parts by mass-Polyaluminum chloride: 3 parts by mass The above ingredients were added to a cylindrical stainless steel container and stirred. Then, it disperse | distributed for 5 minutes with the homogenizer (the product made by IKA, ultra turrax T50), and the aggregation slurry was obtained. Next, a stirrer and a thermometer were installed in the container, and gradually heated with a mantle heater while maintaining proper stirring, and maintained at 50 ° C. for 3 hours. Next, 40 parts by mass of a resin particle dispersion was added, and the resin particles were adhered to the surface of the aggregated particles. It was confirmed with an optical microscope that the thickness of the resin coating layer was increased. Thereafter, the pH of the aggregated particle slurry was adjusted to 7.1, the temperature was raised to 90 ° C., and the mixture was cooled by holding for an appropriate time while checking the degree of coalescence with an optical microscope.
The obtained toner slurry was coarsely removed with a nylon mesh, filtered, cake washed with ion-exchanged water, and then dried with a vacuum dryer for 12 hours. Next, an external addition process was performed in the same procedure as for toner 1 to obtain toner 19.

<Comparative Example 1>
(Production of Toner 20)
Granulation was carried out in the same procedure as in Toner 1 except that Release Agent Particle Dispersion 8 was used instead of Release Agent Particle Dispersion 1 to obtain Toner 20.

<Comparative example 2>
(Preparation of Toner 21)
Granulation was carried out in the same procedure as in Toner 1 except that Release Agent Particle Dispersion 9 was used instead of Release Agent Particle Dispersion 1 to obtain Toner 21.

<Comparative Example 3>
(Production of Toner 22)
Granulation in the same procedure as toner 1 except that the release agent particle dispersion 10 is used instead of the release agent particle dispersion 1, and the resin particle dispersion 2 is used instead of the resin particle dispersion 1. Toner 22 was obtained.

<Comparative Example 4>
(Production of Toner 23)
Granulation in the same procedure as toner 1 except that the release agent particle dispersion 11 is used instead of the release agent particle dispersion 1, and the resin particle dispersion 2 is used instead of the resin particle dispersion 1. Toner 23 was obtained.

<Comparative Example 5>
(Preparation of Toner 24)
Granulation in the same procedure as toner 1 except that the release agent particle dispersion 12 is used instead of the release agent particle dispersion 1, and the resin particle dispersion 3 is used instead of the resin particle dispersion 1. Toner 24 was obtained.

<Comparative Example 6>
(Preparation of Toner 25)
Granulation was performed in the same manner as in the toner 1 except that the release agent particle dispersion 13 was used in place of the release agent particle dispersion 1, whereby a toner 25 was obtained.

<Comparative Example 7>
(Production of Toner 26)
-Ion exchange water: 300 parts by mass-Release agent particle dispersion 8: 20 parts by mass-Resin particle dispersion 5: 180 parts by mass-Polyaluminum chloride: 3 parts by mass The above ingredients were added to a cylindrical stainless steel container and stirred. Then, it disperse | distributed for 5 minutes with the homogenizer (the product made by IKA, ultra turrax T50), and the aggregation slurry was obtained. Next, a stirrer and a thermometer were installed in the container, and gradually heated with a mantle heater while maintaining proper stirring, and maintained at 50 ° C. for 3 hours. Next, 40 parts by mass of a resin particle dispersion was added, and the resin particles were adhered to the surface of the aggregated particles. It was confirmed with an optical microscope that the thickness of the resin coating layer was increased. Thereafter, the pH of the aggregated particle slurry was adjusted to 7.1, the temperature was raised to 90 ° C., and the mixture was cooled by holding for an appropriate time while checking the degree of coalescence with an optical microscope.
The obtained toner slurry was coarsely removed with a nylon mesh, filtered, cake washed with ion-exchanged water, and then dried with a vacuum dryer for 12 hours. Next, an external addition process was performed in the same procedure as for toner 1 to obtain toner 26.

(Method for measuring the amount of sulfur element in the domain part and binder resin part of the release agent)
The amount of sulfur element in the domain part of the release agent and the binder resin part in the toner particle cross section was measured by the method described above.

(Creation of carrier)
Ferrite particles (volume average particle size: 35 μm): 100 parts Toluene: 14 parts Polymethyl methacrylate (weight average molecular weight: 75,000): 1.6 parts The above materials are put in a vacuum degassing kneader and the temperature After stirring at 60 ° C. for 30 minutes, the pressure was reduced and toluene was distilled off to form a resin coating layer to obtain a carrier.

