JP6167949B2 - Method for producing toner for developing electrostatic image and image forming method - Google Patents

Description

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

A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, the electrostatic latent image is developed with a developer containing toner, and visualized through a transfer and fixing process. The developer used here includes a two-component developer composed of a toner and a carrier and a one-component developer using a magnetic toner or a non-magnetic toner alone. The toner is usually produced by using a thermoplastic resin. A kneading and pulverizing method is used in which melt-kneading is performed together with a release agent such as a pigment, a charge control agent, and wax, followed by cooling, fine pulverization, and further classification. In these toners, if necessary, inorganic and organic fine particles for improving fluidity and cleaning properties may be added to the toner particle surface.
In recent years, the oil phase consisting of monomers and colorants, which are the raw materials for the resin, is dispersed in the aqueous phase and directly polymerized into a toner, so that the exposure to the surface is controlled by encapsulating these waxes inside the toner. A production method using a polymerization method has been proposed.
As other means for enabling intentional control of the toner shape and surface structure, Patent Documents 1 and 2 propose a toner manufacturing method using an aggregation and coalescence method.

JP 2005-266598 A JP 2003-215842 A

  An object of the present invention is to provide a method for producing a toner for developing an electrostatic image having good fixing characteristics even under a short-time coalescence condition.

The above-described problems of the present invention have been solved by means described in the following <1> and <9> to <15>. It is described below together with <2> to <8> which are preferred embodiments.
<1> An aggregating step for producing aggregated particles containing at least a binder resin particle and a release agent particle by a wet granulation method, a heating step for heating to an endothermic curve peak temperature of the release agent ± 5 ° C., and an aggregated particle A slow cooling rate that satisfies the following formulas (1) and (2) with the endothermic curve peak temperature ± 5 ° C. of the release agent as the cooling start temperature: In this order, there is a slow cooling process in which the cooling time is T1 minutes at V1 ° C./min, and a rapid cooling process in which the glass resin is rapidly cooled to a temperature below the glass transition temperature of the binder resin at a rate of 8 ° C./min. A method for producing a toner for developing an electrostatic charge image, wherein a cooling temperature in the cooling step is 3.0 ° C. or higher and 10.0 ° C. or lower;
0.5 ≦ V1 ≦ 5.0 (1)
1 ≦ T1 ≦ 20 (2)
<2> The coalescing step has a heating and holding step, a slow cooling step, and a rapid cooling step, which are maintained at 0 to 60 minutes at an endothermic curve peak temperature ± 5 ° C. of the release agent in this order, <1 > A method for producing a toner for developing an electrostatic charge image according to claim 1,
<3> The method for producing a toner for developing an electrostatic charge image according to <2>, wherein the time for maintaining the endothermic curve of the release agent at the endothermic curve peak temperature ± 5 ° C. in the heating and holding step is 0 to 30 minutes,
<4> The method for producing a toner for developing an electrostatic charge image according to <2>, wherein the time for maintaining the endothermic curve peak temperature of the release agent at ± 5 ° C. in the heating and holding step is 0 to 15 minutes,
<5> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <4>, wherein the total time of the coalescence process is 2 minutes to 85 minutes,
<6> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <5>, wherein the endothermic curve peak temperature of the release agent is 60 ° C to 100 ° C.
<7> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <6>, wherein the binder resin has a glass transition temperature of 50 ° C to 70 ° C.
<8> When the endothermic curve peak temperature of the release agent is Tm ° C. and the glass transition temperature of the binder resin is Tg ° C., any one of <1> to <7> satisfying the following formula (3): A method for producing the toner for developing an electrostatic image according to claim 1,
10 ≦ Tm−Tg ≦ 50 (3)
<9> An electrostatic image developing toner obtained by the method for producing an electrostatic image developing toner according to any one of <1> to <8>,
<10> The electrostatic image developer, comprising the toner for developing an electrostatic image according to <9> and a carrier,
<11> A toner cartridge containing the electrostatic image developing toner according to <9>,
<12> A developer cartridge containing the electrostatic image developer according to <10>,
<13> A process cartridge including a developer holder that contains the electrostatic image developer according to <10> and holds and conveys the electrostatic image developer,
<14> An image carrier, a charging unit for charging the image carrier, an exposure unit for exposing the charged image carrier to form an electrostatic latent image on the surface of the image carrier, and a developer containing toner. Developing means for developing the electrostatic latent image to form a toner image, transfer means for transferring the toner image from the image holding member to the surface of the transfer target, and fixing means for fixing the toner image transferred to the surface of the transfer target And the developer is the electrostatic image developing toner according to <9>, or the electrostatic image developer according to <10>,
<15> A latent image forming step of forming an electrostatic latent image on the surface of the image carrier, a developing step of forming a toner image by developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner, A toner for developing an electrostatic charge image according to <9>, comprising: a transfer step of transferring the toner image onto the surface of the transfer member; and a fixing step of fixing the toner image transferred onto the surface of the transfer member; Alternatively, an image forming method using the electrostatic charge image developer according to <10>.

According to the invention described in the above <1>, there is provided a method for producing a toner for developing an electrostatic charge image having good fixing characteristics even under a coalescence condition for a short time as compared with a case where the present configuration is not provided. Provided.
According to the invention described in the above <2>, a method for producing a toner for developing an electrostatic charge image having good fixing characteristics even under a coalescence condition in a shorter time than when the present configuration is not provided. Is provided.
According to the invention described in <3> above, even when the time for maintaining the endothermic peak temperature of the release agent at ± 5 ° C. exceeds 30 minutes, even under a shorter coalescence condition, A method for producing a toner for developing an electrostatic image having good fixing characteristics is provided.
According to the invention described in the above <4>, the fixing agent can be fixed even under a short period of coalescence conditions compared to the case where the endothermic peak temperature of the release agent is maintained at ± 5 ° C. exceeding 15 minutes. A method for producing a toner for developing an electrostatic image having good characteristics is provided.
According to the invention described in <5> above, static characteristics with good fixing characteristics can be obtained even under short-time coalescence conditions, compared to when the total coalescence process time is less than 2 minutes or over 85 minutes. A method for producing a toner for developing a charge image is provided.
According to the invention described in the above <6>, the fixing characteristics are good even under a shorter coalescence condition than when the endothermic curve peak temperature of the release agent is less than 60 ° C. or more than 100 ° C. A method for producing a toner for developing an electrostatic image is provided.
According to the invention described in <7> above, the fixing property is more favorable even in a short time of coalescence conditions than when the glass transition temperature of the binder resin is less than 50 ° C. or more than 70 ° C. A method for producing a toner for developing an electrostatic image is provided.
According to the invention described in <8> above, the electrostatic charge image development has better fixing characteristics even under a short period of coalescence conditions than when Tm-Tg is less than 10 ° C or more than 50 ° C. A method for producing a toner is provided.
According to the invention described in the above <9>, an electrostatic charge image developing toner that is produced under a coalescence condition in a short time and has good fixing characteristics as compared with the case where the present configuration is not provided. The
According to the invention described in <10>, there is provided an electrostatic charge image developer that is produced under a coalescence condition in a short time and has good fixing characteristics as compared with the case where the present configuration is not provided. .
According to the invention described in <11> above, the toner for developing an electrostatic charge image, which is manufactured under a coalescence condition in a short time and has good fixing characteristics, is contained as compared with the case where this configuration is not provided. A toner cartridge is provided.
According to the invention described in the above <12>, an electrostatic charge image developer produced under a coalescence condition in a short time and having excellent fixing characteristics as compared with the case where the present configuration is not provided. A developer cartridge is provided.
According to the invention described in <13> above, an electrostatic charge image developer produced under a short period of coalescence conditions and having good fixing characteristics is accommodated as compared with the case where the present configuration is not provided. A process cartridge is provided.
According to the invention described in <14>, the toner for developing an electrostatic charge image, which is produced under a coalescence condition for a short time and has good fixing characteristics, as compared with the case where the present configuration is not used. An image forming apparatus is provided.
According to the invention described in <15> above, the toner for developing an electrostatic charge image, which is manufactured under a coalescence condition in a short time and has good fixing characteristics, as compared with the case where the present configuration is not provided, is used. An image forming method is provided.

Hereinafter, this embodiment will be described in detail.
In the present embodiment, the description “A to B” represents not only a range between A and B but also a range including A and B at both ends thereof. For example, if “A to B” is a numerical value range, “A or more and B or less” or “B or more and A or less” is represented according to the magnitude of the numerical value.

(Method for producing toner for developing electrostatic image)
The method for producing an electrostatic charge image developing toner (hereinafter, also simply referred to as “toner”) according to the present embodiment is an agglomeration in which agglomerated particles containing at least binder resin particles and release agent particles are produced by a wet granulation method. And a heating step of heating up to an endothermic curve peak temperature of the release agent to ± 5 ° C. and a coalescence step of fusing and coalescing the aggregated particles, and the coalescence step is an endothermic curve peak temperature of the release agent. With a cooling start temperature of ± 5 ° C, a slow cooling step of cooling for a slow cooling time T1 at a slow cooling rate V1 ° C / min satisfying the following formulas (1) and (2) and a rate of 8 ° C / min or more And a rapid cooling step of rapidly cooling to a glass transition temperature or lower of the adhesion resin in this order, and a cooling temperature in the slow cooling step is 3.0 ° C. or higher and 10.0 ° C. or lower.
0.5 ≦ V1 ≦ 5.0 (1)
1 ≦ T1 ≦ 20 (2)

In the so-called agglomeration coalescence method in which the inventors produce toner through an agglomeration step and a coalescence step, when the coalescence step is performed in a short time in order to improve productivity, the release agent in the coalescence step It has been found that the fixing characteristics are deteriorated, such as insufficient domain growth and hot offset.
In Patent Document 1, in order to obtain a suitable release agent domain, a step of heating at a temperature higher than the melting point Tmw of the release agent, cooling from the heating temperature to Tmw at a cooling rate A (° C./min), and Tmw Discloses a method for producing a toner for developing an electrostatic charge image, which comprises a step of cooling to a temperature lower than Tmw at a cooling rate B (° C./min) smaller than the cooling rate A. However, in the Example of patent document 1, it heats for 6 hours at temperature higher than melting | fusing point Tmw of a mold release agent, and it is not enough from a viewpoint of productivity.
Moreover, in patent document 2, it fuse | melts by hold | maintaining for 7 hours after a heating, and productivity is not enough similarly.
As a result of intensive studies, the present inventors have carried out the slow cooling step and the rapid cooling step at a specific cooling rate, so that the domain of the release agent grows in a short time, and the electrostatic image developing toner with high productivity can be obtained. The present inventors have found that a manufacturing method is provided and have completed the present invention.

Although the detailed mechanism is not clear, the slow growth process with a specific slow cooling rate and slow cooling temperature allows the domain growth of the release agent to proceed sufficiently, and then the release agent domain is immobilized by the rapid cooling process. Thus, it is presumed that a toner having excellent fixability can be obtained.
Hereinafter, each process is explained in full detail.

<Aggregation process>
The method for producing a toner for developing an electrostatic charge image according to this embodiment includes an aggregating step of producing aggregated particles containing at least binder resin particles and release agent particles by a wet granulation method. The agglomerated particles contain at least binder resin particles and release agent particles, and may contain other components. Examples of other components include colorants.
As the wet granulation method, a release agent or the like is suspended together with a polymerizable monomer, and a toner constituent material such as a suspension polymerization method in which the polymerizable monomer is polymerized, a binder resin, or a release agent is organically used. There are a solution suspension method in which an organic solvent is removed after being dissolved in a solvent and suspended in an aqueous solvent, and a method in which a resin particle dispersion is produced and heteroaggregated with a particle dispersion such as a release agent . Of these, heteroaggregation is preferred.
The emulsion aggregation and coalescence method (hereinafter sometimes referred to as “emulsion aggregation method”) in which fusion and coalescence are performed after heteroaggregation includes toner particle size controllability, narrow particle size distribution, shape controllability, narrow shape distribution, This method is optimal from the viewpoint of internal dispersion controllability. Hereinafter, a method for producing toner will be described by taking an emulsion aggregation method as an example.

  When the electrostatic charge image developing toner in this embodiment is carried out by an emulsion aggregation method, a binder resin particle dispersion, a release agent particle dispersion, and, if necessary, a colorant particle dispersion or an inorganic particle dispersion. Are mixed to form an aggregated particle dispersion, and then heated to a temperature higher than the melting point of the release agent to fuse the particles, and then a specific cooling step is performed.

(Preparation of binder resin particle dispersion)
The method for dispersing and granulating the binder resin in the aqueous medium can be selected from known methods such as forced emulsification, self-emulsification, and phase inversion emulsification. Among these, the self-emulsification method and the phase inversion emulsification method are preferably applied in consideration of the energy required for emulsification, the particle diameter controllability of the obtained emulsion, stability, and the like. It can also be easily obtained by an emulsion polymerization method and a similar polymerization method in a heterogeneous dispersion system.
The self-emulsification method and the phase inversion emulsification method are described in “Application Technology of Ultrafine Particle Polymer (CMC Publishing)”. As the polar group used for self-emulsification, a carboxy group, a sulfone group and the like are used.

Examples of the disperser used when forming the binder resin particle dispersion include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser. These dispersers are also used for mixing and agglomerating the binder resin particle dispersion and the release agent particle dispersion.
Examples of the dispersion medium in the binder resin particle dispersion, the release agent particle dispersion described later, the colorant dispersion, and other components in the present embodiment include an aqueous medium. Examples of the aqueous medium include water such as distilled water and ion exchange water, and may contain a lower alcohol that is a water-miscible organic solvent. These may be used individually by 1 type and may use 2 or more types together. Among these, the aqueous medium is preferably water such as distilled water or ion exchange water, and ion exchange water is particularly preferred.

When a vinyl monomer is used as the binder resin, an ionic surfactant or the like is used, and preferably an ionic surfactant and a nonionic surfactant are used in combination by an emulsion polymerization method or a seed polymerization method. A resin particle dispersion can be prepared.
The surfactant used here is an anionic surfactant such as sulfate ester, sulfonate, phosphate, or soap; a cationic surfactant such as amine salt or quaternary ammonium salt; polyethylene Nonionic surfactants such as glycols, alkylphenol ethylene oxide adducts, alkyl alcohol ethylene oxide adducts, polyhydric alcohols, and various graft polymers can be mentioned, but those that are particularly limited is not.
When preparing a resin particle dispersion by emulsion polymerization, a small amount of unsaturated acid, for example, acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid, etc. is added as a part of the monomer component, and the resin particle surface A protective colloid layer can be formed on the substrate, and soap-free polymerization is possible, which is particularly preferable.

As the binder resin, a styrene-acrylic resin (a copolymer of styrene and an acrylate ester) and a polyester resin are preferable. The polyester resin preferably contains at least an amorphous polyester resin.
Examples of the acrylic acid ester used for the styrene-acrylic resin include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like. The polymerization of the styrene-acrylic resin is preferably emulsion polymerization using diphenyl oxide disulfonate or a surfactant as an emulsifier. As a polymerization initiator in this case, for example, ammonium persulfate can be used.

The weight average molecular weight Mw of the styrene-acrylic resin is preferably 6,000 to 40,000. It is preferable that the weight average molecular weight Mw is 6,000 or more because the occurrence of uneven fixing is suppressed and the strength against bending resistance of the fixed image is high. Moreover, it is preferable for the weight average molecular weight Mw to be 40,000 or less because of excellent low-temperature fixability.
In the present embodiment, the weight average molecular weight is obtained by molecular weight measurement by a gel permeation chromatography (GPC) method in which tetrahydrofuran (THF) is soluble. The weight average molecular weight of the resin was measured with a THF solvent using a THF soluble material such as TSK-GEL (GMH (manufactured by Tosoh Corporation)), etc., and a molecular weight calibration curve created with a monodisperse polystyrene standard sample was used. Is calculated.

The polyester resin is synthesized from, for example, a polyvalent carboxylic acid component and a polyhydric alcohol component. In the present embodiment, a commercially available product may be used as the polyester resin, or a synthesized product may be used.
As described above, the polyester resin preferably contains at least an amorphous polyester resin, and may contain a crystalline polyester resin together with the amorphous polyester resin. Here, “crystallinity” such as crystalline polyester means that in differential scanning calorimetry (DSC), it has a clear endothermic peak, not a step-like endothermic amount change. It means that the half-value width of the endothermic peak when measured at a temperature rate of 10 ° C./min is within 15 ° C. On the other hand, a resin whose half width exceeds 15 ° C. or a resin in which no clear endothermic peak is observed means an amorphous resin (amorphous polymer), but as an amorphous resin used in this embodiment, It is preferable to use a resin that does not have a clear endothermic peak.

Examples of the polyvalent carboxylic acid component include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12 Aliphatic dicarboxylic acids such as dodecane dicarboxylic acid, 1,14-tetradecane dicarboxylic acid, 1,18-octadecane dicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid Furthermore, these anhydrides and lower alkyl esters thereof are also included, but not limited thereto.
Examples of the trivalent or higher carboxylic acid component include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic acid. And their anhydrides and their lower alkyl esters.
These may be used individually by 1 type and may use 2 or more types together.

Moreover, as a polyvalent carboxylic acid component, the dicarboxylic acid component which has a sulfonic acid group other than the said aliphatic dicarboxylic acid and aromatic dicarboxylic acid may be contained.
Further, as the polyvalent carboxylic acid component, in addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid component having a double bond may be contained.

  As the polyhydric alcohol component, an aliphatic diol is preferable, and a linear aliphatic diol having 7 to 20 carbon atoms in the main chain portion is more preferable. It is preferable that the aliphatic diol is a linear type because a low melting temperature can be obtained. Further, when the carbon number of the main chain portion is 7 or more, the low-temperature fixability is excellent. Moreover, when the carbon number of the main chain portion is 20 or less, it is easy to obtain. The number of carbon atoms in the main chain portion is more preferably 14 or less.

Specific examples of the aliphatic diol suitably used for the synthesis of the polyester resin 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-tride Examples include, but are not limited to, candiol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, and the like. Among these, considering availability, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferable.
Trivalent or higher alcohols can also be used as the polyhydric alcohol component, and examples thereof include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These may be used individually by 1 type and may use 2 or more types together.

  Among the polyhydric alcohol components, the content of the aliphatic diol is preferably 80 mol% or more, and more preferably 90 mol% or more. It is preferable for the content of the aliphatic diol to be 80 mol% or more because it is excellent in toner blocking resistance, image storage stability and low-temperature fixability.

  If necessary, a polycarboxylic acid or a polyhydric alcohol may be added at the final stage of the synthesis for the purpose of adjusting the acid value or the hydroxyl value. Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid, and other aromatic carboxylic acids, maleic anhydride, fumaric acid, succinic acid, alkenyl Examples thereof include aliphatic carboxylic acids such as succinic anhydride and adipic acid, and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid.

  There is no restriction | limiting in particular in the manufacturing method of the said polyester resin, It can manufacture with the general polyester polymerization method which makes a polyhydric carboxylic acid component and a polyhydric alcohol component react. For example, direct polycondensation, transesterification, and the like are used depending on the type of monomer. The molar ratio (acid component / alcohol component) for reacting the polyvalent carboxylic acid component with the polyhydric alcohol component is usually about 1/1, although it varies depending on the reaction conditions and the like. The polyester resin can be produced at a polymerization temperature of 180 to 230 ° C., and the reaction system is reduced in pressure as necessary, and the reaction is carried out while removing water and alcohol generated during condensation.

  Examples of the catalyst used in the production of the polyester resin include alkali metal compounds such as sodium and lithium, alkaline earth metal compounds such as magnesium and calcium, zinc, manganese, antimony, titanium, tin, zirconium, and germanium. And metal compounds such as phosphorous compounds, phosphoric acid compounds, and amine compounds.

The weight average molecular weight (Mw) of the polyester resin is preferably 6,000 to 35,000. When the weight average molecular weight (Mw) is 6,000 or more, fixing unevenness is suppressed and the strength against bending resistance of a fixed image is excellent, which is preferable. Further, it is preferable that the weight average molecular weight Mw is 35,000 or less because of excellent low-temperature fixability.
The acid value of the polyester resin is preferably 5 to 25 mgKOH / g, more preferably 8 to 20 mgKOH / g, and still more preferably 10 to 18 mgKOH / g. When the acid value is within the above range, the toner has good affinity for paper and good chargeability.

The glass transition temperature (Tg) of the binder resin is preferably 40 to 80 ° C. It is preferable that the binder resin has a glass transition temperature of 40 ° C. or higher because it is excellent in toner storage stability and fixed image storage stability. Further, when the glass transition temperature is 80 ° C. or lower, the low-temperature fixability is excellent.
The glass transition temperature of the binder resin is more preferably 45 to 75 ° C, and further preferably 50 to 70 ° C.

  The average particle size of the binder resin particles is preferably 1 μm or less, more preferably 0.01 to 1 μm. When the average particle size of the binder resin particles is within the above range, the particle size distribution of the finally obtained electrostatic image developing toner is narrow, the generation of free particles is suppressed, and the uneven distribution between the toners is further suppressed. This is advantageous in that it decreases, disperses well in the toner, and reduces variations in performance and reliability. The average particle diameter of the binder resin particles can be measured using, for example, a microtrack.

(Preparation of release agent particle dispersion)
The release agent particle dispersion is prepared by dispersing the release agent in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid or a polymer base, and heating and melting to a temperature higher than the melting point. It can be carried out by preparing a dispersion of release agent particles of 1 μm or less using a homogenizer or pressure discharge type disperser that can be applied.

In the present embodiment, the release agent includes low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene, silicones having a softening point, fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide. , Carnauba wax, rice wax, candelilla wax, plant waxes such as tree wax and jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc. Mineral waxes, petroleum waxes, ester waxes of higher fatty acids and higher alcohols such as stearyl stearate and behenyl behenate, butyl stearate, propyl oleate, monostearate glyceride, di Higher esters such as ester waxes of higher fatty acids such as tea glyceride, pentaerythritol tetrabehenate and unit price or polyhydric lower alcohol, diethylene glycol monostearate, dipropylene glycol distearate, distearic diglyceride, tetrastearic acid triglyceride Examples include ester waxes composed of a fatty acid and a polyhydric alcohol multimer, sorbitan higher fatty acid ester waxes such as sorbitan monostearate, and higher cholesterol fatty acid ester waxes such as cholesteryl stearate.
Among these, mineral / petroleum waxes, ester waxes, and plant waxes are preferably used as the release agent.
These release agents may be used alone or in combination of two or more.

The endothermic peak temperature of the release agent is preferably 60 ° C to 100 ° C. When the endothermic peak temperature of the release agent is 60 ° C. or higher, the exposure of the release agent to the toner surface is small, and the fluidity and chargeability of the toner are difficult to be disturbed. It is ensured and the occurrence of hot offset is prevented. The endothermic peak temperature of the release agent is more preferably 65 ° C to 98 ° C, and further preferably 70 to 95 ° C.
The endothermic peak temperature of the release agent is measured according to JIS 7121-1987 using a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001). The melting point of a mixture of indium and zinc is used for temperature correction of the detection unit of this apparatus, and the heat of fusion of indium is used for correction of heat quantity. The sample is put in an aluminum pan, and an aluminum pan containing the sample and an empty aluminum pan for control are set, and measurement is performed from room temperature at a heating rate of 10 ° C./min. The endothermic peak temperature is defined as the endothermic curve peak temperature (endothermic peak temperature) measured by the suggested scanning calorimeter with the temperature at the top of the maximum endothermic peak among the endothermic peaks of the DSC curve obtained by the measurement.
In addition, when it has a some mold release agent as a mold release agent, it is preferable that the endothermic peak temperature of all the mold release agents exists in the said range.

In this embodiment, when the endothermic peak temperature of the release agent is Tm ° C. and the glass transition temperature of the binder resin is Tg ° C., it is preferable to satisfy the following formula (3).
10 ≦ Tm−Tg ≦ 50 (3)
When the difference between Tm and Tg is within the above range, it is possible to achieve both control of toner shape and securing of releasability.
Tm-Tg is more preferably 20 to 50 ° C, and further preferably 30 to 50 ° C.
When a plurality of release agents and / or binder resins are contained, it is preferable that the maximum content of the release agent and the maximum content of the binder resin satisfy at least the above formula (3). More preferably, the combination of the release agent and the binder resin satisfies the above formula (3).

  The content of the release agent in the toner is preferably 0.5 to 15% by weight, and more preferably 1.0 to 12% by weight. When the content of the release agent is 0.5% by weight or more, the releasability is good particularly in oil-less fixing, and when it is 15% by weight or less, the toner has excellent fluidity and image quality and image quality. This is preferable because the formation reliability is improved.

In the present embodiment, the aggregated particles may contain other components in addition to the binder resin particles and the release agent particles, and specific examples include colorant particles and inorganic particles.
(Preparation of colorant particle dispersion)
The colorant particle dispersion can be prepared by any dispersion method using a colorant in a dispersion medium such as water, for example, a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill, or the like. Is not to be done.

The colorant contained in the toner may be a dye or a pigment, but a pigment is desirable from the viewpoint of light resistance and water resistance.
In the present embodiment, examples of the pigment used as the colorant include the following.
Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa yellow, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow NCG. Is mentioned. Specifically, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 93 and the like, and C.I. I. Pigment Yellow 74 is preferable. As a yellow pigment, the 1 type (s) or 2 or more types of the said pigment can be used together.
Examples of black pigments include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.
Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange GG, indanthrene brilliant orange RK, indanthrene brilliant oren GK and the like.

  Examples of red pigments include bengara, cadmium red, red lead, mercury sulfide, quinacridone, watch young red, permanent red 4R, resol red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake, rake. Examples include Red C, Rose Bengal, Eoxin Red, Alizarin Lake and the like.

Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate and so on.
Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.
Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

  Moreover, dye can also be used as a coloring agent as needed. Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue. Moreover, these can be used individually or in mixture, and also in the state of a solid solution.

In the present embodiment, the average particle diameter of the colorant particles is preferably 0.8 μm or less, more preferably 0.05 to 0.5 μm. It is preferable that the average particle diameter of the colorant particles is 0.8 μm or less because a toner having a narrow particle size distribution is obtained, generation of free particles is suppressed, and performance and reliability are improved. It is preferable that the average particle diameter of the colorant particles is 0.05 μm or more because high colorability is obtained and toner shape controllability is excellent.
Further, the number% of particles of 0.8 μm or more is preferably less than 10%, and substantially preferably 0%. The presence of such coarse particles may impair the stability of the agglomeration process and broaden the particle size distribution as well as the liberation of coarse colored particles.
The number% of particles of 0.05 μm or less is preferably 5% or less. The presence of such fine particles impairs the shape controllability in the fusion process, and there is a possibility that a so-called smooth particle having an average circularity of 0.940 or more cannot be obtained. On the other hand, when the average particle diameter, coarse particles, and fine particles of the colorant particles are within the above ranges, there is no such defect, and uneven distribution between the toners is reduced, and dispersion in the toners is improved. Further, it is advantageous that the variation in reliability is reduced.

  The average particle diameter of the colorant particles can be measured using, for example, a microtrack. The amount of the colorant added is preferably set in the range of 1 to 20% by weight with respect to the toner particles.

[Other additives]
In addition to the above components, the toner may contain various components such as an internal additive and a charge control agent as necessary.
Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, manganese, nickel, and magnetic materials such as alloys, compounds containing these metals, and the like. An amount not used is used.
The charge control agent is not particularly limited, but when a color toner is used, a colorless or light color is preferably used. Examples include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments. From the viewpoint of controlling strength and reducing wastewater contamination, a material that is difficult to dissolve in water is preferred. In the present embodiment, the toner may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  A surfactant may be used for the purpose of stabilizing the dispersion of each dispersion. 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, etc. And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable.

  Specific examples of anionic surfactants include dialkyls such as fatty acid soaps, sulfates, sodium alkylnaphthalenesulfonates, naphthalenesulfonate formalin condensates, alkylsulfonates, alkylphosphates, sodium dioctylsulfosuccinate. Examples include sulfosuccinates and sulfosuccinates such as disodium lauryl sulfosuccinate.

  Specific examples of the cationic surfactant include amine salts such as laurylamine hydrochloride and stearylamine hydrochloride, and quaternary ammonium salts such as lauryltrimethylammonium chloride and dilauryldimethylammonium chloride.

The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant.
Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, alkylphenyl ethers such as polyoxyethylene octylphenyl ether, alkyl esters such as polyoxyethylene laurate, polyoxyethylene Alkylamines such as laurylamino ether, alkylamides such as polyoxyethylene lauric acid amide, vegetable oil ethers such as polyoxyethylene castor oil ether, alkanolamides such as lauric acid diethanolamide, polyoxyethylene sorbitan monolaur Examples include sorbitan ester ethers such as rate.
The said surfactant may be used individually by 1 type, and may use 2 or more types together. Moreover, as content in each dispersion liquid of surfactant, it is generally a small amount, and specifically, it is preferable that it is the range of 0.01 to 10 weight%, More preferably, it is 0.05 to It is in the range of 5% by weight, more preferably in the range of 0.1 to 2% by weight. When the content is 0.01% by weight or more, each dispersion such as a resin particle dispersion, a colorant dispersion, and a release agent dispersion is stabilized, and aggregation and release of specific particles are suppressed. . Further, if it is 10% by weight or less, a narrow particle size distribution can be obtained, and the particle size can be easily controlled, which is preferable. In general, a suspension polymerization toner dispersion having a large particle size is stable even if the amount of the surfactant used is small. As the amount of the surfactant is increased, the environmental stability of charging of the toner is lowered. Therefore, it is preferable that the addition amount of the surfactant is small.

  In addition, an aqueous polymer that is solid at room temperature (25 ° C.) can also be used. Specifically, cellulose compounds such as carboxymethyl cellulose and hydroxypropyl cellulose, polyvinyl alcohol, gelatin, starch, gum arabic and the like are used.

(Preparation of aggregated particle dispersion)
The agglomerated particle dispersion is prepared by mixing the binder resin particle dispersion, the release agent particle dispersion, and, if necessary, the colorant particle dispersion and the inorganic particle dispersion prepared as described above. Is called. In that case, it is preferable to heat a liquid mixture to Tg of binder resin, or its vicinity as needed.
The aggregating method in the aggregating step is not particularly limited, and the stability of the emulsion by the aggregating method conventionally used in the agglomeration and coalescence method of toner, for example, temperature increase, pH change, addition of a coagulant, etc. And a method of stirring with a disperser or the like is used.

In this embodiment, the binder resin particle dispersion and the release agent particle dispersion are mixed, and an aggregating agent is added to cause aggregation between the binder resin particles and the release agent particles, which corresponds to the toner diameter. It is preferable to form aggregated particles. In addition to the binder resin particle dispersion and the release agent particle dispersion, a colorant particle dispersion, an inorganic particle dispersion, and the like may be added.
The above production method is a method in which the raw material dispersions are mixed together and agglomerated and fused, but the amount of polar ionic surfactant contained in the dispersion is balanced in the initial stage of the aggregation process. It is shifted in advance, for example, ionically neutralized using a flocculant to form core aggregated particles below the glass transition temperature of the binder resin, and after stabilization, core aggregated particles or Polarity and amount to compensate for the above-mentioned balance deviation as the second stage, if necessary after stabilization by slightly heating at a high temperature below the glass transition temperature or melting temperature of the resin contained in the additional particles And then, if necessary, stabilized by slightly heating at a temperature not higher than the glass transition temperature of the resin contained in the core aggregated particles or additional particles, and then added to the glass transition temperature or higher. Fusing and coalescing leave the particles added in the second step were deposited on the surface of the core aggregated particles and are preferred.
In the second step, the coating layer may be formed by adding the binder resin particle dispersion and attaching the binder resin particles to the surface of the aggregated particles formed in the first step ( Adhesion process). Thereby, a toner having a core / shell structure constituted by a so-called core layer and a coating layer (shell) covering the core layer is obtained.
The method for stopping the growth of the aggregated particles may be selected from known methods such as changing the pH.

The aggregating step is preferably performed at a temperature 20 ° C. to 5 ° C. lower than the glass transition temperature of the binder resin contained in the core agglomerated particles or the additional particles, and more preferably 15 ° C. to 8 ° C. preferable.
Specifically, although depending on the glass transition temperature of the binder resin, the aggregation step is preferably performed at 40 ° C. to 50 ° C., more preferably 42 ° C. to 48 ° C.

Moreover, it is preferable to add an aggregating agent when preparing the above-mentioned aggregated particle dispersion. The flocculant used is not particularly limited, but a surfactant having a polarity opposite to that of the surfactant used in the release agent particle dispersion, the colorant particle dispersion, etc., and a divalent or higher inorganic metal salt or metal complex. Can be suitably used. In particular, the use of an inorganic metal salt or metal complex is preferable because the amount of the surfactant used can be reduced and the charging characteristics are improved.
The aggregating agent is not particularly limited, but a metal salt of an inorganic acid is preferable in consideration of the stability of the agglomerated particles, the stability of the aggregating agent with respect to heat and time, and removal during washing. Specific examples include metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate. In this embodiment, the final toner is used. From the viewpoint of controlling the viscosity at the time of fixing the particles, an aggregating agent containing aluminum (for example, polyaluminum chloride, aluminum sulfate, potassium alum, etc.) is preferable.
In order to obtain a sharper particle size distribution, even if the valence of the inorganic metal salt is monovalent to bivalent, bivalent to trivalent, trivalent to tetravalent, and the same valence, the polymerization type inorganic metal salt weight Combined is more suitable.
The amount of these flocculants added varies depending on the valence of the charge, but all of them are small, and in the case of monovalent, about 3% by weight or less relative to the total amount of toner, and in the case of bivalent, about 1% by weight or less. In the case of trivalent, it is about 0.5% by weight or less. Since the amount of the flocculant is preferably small, it is preferable to use a compound having a large valence.

<Heating process>
The method for producing an electrostatic charge image developing toner of the present embodiment includes a heating step of heating from the aggregation temperature in the aggregation step to the endothermic peak temperature of the release agent ± 5 ° C.
As described above, the aggregation temperature, which is the heating start temperature in the heating step, is preferably 5 to 20 ° C. lower than the glass transition temperature of the binder resin.
Although the heating rate in a heating process is not specifically limited, It is preferable that it is 0.1-10 degreeC / min, It is more preferable that it is 0.5-7 degreeC / min, It is that it is 1-5 degreeC / min. Further preferred.
A heating rate within the above range is preferable in that the amount of fine particles generated can be suppressed to a small amount.
In addition, although the said heating rate may be fixed and may change in a heating process, it is preferable that it exists in the range of said heating rate throughout the heating process. Further, a constant heating rate is particularly preferable.
When two or more release agents are used, the release agent having the highest content in the toner is heated to an endothermic peak temperature of ± 5 ° C. The same applies to the endothermic peak temperature of the release agent.

<Joint process>
The method for producing an electrostatic charge image developing toner according to the present embodiment includes a coalescing step of fusing and coalescing the aggregated particles obtained in the above-described aggregation step. In the coalescence process, the endothermic curve peak temperature of the release agent ± 5 ° C. is used as the cooling start temperature, and the cooling is performed at a slow cooling rate V1 ° C./min that satisfies the following formulas (1) and (2). The cooling process and the rapid cooling process for rapidly cooling to the glass transition temperature of the binder resin or lower at a rate of 10 ° C./min or higher in this order, and the cooling temperature in the slow cooling process is 3.0 ° C. or higher and 10.0 It is below ℃.
0.5 ≦ V1 ≦ 5.0 (1)
1 ≦ T1 ≦ 20 (2)

  In addition, it is preferable that a coalescence process has the heating holding process, the slow cooling process, and the rapid cooling process which are maintained for 0 minute-60 minutes at the endothermic peak temperature +/- 5 degreeC of a mold release agent in this order. Hereinafter, the heating and holding step, the slow cooling step, and the rapid cooling step will be described in detail.

<Heat holding process>
In this embodiment, it is preferable that a coalescing process has a heating holding process maintained at the endothermic peak temperature ± 5 ° C. of the release agent for 0 minutes to 60 minutes. Note that “maintain 0 to 60 minutes” means that the time to maintain is 60 minutes or less or that there is no time to maintain (it is 0 minutes).
In the heating and holding step, if the time to maintain exceeds 0 minutes, it may be maintained in the range of the endothermic peak temperature ± 5 ° C. of the release agent, and the temperature may change in the heating and holding step, It is preferable to maintain at a constant temperature.

In the heating and holding step, the time for maintaining the endothermic peak temperature of the release agent at ± 5 ° C. is 0 to 60 minutes. When it exceeds 60 minutes, productivity will fall. The conventional method for producing a toner for developing an electrostatic image requires a heating and holding step for 3 hours (180 minutes or more). However, in the method for producing a toner for developing an electrostatic image of this embodiment, a specific slow cooling step is required. And by having a rapid cooling process, the time of a heating holding process can be shortened significantly, and the time of the whole unification process can be shortened. As a result, a method for producing an electrostatic charge image developing toner with high productivity is provided.
The time for maintaining the endothermic peak temperature of the release agent at ± 5 ° C. is preferably 0 to 30 minutes, more preferably 0 to 15 minutes, and 0 minutes, that is, no time to maintain. Is most preferred. In this case, after the agglomeration step, heating is performed from the agglomeration temperature to the endothermic peak temperature of the release agent ± 5 ° C., and the gradual cooling step is performed without maintenance.

The heating and holding temperature in the heating and holding step is the endothermic peak temperature of the release agent ± 5 ° C., more preferably ± 3 ° C. of the endothermic peak of the release agent, and further preferably ± 1 ° C.
When heated and held at a temperature higher than 5 ° C. higher than the endothermic peak of the release agent, there is a problem that the presence of the release agent on the toner surface increases and the fluidity deteriorates. In addition, when heated and held at a temperature exceeding 5 ° C. lower than the endothermic peak of the release agent, domain growth of the release agent is not promoted.

  If necessary, an acid or a base may be added for the purpose of avoiding coalescence of the aggregated particles in the heating and holding step or the slow cooling step. In particular, when a polyester resin having an acid value is used as a binder resin, when the heating and holding process starts or when the heating and holding process has a maintenance time of 0 minutes (when the heating and holding process is not provided) It is preferable to add an acid at the start of the slow cooling step. Examples of the acid include nitric acid, hydrochloric acid, acetic acid and the like, and nitric acid is preferable.

<Slow cooling process>
In this embodiment, the coalescing step is a slow cooling time at a slow cooling rate V1 ° C./min satisfying the following formulas (1) and (2), with the endothermic curve peak temperature ± 5 ° C. of the release agent as the cooling start temperature. A slow cooling step of cooling for T1 minutes. Moreover, the cooling temperature in a slow cooling process is 3.0 degreeC or more and 10.0 degrees C or less.
0.5 ≦ V1 ≦ 5.0 (1)
1 ≦ T1 ≦ 20 (2)

As shown in the formula (1), the slow cooling rate V1 is 0.5 ° C./min to 5.0 ° C./min. When the slow cooling rate is less than 0.5 ° C./min, it becomes difficult to control the presence ratio of the release agent on the toner surface, and the fluidity deteriorates. Further, when the slow cooling temperature exceeds 5.0 ° C./min, the domain of the release agent does not grow sufficiently, and as a result, a sufficient amount of wax does not exist on the toner surface at the time of fixing, and hot offset occurs. Problems such as being unable to be suppressed occur.
The slow cooling rate is preferably 0.7 ° C / min to 3 ° C / min, more preferably 1 ° C / min to 1.5 ° C / min.
The slow cooling rate may be a constant rate or may change during the slow cooling step, but is 0.5 ° C./min to 5.0 ° C./min throughout the slow cooling step. Among these, it is preferable that the slow cooling process is performed at a constant cooling rate.

The slow cooling time T1 is 1 minute to 20 minutes. When the slow cooling time is less than 1 minute, the domain growth of the release agent is not sufficient, and as a result, a sufficient amount of wax does not exist on the toner surface at the time of fixing, causing problems such as hot offset. When the slow cooling time exceeds 20 minutes, the presence of the release agent on the toner surface increases and the fluidity deteriorates.
The slow cooling time T1 is preferably 3 minutes to 18 minutes, and more preferably 5 minutes to 15 minutes.

The cooling temperature in the slow cooling step is 3.0 ° C. or higher and 10.0 ° C. or lower. When the cooling temperature is less than 3.0 ° C. or exceeds 10 ° C., it becomes difficult to control the domain growth of the release agent and the toner shape.
The cooling temperature is preferably 4 ° C to 8 ° C, and more preferably 5 ° C to 7 ° C.
The cooling temperature means a temperature lowered by cooling at a gradual cooling time T1 at a gradual cooling rate V1 ° C./min. When the slow cooling step is performed at a constant cooling rate V1 ° C./min, the cooling temperature in the slow cooling step is represented by V1 × T1.

<Rapid cooling process>
In the present embodiment, the coalescing step has a rapid cooling step of rapidly cooling to the glass transition temperature or lower of the binder resin at a rate of 8 ° C./min or more.
The cooling rate in the rapid cooling step is 8 ° C./min or more. When the cooling rate is less than 8 ° C./toner shape controllability and productivity are lowered.
The cooling rate in the rapid cooling step is preferably 10 to 40 ° C./min, and more preferably 10 to 30 ° C./min.
The cooling rate in the rapid cooling step may be constant or may vary within a range of 10 ° C./min or more, but is preferably a constant cooling rate.

In the rapid cooling step, rapid cooling is performed to a temperature below the glass transition temperature of the binder resin. When two or more kinds of binder resins are used, rapid cooling is performed to the glass transition temperature or lower of the binder resin having the lowest glass transition temperature.
In addition, it is preferable to rapidly cool to a temperature lower by 5 ° C. or more from the glass transition temperature of the binder resin, more preferably to cool to a temperature lower by 10 ° C. or more, more preferably to cool to a temperature lower by 20 ° C. or more. . Within the above range, a toner having a good surface state can be obtained, which is preferable.

  In this embodiment, it is preferable that the time of the unification process including a heating holding process, a slow cooling process, and a rapid cooling process is 2 minutes-85 minutes, It is more preferable that it is 3 minutes-50 minutes, 5 More preferably, it is from 20 minutes to 20 minutes. It is preferable that the time of the coalescing step is within the above-mentioned range because the toner for developing an electrostatic image having excellent productivity and shortening the coalescing step and excellent reliability can be obtained.

(Other processes)
<Washing step, solid-liquid separation step, and drying step>
After completion of the aggregation process and the coalescence process, toner is obtained as coalesced particles. After completion of the aggregation process and the coalescence process, a desired toner may be obtained through an arbitrary washing process, solid-liquid separation process, and drying process.
In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Further, the drying process is not particularly limited, but vacuum drying, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

<External addition process>
The toner particles obtained as described above may further have an external addition step of adding an external additive. The external addition step may be a wet external addition step or a dry external addition step, and is not particularly limited, but is preferably a dry external addition step from the viewpoint of not requiring a drying step.
Examples of the mixer used in the dry external addition method include known mixers such as a V-type blender, a Henschel mixer, and a Redige mixer.

Examples of the external additive include inorganic particles and organic particles, and these particles are preferably added to the surface of the toner particles while applying a shearing force.
Examples of inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, Examples include Bengala, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, and silicon nitride. Among them, silica particles and titanium oxide particles are preferable, and particles subjected to hydrophobic treatment (surface treatment) are particularly preferable.
Inorganic particles are generally used for the purpose of improving fluidity. The primary particle size of the inorganic particles is preferably in the range of 1 to 200 nm, and the addition amount is preferably in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the toner.

Organic particles are generally used for the purpose of improving cleaning properties and transfer properties, specifically, fluorine resin powders such as polyvinylidene fluoride and polytetrafluoroethylene, fatty acid metal salts such as zinc stearate and calcium stearate, Examples include polystyrene and polymethyl methacrylate.
These external additives may be used alone or in combination of two or more.

(Toner characteristics)
In this embodiment, the average circularity of the electrostatic charge image developing toner is preferably 0.950 to 0.985. The closer the toner shape is to a perfect sphere, the more advantageous in terms of developability and transferability. The average circularity of the toner is more preferably 0.955 to 0.980. When the average circularity is within the above range, transfer efficiency and image density are improved, high-quality image formation is performed, and the cleaning property of the surface of the photoreceptor (image holding member) is enhanced.
The average circularity is preferably measured with FPIA-3000 manufactured by Sysmex. This system employs a method in which particles dispersed in water or the like are measured by a flow-type image analysis method, and the aspirated particle suspension is guided to a flat sheath flow cell and converted into a flat sample flow by the sheath liquid. It is formed. By irradiating the sample stream with stroboscopic light, the passing particles are captured as a still image by the CCD camera through the objective lens. The captured particle image was subjected to two-dimensional image processing, and the equivalent circle diameter and circularity were calculated from the projected area and the perimeter. The equivalent circle diameter was calculated as the equivalent circle diameter from the area of the two-dimensional image with respect to each photographed particle. Regarding the circularity, at least 4,000 or more images were analyzed, and the average circularity was obtained by performing statistical processing.
Circularity = circle equivalent diameter perimeter / perimeter = [2 × (Aπ) 1/2] / PM
In the above formula, A represents the projected area, and PM represents the perimeter.
In addition, HPF mode (high resolution mode) was used for the measurement, and the dilution factor was 1.0. In the data analysis, the number particle size analysis range was set to 2.0 to 30.1 μm and the circularity analysis range was set to a range of 0.40 to 1.00 for the purpose of removing measurement noise.
In the exemplary embodiment, the electrostatic charge image developing toner has a volume average particle diameter of preferably 3 to 9 μm, more preferably 3.1 to 8.5 μm, and still more preferably 3.2 to 8.0 μm. If the volume average particle diameter is 3 μm or more, the fluidity is unlikely to decrease and the chargeability is easily maintained. If the volume average particle size is 9 μm or less, the resolution is hardly lowered. The volume average particle size is measured with a measuring device such as Coulter Multisizer II (manufactured by Beckman Coulter, Inc.). For a toner having a distribution in particle size, the particle size is about 50,000. The particle diameter corresponding to 50% of the volume particle diameter is defined as the volume average particle diameter.

(Electrostatic image developer)
The electrostatic image developing toner of this embodiment is used as a non-magnetic one-component developer or two-component developer. When used as a two-component developer, it is used by mixing with a carrier.
The carrier that can be used in the two-component developer is not particularly limited, and a known carrier is used. Examples thereof include magnetic metals such as iron oxide, nickel and cobalt, magnetic oxides such as ferrite and magnetite, resin-coated carriers having a resin coating layer on the surface of the core material, and magnetic dispersion carriers. Further, a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin may be used.

Coating resins and matrix resins used for carriers include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic. Examples include, but are not limited to, acid copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenol resins, and epoxy resins.
Examples of the conductive material include metals such as gold, silver and copper, carbon black, titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, tin oxide, and carbon black, but are not limited thereto. It is not something.

  Examples of the carrier core material include magnetic metals such as iron, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. However, in order to use the carrier for the magnetic brush method, a magnetic material is used. Preferably there is. The volume average particle diameter of the carrier core material is preferably in the range of 10 μm to 500 μm, and more preferably in the range of 30 μm to 100 μm.

In order to coat the surface of the carrier core material with a resin, there may be mentioned 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. 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 an immersion method in which the carrier core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed onto the surface of the carrier core material, and the carrier core material is fluidized air. A fluidized bed method in which the coating layer forming solution is sprayed in a state of being suspended by the above, a kneader coater method in which the carrier core material and the coating layer forming solution are mixed in a kneader coater, and the solvent is removed.

  The mixing ratio (weight ratio) of the electrostatic image developing toner of the exemplary embodiment and the carrier in the two-component developer is preferably in the range of toner: carrier = 1: 100 to 30: 100. : More preferably, it is in the range of 100 to 20: 100.

(Image forming method)
The electrostatic image developer (electrostatic image developing toner) is used in an image forming method of an electrostatic image developing system (electrophotographic system).
The image forming method of the present embodiment includes a latent image forming step of forming an electrostatic latent image on the surface of the image carrier, and developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner. A developing step for forming an image, a transferring step for transferring the toner image to the surface of the transfer member, and a fixing step for fixing the toner image transferred to the surface of the transfer member. The toner for developing an electrostatic charge image of the form or the electrostatic charge image developer of the present embodiment is used.
In addition to the above steps, a cleaning step for cleaning the developer remaining on the image carrier may be provided.

Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. Note that the image forming method of the present embodiment can be carried out by using a known image forming apparatus such as a copying machine or a facsimile machine.
The electrostatic latent image forming step is a step of forming an electrostatic latent image on an image carrier (photoconductor).
The developing step is a step of developing the electrostatic latent image with a developer layer on a developer holding member to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developing toner of this embodiment.
The transfer step is a step of transferring the toner image onto a transfer target. Examples of the transfer medium in the transfer process include an intermediate transfer medium and a recording medium such as paper.
In the fixing step, for example, there is a method of forming a copy image by fixing the toner image transferred onto the transfer paper by a heating roller fixing device in which the temperature of the heating roller is set to a constant temperature.
The cleaning step is a step of cleaning the electrostatic charge image developer remaining on the image carrier.
In the image forming method of the present embodiment, it is more preferable that the cleaning step includes a step of removing the electrostatic charge image developer remaining on the image carrier with a cleaning blade.
As the recording medium, known media can be used, for example, paper used for electrophotographic copying machines, printers, OHP sheets, etc. For example, the surface of plain paper is made of resin, etc. Coated coated paper, art paper for printing, and the like can be suitably used.

  The image forming method of the present embodiment may further include a recycling step. The recycling step is a step of transferring the electrostatic image developing toner collected in the cleaning step to the developer layer. The image forming method including the recycling process is performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. Further, the present invention may be applied to a recycling system that collects toner simultaneously with development.

(Image forming device)
The image forming apparatus according to this embodiment includes an image carrier, a charging unit that charges the image carrier, and an exposure unit that exposes the charged image carrier to form an electrostatic latent image on the surface of the image carrier. Developing means for developing the electrostatic latent image with a developer containing toner to form a toner image; transfer means for transferring the toner image from the image holding member to the surface of the transferred body; and the transferred body Fixing means for fixing the toner image transferred on the surface, and the developer for developing an electrostatic image of the present embodiment or the electrostatic image developer of the present embodiment is used as the developer. .
Further, in addition to the above means, a cleaning means for cleaning the image carrier may be provided.
The image forming apparatus according to the present exemplary embodiment is not particularly limited as long as it includes at least the image holding member, the charging unit, the exposure unit, the developing unit, the transfer unit, and the fixing unit as described above. However, it may contain a cleaning means, a static elimination means, etc. as needed.
In the transfer unit, the transfer may be performed twice or more using an intermediate transfer member. Examples of the transfer medium in the transfer unit include an intermediate transfer medium and a recording medium such as paper.

The image carrier and each of the above-described units can preferably use the configurations described in the respective steps of the image forming method. As each of the above-described means, a known means in the image forming apparatus can be used. In addition, the image forming apparatus according to the present embodiment may include means and devices other than the above-described configuration. Further, the image forming apparatus according to the present embodiment may simultaneously perform a plurality of the above-described means.
Examples of the cleaning means for cleaning the electrostatic charge image developer remaining on the image holding member include a cleaning blade and a cleaning brush, and a cleaning blade is preferable. Preferred examples of the cleaning blade material include urethane rubber, neoprene rubber, and silicone rubber.

(Toner cartridge, developer cartridge, and process cartridge)
The toner cartridge of this embodiment is a toner cartridge that contains at least the toner for developing an electrostatic charge image of this embodiment.
The developer cartridge of this embodiment is a developer cartridge that contains at least the electrostatic charge image developer of this embodiment.
The process cartridge of the present embodiment is a process cartridge including a developer holder that contains an electrostatic charge image developer and holds and conveys the electrostatic charge image developer, and is formed on the surface of the image carrier. Developing means for developing the electrostatic latent image formed with the electrostatic image developing toner or the electrostatic image developer to form a toner image, an image holding member, and a charging means for charging the surface of the image holding member And at least one selected from the group consisting of cleaning means for removing the toner remaining on the surface of the image carrier, and the electrostatic image developing toner of the present embodiment, or of the present embodiment. The process cartridge preferably contains at least an electrostatic charge image developer.

The toner cartridge of this embodiment is preferably detachable from the image forming apparatus. That is, in the image forming apparatus having a configuration in which the toner cartridge can be attached and detached, the toner cartridge of the present embodiment in which the toner of the present embodiment is stored is preferably used.
The developer cartridge of the present embodiment is not particularly limited as long as it contains the electrostatic charge image developer containing the electrostatic charge image developing toner of the present embodiment. The developer cartridge is, for example, attached to and detached from an image forming apparatus including a developing unit, and includes the electrostatic image developer according to the present embodiment as a developer to be supplied to the developing unit. Is stored.
The developer cartridge may be a cartridge that stores toner and a carrier, or may be a cartridge that stores toner alone and a cartridge that stores a carrier separately.
It is preferable that the process cartridge of the present embodiment is attached to and detached from the image forming apparatus.
In addition, the process cartridge according to the present embodiment may include other members such as a static elimination unit as necessary.
As the toner cartridge and the process cartridge, known configurations may be adopted. For example, Japanese Patent Application Laid-Open Nos. 2008-209489 and 2008-233736 are referred to.

  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 weight” and “% by weight”.

(Various measurement methods)
<Measurement of acid value>
The acid value was measured according to JIS K0070 and measured using a neutralization titration method. That is, an appropriate amount of sample was taken, 100 ml of a solvent (diethyl ether / ethanol mixed solution) and a few drops of an indicator (phenolphthalein solution) were added, and the mixture was shaken sufficiently until the sample was completely dissolved on a water bath. . This was titrated with a 0.1 mol / l potassium hydroxide ethanol solution, and the end point was when the indicator was light red for 30 seconds. When the acid value is A, the sample amount is S (g), the 0.1 mol / l potassium hydroxide ethanol solution used for the titration is B (ml), and f is the factor of the 0.1 mol / l potassium hydroxide ethanol solution. ,
A = (B × f × 5.611) / S
Calculated as

<Measuring method of glass transition temperature and endothermic peak temperature>
The glass transition temperature and the endothermic peak temperature were measured according to JIS 7121-1987 using a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001). The melting point of a mixture of indium and zinc was used for temperature correction of the detection part of this apparatus, and the heat of fusion of indium was used for correction of heat quantity. The sample was put in an aluminum pan, an aluminum pan containing the sample and an empty aluminum pan for control were set, and the measurement was performed at a heating rate of 10 ° C./min.
Regarding the endothermic peak temperature, among the endothermic peaks of the DSC curve obtained by measurement, the peak temperature of the endothermic peak was determined as the endothermic curve peak temperature by the suggested scanning calorimeter.
Moreover, about the glass transition temperature, it was set as the glass transition temperature with the temperature of the intersection of the extended line of the base line in the endothermic part of the DSC curve obtained by the measurement, and the rising line.

<Measurement of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) (polystyrene conversion) of the polyester resin was measured using GPC (manufactured by Tosoh Corporation: HLC-8120). The column used was TSKgel SuperHM-M (15 cm) manufactured by Tosoh Corporation, and the GPC spectrum was measured using a THF solvent. The molecular weight of the polyester resin was calculated using a molecular weight calibration curve created with a monodisperse polystyrene standard sample.

<Calculation of average circularity>
For measurement of the average circularity of the toner, FPIA3000 (manufactured by Sysmex) was used. A toner dispersion for measurement was prepared as follows. First, 30 ml of ion-exchanged water was placed in a 100 ml beaker, and 5 drops of a 20% aqueous solution of a surfactant (sodium dodecylbenzenesulfonate) was added dropwise thereto as a dispersant. 20 mg of toner was put in this liquid, and ultrasonic dispersion was performed for 3 minutes to prepare a dispersion. The average circularity was calculated by measuring this dispersion using FPIA 3000 and measuring 4,500.

<Measurement method of toner volume average particle size>
Using a Coulter Multisizer II (manufactured by Beckman Coulter, Inc.) measuring device, the volume average particle diameter of the toner was measured. As the electrolytic solution, ISOTON-II (manufactured by Beckman Coulter, Inc.) was used.
As a measurement method, 0.5 mg of a measurement sample was added to 2 ml of a 5% aqueous solution of a surfactant (sodium dodecylbenzenesulfonate) as a dispersant, and this was added to 100 ml of the electrolytic solution. The electrolyte solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and with the Coulter Multisizer II, an aperture having an aperture diameter of 100 μm is used. The particle size distribution of the range of particles was measured. The number of particles measured is 50,000. For the measured particle size distribution, a cumulative distribution was drawn from the smaller diameter side with respect to the divided particle size range (channel), and the particle size at 50% cumulative was defined as the volume average particle size.

<Measuring method of average particle diameter of resin particles / release agent particles / pigment particles>
Using a laser diffraction particle size distribution analyzer (LA-700: manufactured by HORIBA, Ltd.), the volume average particle diameter of resin particles, release agent particles, and pigment particles was measured.
As a measuring method, a sample in a dispersion was prepared so as to have a solid content of about 2 g, and ion exchange water was added thereto to make about 40 ml. This was put into the cell until an appropriate concentration was reached, waited for 2 minutes, and measured when the concentration in the cell became almost stable.
The volume average particle diameter of each obtained channel was accumulated from the smaller volume average particle diameter, and the volume average particle diameter was determined to be 50%.

(Production of toner)
<Synthesis of polyester resin>
In a heat-dried two-necked flask, 80 mol parts of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 10 mol parts of ethylene glycol, 10 mol parts of cyclohexanediol, and terephthalic acid After 80 parts by mole, 10 parts by mole of isophthalic acid, and 10 parts by mole of n-dodecenyl succinic acid, dibutyltin oxide is added as a catalyst, nitrogen gas is introduced into the container, and the temperature is raised in an inert atmosphere. A copolycondensation reaction was performed at 150 to 230 ° C. for about 12 hours, and then the pressure was gradually reduced at 210 to 250 ° C. to synthesize polyester resin (1).
The weight average molecular weight (Mw) of the obtained polyester resin was 17,100. Moreover, the acid value of the polyester resin was 12.5 mgKOH / g.
Furthermore, the glass transition temperature of the polyester resin was measured using a differential scanning calorimeter (DSC) and obtained by analyzing according to JIS standards (see JIS K-7121).
As a result, a stepwise endothermic change was observed without showing a clear peak. The glass transition temperature (Tg) at the midpoint of the stepwise endothermic change was 58 ° C.

<Preparation of dispersion>
[Preparation of polyester resin dispersion]
-Polyester tree: 100 parts by weight-Ethyl acetate: 70 parts by weight-Isopropyl alcohol: 15 parts by weight A mixed solvent of ethyl acetate and isopropyl alcohol is added to a separable flask, and the resin is gradually added thereto. The mixture was stirred with a three-one motor and completely dissolved to obtain an oil phase.
To this stirred oil phase, a 10% by weight aqueous ammonia solution is gradually added dropwise with a dropper so that the total amount becomes 3 parts by weight, and 230 parts by weight of ion-exchanged water is gradually added dropwise at a rate of 10 ml / min. Phase-emulsification was performed, and the solvent was removed while the pressure was reduced with an evaporator to obtain a “polyester resin dispersion” containing “polyester resin”. The volume average particle diameter of the resin particles dispersed in this dispersion was 180 nm. The resin particle concentration of the dispersion was adjusted to 20% by weight with ion exchange water.

[Preparation of styrene acrylic resin particle dispersion]
Styrene (Wako Pure Chemical Industries, Ltd.): 325 parts by weight n-Butyl acrylate (Mitsubishi Chemical Corporation): 75 parts by weight β-carboxyethyl acrylate (Rhodia Nikka Co., Ltd.): 9 1 part by weight decanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.): 1.5 parts by weight dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.): 2.7 parts by weight In order to prepare a solution by dissolving, a surfactant solution in which 4 parts by weight of an anionic surfactant (Dow Fax 2A1 manufactured by Dow Chemical Co., Ltd.) was dissolved in 550 parts by weight of ion-exchanged water was placed in a flask. 413.2 parts by weight of the solution was added, dispersed and emulsified, and 50 parts by weight of ion-exchanged water in which 6 g of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes. Next, after sufficiently replacing the system with nitrogen, the emulsion solution in the flask is heated with stirring in an oil bath until the system reaches 70 ° C., and emulsion polymerization is continued for 5 hours to disperse the styrene acrylic resin particles. A liquid was obtained. When the styrene acrylic resin particles were separated from the styrene acrylic resin particle dispersion and examined for physical properties, the center diameter was 200 nm, the solid content in the dispersion was 41% by weight, the glass transition temperature (Tg) was 51.7 ° C., weight The average molecular weight (Mw) was 33,000.

[Preparation of release agent dispersion 1]
・ Paraffin wax (Nippon Seiwa Co., Ltd., FNP92, melting point 92 ° C.): 45 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 5 parts ・ Ion-exchanged water: 200 parts The above was mixed, heated to 95 ° C., and dispersed using a homogenizer (manufactured by IKA, Ultra Turrax T50). Thereafter, dispersion treatment was performed using a Menton Gorin high-pressure homogenizer (Gorin) to prepare a release agent dispersion 1 (solid content concentration: 20%) in which the release agent was dispersed. The volume average particle size of the release agent particles was 0.19 μm.

[Preparation of release agent dispersion 2]
・ Polyethylene wax (Baker Petrolite, POLYWAX725, melting point 103 ° C.): 45 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 5 parts ・ Ion-exchanged water: 200 parts or more Then, it was heated to 120 ° C. and dispersed using a homogenizer (manufactured by IKA, Ultra Turrax T50). Thereafter, dispersion treatment was performed using a Manton Gorin high-pressure homogenizer (Gorin Co., Ltd.) to prepare a release agent dispersion 2 (solid content concentration: 20%) in which the release agent was dispersed. The volume average particle size of the release agent particles was 0.23 μm.

(Preparation of colorant dispersion)
Cyan pigment (Daiichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)): 1,000 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R): 15 parts Exchange water: 9,000 parts or more were mixed and dissolved, and dispersed for 10 minutes with a homogenizer (IKA Ultra Tarrax) to obtain a colorant dispersion having a center particle size of 0.16 nm and a solid content of 20%.

<Creation of carrier>
100% of ferrite particles (manufactured by Powdertech Co., Ltd., average particle size 50 μm) and polymethyl methacrylate resin (manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight 95,000, weight average molecular weight 10,000 or less) ) Put 1.5 parts in a pressure kneader together with 500 parts of toluene, stir and mix at room temperature for 15 minutes, then elevate the temperature to 70 ° C. while mixing under reduced pressure to distill off the toluene, then cool down, and cool to a 105 μm sieve. To obtain a resin-coated ferrite carrier.

(Production of toner)
<Example 1: Production of toner (1)>
Polyester resin dispersion liquid: 267 parts Colorant dispersion liquid: 25 parts Release agent dispersion liquid 1:40 parts Anionic surfactant (Taika Power BN2060 manufactured by Teika Co., Ltd.): 2.0 parts The mixture was placed in a 2 L cylindrical stainless steel container, and 12 parts of 0.3 M nitric acid aqueous solution was added to adjust the pH to 2.7.
Next, 100 parts of an aqueous 10% aluminum sulfate solution was added dropwise as a flocculant while applying a shearing force at 1,000 rpm with Ultraturrax (manufactured by IKA Japan). In addition, since the viscosity of the raw material mixture increased during the dropping of the flocculant, the dropping speed was reduced when the viscosity increased, and care was taken so that the flocculant was not biased to one place. When the dropping of the flocculant was completed, the number of rotations was further increased to 6,000 rpm and the mixture was stirred for 5 minutes to sufficiently mix the flocculant and the raw material mixture.
Next, the raw material mixture was stirred at 550 rpm to 650 rpm while being heated to 35 ° C. with a mantle heater. After stirring for 60 minutes, after confirming that the primary particle diameter was stably formed using Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter, Inc.), 0.5 ° C. was used to grow aggregated particles. The temperature was raised to 45 ° C. at a rate of 1 minute. The growth of the agglomerated particles is confirmed at any time using Multisizer II. The agglomeration temperature and the number of rotations of stirring are changed depending on the agglomeration speed.

On the other hand, for coating aggregated particles, 190 parts of polyester resin dispersion (1) was added with 38 parts of ion-exchanged water and mixed to prepare a resin particle dispersion for coating prepared in advance to pH 2.7. When the aggregated particles grew to 5.8 μm in the aggregation step, the coating resin particle dispersion was added and held for 10 minutes with stirring. Thereafter, in order to stop the growth of the coated aggregated particles (adhered particles), a 1M aqueous sodium hydroxide solution was added to control the pH of the raw material mixture to 8.0.
Next, in order to fuse the aggregated particles, the temperature was raised to 92 ° C. at a temperature raising rate of 1 ° C./min while controlling the pH to 8.0. When the temperature reached 92 ° C., 20 parts of a 0.3M nitric acid aqueous solution was added, and the aggregated particles were fused while slowly cooling at 1.3 ° C./min for 5 minutes. Until cooled. Thereafter, filtration was performed, and re-dispersion in 3 liters of ion exchange water and solid-liquid separation by Nutsche suction filtration were repeated 6 times to obtain a wet cake. Next, vacuum drying was performed for 12 hours to obtain toner base particles (1) having an average volume particle diameter of 6.0 μm and an average circularity of 0.966.

  Next, 1.5 parts by weight of hydrophobic silica (manufactured by Cabot, TS720) was added to 50 parts by weight of the toner base particles, and blended by a sample mill to obtain an externally added toner. Next, the externally added toner and the resin-coated ferrite carrier were mixed to prepare a developer having a toner concentration of 7% by weight.

<Production of Toner (2)>
Similar to Toner (1) except that 5 minutes slow cooling at 1.3 ° C./minute is changed to 5 minutes slow cooling at 1.0 ° C./minute and the temperature drop rate is changed to 15 ° C./minute. Toner (2) was produced. Toner base particles (2) had an average volume particle size of 6.1 μm and an average circularity of 0.968. Externally added toner and developer were obtained in the same manner as in toner (1).

<Manufacture of toner (3)>
Toner (3) was produced in the same manner as toner (1), except that the slow cooling at 1.3 ° C./min for 5 minutes was changed to the slow cooling at 1.5 ° C./min for 5 minutes. Toner base particles (3) had an average volume particle size of 6.0 μm and an average circularity of 0.965. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (4)>
Toner (4) was produced in the same manner as Toner (1), except that slow cooling for 5 minutes at 1.3 ° C / min was changed to slow cooling for 10 minutes at 1.0 ° C / min. Toner base particles (4) had an average volume particle size of 6.0 μm and an average circularity of 0.965. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (5)>
Similar to Toner (1) except that 5 minutes slow cooling at 1.3 ° C / minute was changed to 3 minutes slow cooling at 1.0 ° C / minute and the temperature drop rate was changed to 20 ° C / minute. Toner (5) was produced. Toner base particles (5) had an average volume particle size of 6.1 μm and an average circularity of 0.972. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (6)>
Toner (6) was produced in the same manner as Toner (1), except that the slow cooling for 5 minutes at 1.3 ° C / min was changed to the slow cooling for 3 minutes at 1.5 ° C / min. Toner base particles (6) had an average volume particle size of 6.2 μm and an average circularity of 0.968. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (7)>
Toner (7) was produced in the same manner as Toner (1), except that the slow cooling for 5 minutes at 1.3 ° C / min was changed to the slow cooling for 3 minutes at 3.0 ° C / min. Toner base particles (7) had an average volume particle size of 6.1 μm and an average circularity of 0.966. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (8)>
Toner (8) was produced in the same manner as Toner (1), except that slow cooling for 5 minutes at 1.3 ° C / min was changed to slow cooling for 5 minutes at 0.7 ° C / min. Toner base particles (8) had an average volume particle size of 6.0 μm and an average circularity of 0.969. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (9)>
A toner (9) was produced in the same manner as the toner (1) except that the slow cooling for 5 minutes at 1.3 ° C./min was changed to the slow cooling for 10 minutes at 0.7 ° C./min. Toner base particles (9) had an average volume particle size of 6.2 μm and an average circularity of 0.965. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (10)>
A toner (10) was produced in the same manner as the toner (1) except that the slow cooling for 5 minutes at 1.3 ° C / min was changed to the slow cooling for 10 minutes at 0.5 ° C / min. Toner base particles (10) had an average volume particle size of 6.0 μm and an average circularity of 0.972. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (11)>
Toner (11) was produced in the same manner as Toner (1), except that slow cooling for 5 minutes at 1.3 ° C / min was changed to slow cooling for 20 minutes at 0.5 ° C / min. Toner base particles (11) had an average volume particle size of 6.1 μm and an average circularity of 0.965. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (12)>
Similar to Toner (1) except that 5 minutes slow cooling at 1.3 ° C./min was changed to 1 minute slow cooling at 3.0 ° C./min and the temperature drop rate was changed to 25 ° C./min. Toner (12) was produced. Toner base particles (12) had an average volume particle size of 6.1 μm and an average circularity of 0.970. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (13)>
Toner (13) was produced in the same manner as Toner (1), except that slow cooling for 5 minutes at 1.3 ° C / min was changed to slow cooling for 1 minute at 5.0 ° C / min. Toner base particles (13) had an average volume particle size of 6.0 μm and an average circularity of 0.968. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (14)>
A toner (14) was produced in the same manner as the toner (1) except that the slow cooling for 5 minutes at 1.3 ° C / min was changed to the slow cooling for 10 minutes at 1.3 ° C / min. Toner base particles (14) had an average volume particle size of 6.1 μm and an average circularity of 0.962. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (15)>
Toner (15) was produced in the same manner as Toner (1), except that slow cooling at 1.3 ° C / min for 5 minutes was changed to slow cooling at 1.0 ° C / min for 15 minutes. Toner base particles (15) had an average volume particle size of 6.2 μm and an average circularity of 0.961. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (16)>
Toner (16) was produced in the same manner as Toner (1), except that slow cooling at 1.3 ° C / min for 5 minutes was changed to slow cooling at 1.5 ° C / min for 10 minutes. Toner base particles (16) had an average volume particle size of 6.0 μm and an average circularity of 0.962. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (17)>
Toner (17) was produced in the same manner as Toner (1), except that slow cooling at 1.3 ° C / min for 5 minutes was changed to slow cooling at 0.7 ° C / min for 15 minutes. Toner base particles (17) had an average volume particle size of 6.0 μm and an average circularity of 0.962. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (18)>
A toner (18) was produced in the same manner as the toner (1) except that the slow cooling at 1.3 ° C./min for 5 minutes was changed to 0.7 ° C./min for 20 minutes. Toner base particles (18) had an average volume particle size of 6.1 μm and an average circularity of 0.959. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (19)>
A toner (19) was produced in the same manner as the toner (1) except that the slow cooling at 1.3 ° C / min for 5 minutes was changed to 0.7 ° C / min for 3 minutes. Toner base particles (19) had an average volume particle size of 6.2 μm and an average circularity of 0.977. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (20)>
A toner (20) was produced in the same manner as the toner (1) except that the slow cooling at 1.3 ° C / min for 5 minutes was changed to 1.0 ° C / min for 1 minute. Toner base particles (20) had an average volume particle size of 6.1 μm and an average circularity of 0.977. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (21)>
Toner (21) was produced in the same manner as Toner (1), except that slow cooling for 5 minutes at 1.3 ° C / min was changed to slow cooling for 1 minute at 1.5 ° C / min. Toner base particles (21) had an average volume particle size of 6.1 μm and an average circularity of 0.976. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (22)>
A toner (22) was produced in the same manner as the toner (1) except that the slow cooling at 1.3 ° C / min for 5 minutes was changed to the slow cooling at 3.0 ° C / min for 5 minutes. Toner base particles (22) had an average volume particle size of 6.3 μm and an average circularity of 0.962. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (23)>
A toner (23) was produced in the same manner as the toner (1) except that the slow cooling for 5 minutes at 1.3 ° C / min was changed to the slow cooling for 3 minutes at 5.0 ° C / min. Toner base particles (23) had an average volume particle size of 6.0 μm and an average circularity of 0.963. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (24)>
A toner (24) was produced in the same manner as the toner (1) except that the slow cooling at 1.3 ° C / min for 5 minutes was changed to the slow cooling at 0.5 ° C / min for 5 minutes. Toner base particles (24) had an average volume particle size of 6.2 μm and an average circularity of 0.976. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (25)>
Toner (25) was produced in the same manner as Toner (1), except that slow cooling for 5 minutes at 1.3 ° C / min was changed to slow cooling for 22 minutes at 0.5 ° C / min. Toner base particles (25) had an average volume particle size of 6.0 μm and an average circularity of 0.962. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (26)>
Toner (26) was produced in the same manner as Toner (1), except that slow cooling for 5 minutes at 1.3 ° C / min was changed to slow cooling for 20 minutes at 0.2 ° C / min. Toner base particles (26) had an average volume particle size of 6.1 μm and an average circularity of 0.965. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (27)>
Toner (27) was produced in the same manner as Toner (1), except that slow cooling at 1.3 ° C./min for 5 minutes was changed to slow cooling at 6 ° C./min for 1 minute. Toner base particles (27) had an average volume particle size of 6.1 μm and an average circularity of 0.967. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (28)>
Toner (28) was produced in the same manner as Toner (1), except that slow cooling at 1.3 ° C / min for 5 minutes was changed to slow cooling at 5.0 ° C / min for 0.5 minutes. Toner base particles (28) had an average volume particle size of 6.3 μm and an average circularity of 0.979. Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (29)>
Aggregated particles were formed in the same manner as in Example 1, and the temperature was raised to 95 ° C. in order to fuse the aggregated particles.
When 95 ° C. is reached, 7 parts of 0.3M nitric acid aqueous solution is added, and the aggregated particles are fused while slowly cooling at 0.5 ° C./min for 20 minutes, then to 40 ° C. at a temperature decrease rate of 10 ° C./min. Cooled down. Thereafter, filtration was performed, and re-dispersion in ion-exchanged water and solid-liquid separation by Nutsche suction filtration were repeated 6 times to obtain a wet cake. Next, vacuum drying was performed for 12 hours to obtain toner base particles (29) having an average volume particle diameter of 5.8 μm and an average circularity of 0.964.
Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (30)>
Aggregated particles were formed in the same manner as in Example 1, and the temperature was raised to 87 ° C. in order to fuse the aggregated particles.
When the temperature reached 87 ° C., 30 parts of a 0.3M nitric acid aqueous solution was added, and the aggregated particles were fused while gradually cooling at 5 ° C./min for 1 minute, and then cooled to 40 ° C. at a temperature decrease rate of 8 ° C./min. . Thereafter, filtration was performed, and re-dispersion in ion-exchanged water and solid-liquid separation by Nutsche suction filtration were repeated 6 times to obtain a wet cake. Next, vacuum drying was performed for 12 hours to obtain toner base particles (30) having an average volume particle size of 6.1 μm and an average circularity of 0.963.
Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (31)>
Aggregated particles were formed in the same manner as in Example 1, and the temperature was raised to 89 ° C. in order to fuse the aggregated particles.
When the temperature reached 89 ° C., 30 parts of a 0.3 M nitric acid aqueous solution was added, and the aggregated particles were fused while slowly cooling at 3 ° C./min for 1 minute, and then cooled to 40 ° C. at a temperature decrease rate of 10 ° C./min. . Thereafter, filtration was performed, and re-dispersion in ion-exchanged water and solid-liquid separation by Nutsche suction filtration were repeated 6 times to obtain a wet cake. Next, vacuum drying was performed for 12 hours to obtain toner base particles (31) having an average volume particle size of 6.0 μm and an average circularity of 0.966.
Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (32)>
Aggregated particles were formed in the same manner as in Example 1 except that the release agent dispersion 2 was used instead of the release agent dispersion 1, and the temperature was raised to 99 ° C. in order to fuse the aggregated particles.
When the temperature reached 89 ° C., 12 parts of 0.3 M nitric acid aqueous solution was added, and the aggregated particles were fused while slowly cooling at 1 ° C./min for 5 minutes, and then cooled to 40 ° C. at a temperature decrease rate of 28 ° C./min. . Thereafter, filtration was performed, and re-dispersion in ion-exchanged water and solid-liquid separation by Nutsche suction filtration were repeated 6 times to obtain a wet cake. Next, vacuum drying was performed for 12 hours to obtain toner base particles (32) having an average volume particle diameter of 5.9 μm and an average circularity of 0.967.
Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (33)>
-Styrene acrylic resin particle dispersion: 267 parts-Colorant dispersion: 25 parts-Release agent dispersion: 1:40 parts-Anionic surfactant (Taika PowerBN2060, manufactured by Teika Co., Ltd.): 2.0 parts Was put into a cylindrical stainless steel container, and 100 parts of 10% aqueous solution of aluminum sulfate was added dropwise as a flocculant while applying a shearing force at 1,000 rpm with Ultraturrax (manufactured by IKA Japan). In addition, since the viscosity of the raw material mixture increased during the dropping of the flocculant, the dropping speed was reduced when the viscosity increased, and care was taken so that the flocculant was not biased to one place. When the dropping of the flocculant was completed, the number of rotations was further increased to 6,000 rpm and the mixture was stirred for 5 minutes to sufficiently mix the flocculant and the raw material mixture.
Next, the raw material mixture was stirred at 550 rpm to 650 rpm while being heated to 40 ° C. with a mantle heater. After stirring for 60 minutes, after confirming that the primary particle diameter was stably formed using Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter, Inc.), 0.5 ° C. was used to grow aggregated particles. The temperature was raised to 48 ° C. at a rate of 1 minute. The growth of the agglomerated particles is confirmed at any time using Multisizer II. The agglomeration temperature and the number of rotations of stirring are changed depending on the agglomeration speed.
On the other hand, for coating aggregated particles, 38 parts of ion-exchanged water was added to 190 parts of styrene acrylic resin particle dispersion and mixed. When the aggregated particles grew to 5.8 μm in the aggregation step, the coating resin particle dispersion was added and held for 10 minutes with stirring. Thereafter, in order to stop the growth of the coated aggregated particles (adherent particles), a 1M aqueous sodium hydroxide solution was added to control the pH of the raw material mixture to 7.0.
Next, in order to fuse the aggregated particles, the temperature was raised to 92 ° C. at a temperature raising rate of 1 ° C./min while controlling the pH to 8.0. When the temperature reached 92 ° C., 30 parts of a 0.3M nitric acid aqueous solution was added, and the aggregated particles were fused while slowly cooling at 1 ° C./min for 5 minutes, and then cooled to 40 ° C. at a temperature decrease rate of 10 ° C./min. did. Thereafter, filtration was performed, and re-dispersion in 3 liters of ion exchange water and solid-liquid separation by Nutsche suction filtration were repeated 6 times to obtain a wet cake. Next, vacuum drying was performed for 12 hours to obtain toner base particles (33) having an average volume particle size of 6.0 μm and an average circularity of 0.964.
Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (34)>
Aggregated particles were formed in the same manner as in Example 1, and the temperature was raised to 87 ° C. in order to fuse the aggregated particles.
When the temperature reached 87 ° C., 23 parts of 0.3 M nitric acid aqueous solution was added, and the aggregated particles were fused while slowly cooling at 0.5 ° C./min for 3 minutes. Cooled down. Thereafter, filtration was performed, and re-dispersion in ion-exchanged water and solid-liquid separation by Nutsche suction filtration were repeated 6 times to obtain a wet cake. Next, vacuum drying was performed for 12 hours to obtain toner base particles (34) having an average volume particle size of 5.8 μm and an average circularity of 0.964.
Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (35)>
Aggregated particles were formed in the same manner as in Example 1, and the temperature was raised to 99 ° C. in order to fuse the aggregated particles. When 99 ° C. was reached, 12 parts of 0.3M nitric acid aqueous solution was added, and the aggregated particles were fused while slowly cooling at 1 ° C./min for 5 minutes. . Thereafter, filtration was performed, and re-dispersion in ion-exchanged water and solid-liquid separation by Nutsche suction filtration were repeated 6 times to obtain a wet cake. Next, vacuum drying was performed for 12 hours to obtain toner mother particles (35) having an average volume particle size of 5.7 μm and an average circularity of 0.968.
Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (36)>
Aggregated particles were formed in the same manner as in Example 1, and the temperature was raised to 83 ° C. in order to fuse the aggregated particles. When the temperature reached 83 ° C., 45 parts of a 0.3 M nitric acid aqueous solution was added, and the aggregated particles were fused while slowly cooling at 1 ° C./min for 5 minutes, and then cooled to 40 ° C. at a temperature decrease rate of 10 ° C./min. . Thereafter, filtration was performed, and re-dispersion in ion-exchanged water and solid-liquid separation by Nutsche suction filtration were repeated 6 times to obtain a wet cake. Next, vacuum drying was performed for 12 hours to obtain toner mother particles (36) having an average volume particle of 6.1 μm and an average circularity of 0.965.
Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (37)>
Aggregated particles were formed in the same manner as in Example 1, and the temperature was raised to 92 ° C. in order to fuse the aggregated particles. When the temperature reached 92 ° C., 18 parts of a 0.3 M nitric acid aqueous solution was added, and the aggregated particles were fused while slowly cooling at 1 ° C./min for 5 minutes, and then cooled to 40 ° C. at a temperature decrease rate of 1 ° C./min. . Thereafter, filtration was performed, and re-dispersion in ion-exchanged water and solid-liquid separation by Nutsche suction filtration were repeated 6 times to obtain a wet cake. Next, vacuum drying was performed for 12 hours to obtain toner mother particles (37) having an average volume particle of 6.1 μm and an average circularity of 0.990.
Externally added toner and developer were obtained in the same manner as in toner (1).

<Production of Toner (38)>
Aggregated particles were formed in the same manner as in Example 1, and the temperature was raised to 92 ° C. in order to fuse the aggregated particles. When the temperature reached 92 ° C., 20 parts of a 0.3M nitric acid aqueous solution was added, and the aggregated particles were fused while slowly cooling at 1 ° C./min for 5 minutes, and then cooled to 60 ° C. at a temperature decrease rate of 10 ° C./min. . Thereafter, filtration was performed, and re-dispersion in 3 liters of ion exchange water and solid-liquid separation by Nutsche suction filtration were repeated 6 times to obtain a wet cake. Next, vacuum drying was performed for 12 hours to obtain toner base particles (38) having an average volume particle of 6.0 μm and an average circularity of 0.962.
Externally added toner and developer were obtained in the same manner as in toner (1).

(Evaluation)
<Fixability evaluation>
For fixing evaluation, a modified machine of DocuCentreColor500 manufactured by Fuji Xerox was used. In this apparatus, a halogen lamp of 900 W is built in a heating roll as a heating means for the nip portion in the fixing machine, and the set fixing temperature of the fixing machine is variable in a range of 70 ° C. to 200 ° C. This fixing test is repeated for each toner while changing the fixing temperature from 70 ° C. to 200 ° C. in steps of 5 ° C., and the occurrence of offset is visually confirmed. did. The evaluation criteria are as follows. The results are shown in Table 1.
-Evaluation criteria-
A: Offset temperature is 190 ° C. or higher B: Offset generation temperature is 180 ° C. or higher and lower than 190 ° C. C: Offset generation temperature is 170 ° C. or higher and lower than 180 ° C. D: Offset temperature is lower than 170 ° C. There is no practical problem.

<Powder flowability evaluation>
The toner obtained by the above method was left in an environment of 55 ° C./50% RH for 24 hours.
Thereafter, 2 g of the toner is weighed, placed on a sieve having an opening of 32 μm, vibrated for 30 seconds, the amount remaining on the sieve is weighed, the degree of aggregation of the toner is calculated from the following formula, and the powder fluidity is evaluated. did.
Formula: Toner aggregation degree (%) = (Amount of toner remaining on sieve (g) / 2 g) × 100
The evaluation criteria are as follows. The results are shown in Table 1.
-Evaluation criteria-
A: Less than 3% B: 3% or more and less than 6% C: 6% or more and less than 10% D: 10% or more If the evaluation is A to C, there is no practical problem.

Claims (9)

An aggregating step for producing aggregated particles containing at least binder resin particles and release agent particles by a wet granulation method;
A heating step of heating to the endothermic curve peak temperature ± 5 ° C. of the release agent;
A coalescing process for fusing and coalescing the agglomerated particles,
Slow cooling satisfying the following formulas (1) and (2), where the coalescence step is the temperature reached in the heating step immediately after the heating step , with the endothermic curve peak temperature ± 5 ° C. of the release agent as the cooling start temperature. A slow cooling step of cooling at a rate of V1 ° C./min for a slow cooling time T1 and a rapid cooling step of rapidly cooling to a glass transition temperature of the binder resin at a rate of 8 ° C./min or more in this order,
In the gradual cooling step , the cooling temperature, which is the lowered temperature (V1 × T1) by cooling at the gradual cooling time T1 minutes at the gradual cooling rate V1 ° C./min, is 3.0 ° C. or higher and 10.0 ° C. or lower. A method for producing a toner for developing an electrostatic charge image.
0.5 ≦ V1 ≦ 5.0 (1)
1 ≦ T1 ≦ 20 (2)   2. The electrostatic charge image development according to claim 1, wherein in the heating step and the slow cooling step, the time during which the temperature of the system falls within the range of the endothermic curve peak temperature ± 5 ° C. of the release agent is 0 minutes to 60 minutes. Of manufacturing toner.   2. The electrostatic charge image development according to claim 1, wherein in the heating step and the slow cooling step, the time during which the temperature of the system falls within the range of the endothermic curve peak temperature ± 5 ° C. of the release agent is 0 to 30 minutes. Of manufacturing toner.   2. The electrostatic charge image development according to claim 1, wherein in the heating step and the slow cooling step, the time during which the temperature of the system falls within the range of the endothermic curve peak temperature ± 5 ° C. of the release agent is 0 to 15 minutes. Of manufacturing toner.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein the total process time is 2 minutes to 85 minutes.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 5, wherein the endothermic curve peak temperature of the release agent is 60 ° C to 100 ° C.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 6, wherein the binder resin has a glass transition temperature of 50C to 70C. The electrostatic charge image according to claim 1, wherein the endothermic curve peak temperature of the release agent is Tm ° C. and the glass transition temperature of the binder resin is Tg ° C., and the following formula (3) is satisfied. A method for producing a developing toner.
10 ≦ Tm−Tg ≦ 50 (3) A latent image forming step for forming an electrostatic latent image on the surface of the image carrier;
A developing step of developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner to form a toner image;
A transfer step of transferring the toner image to the surface of the transfer target; and
A fixing step of fixing the toner image transferred to the surface of the transfer material,
The toner for developing an electrostatic charge image obtained by the method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 8 as a developer , or the toner according to any one of claims 1 to 8. An image forming method using an electrostatic charge image developer, comprising: an electrostatic charge image developing toner obtained by a method for producing an electrostatic charge image developing toner; and a carrier .