(Preparation of electrostatic charge image developer)
To 100 parts of the carrier, 5 parts of the toner was mixed, stirred for 20 minutes at 40 rpm using a V-blender, and sieved with a sieve having an opening of 250 μm to obtain a developer.

(Peelability evaluation)
The prepared developer is set in the developer of the color copying machine “DocuCentre-II C4300” manufactured by Fuji Xerox Co., Ltd. modified so that the roll temperature of the fixing device can be changed, and 10,000 images are continuously formed. It was.
The output image and paper are as follows.
Output image: Full solid image with 1 mm margin at the tip Image toner amount: 5.0 g / m ²
Paper: ST paper (A3 longitudinal, basis weight: 52.3 g / m ² , manufactured by Fuji Xerox Co., Ltd.)
The fixing of the image was performed by setting the sheet conveying speed of the fixing device to 165 mm per second and setting the temperature of the fixing device (fixing temperature) to 180 ° C.
The contact width at the contact portion of the fixing device was 6.0 mm, and the passage time of the paper at the contact portion of the fixing device was 36.4 ms.
100 sheets of images were continuously formed, and the number of sheets in which the paper was wound around the fixing member was evaluated according to the following criteria.
A: No winding occurs B: One or two windings occur C: Three or more windings occur

(Granulation property evaluation)
Using the Coulter Counter TA-II type (manufactured by Beckman Coulter, Inc.), the produced toner is volume average particle size, volume particle size distribution index (D84% / D50%), number average particle size, number particle size distribution. An index (D16% / D50%) was determined. As a measurement method, 0.5 to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, as a dispersant. This was added to 100 to 150 ml of the electrolytic solution, dispersed with an ultrasonic disperser for about 3 minutes, particles of 2 to 60 μm were measured by the Coulter Counter TA-II type, and evaluated according to the following criteria.
A: Volume particle size distribution index is 1.00 to 1.20, and number particle size distribution index is 1.10 to 1.25.
B: Volume particle size distribution index is 1.21-1.30, and number particle size distribution index is 1.26-1.30.
C: Volume particle size distribution index is 1.31-2.00, and number particle size distribution index is 1.31-2.00.

From the above results, it can be seen that the toner of this example can provide an image having excellent peelability from the fixing member as compared with the toner of the comparative example.
It can also be seen that the toner of this example is excellent in granulation properties.

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

Claims (9)

Having toner particles including a binder resin and a release agent;
When the amount of sulfur element in the domain part of the release agent obtained by analyzing the cross section of the toner particles with an energy dispersive X-ray analyzer (EDX) is B, the value of B is 0.2 atomic% or more and 1.5. An electrostatic charge image developing toner having an atomic% or less.   The value of B / A is 1.1 or more and 2.6 or less, where A is the amount of sulfur element in the binder resin portion obtained by analyzing the cross section of the toner particles with an energy dispersive X-ray analyzer (EDX). Item 2. The toner for developing an electrostatic charge image according to Item 1. Heating the release agent above the melting temperature,
Using a disperser to disperse the release agent in the aqueous medium; and
Cooling the release agent particle dispersion,
Including the step of adding a surfactant to the release agent, the aqueous medium, a mixture containing them, or the release agent particle dispersion, at least once before and after the dispersion step,
The ratio M _a / M _b between the amount M _b of the surfactant added before the dispersing step and the amount M _a of the surfactant added after the dispersing step is 0.2 or more and 2 A method for producing a release agent particle dispersion which is 3 or less. A release agent particle dispersion prepared by the method for manufacturing a release agent particle dispersion according to claim 3 and a resin particle dispersion are mixed at least to aggregate the release agent particles and the resin particles to aggregate particles. Forming steps, and
A method for producing a toner for developing an electrostatic charge image, comprising: heating the aggregated particle dispersion in which the aggregated particles are dispersed to fuse and coalesce the aggregated particles to form toner particles.   An electrostatic charge image developer comprising the toner for developing an electrostatic charge image according to claim 1. Containing the toner for developing an electrostatic image according to claim 1;
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for accommodating the electrostatic charge image developer according to claim 5 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;
Developing means for containing the electrostatic charge image developer according to claim 5 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising: A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic image developer according to claim 5;
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: