JPH11327201A - Toner for developing electrostatic charge image, its reduction, electrostatic charge image developer and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for developing an electrostatic charge image inhibiting the liberation of a releasing agent from the toner, excellent in fixability, electrostatic chargeability and powder characteristics, simultaneously satisfying such various characteristics as electrostatic chargeability, developing performance, transferability, fixability and cleanability and excellent particularly in image smoothness, transparency, color mixing property and color forming property, to provide a method for producing the toner, to obtain an electrostatic charge image developer and to provide an image forming method. SOLUTION: Relating to a toner for developing an electrostatic charge image contg. a resin, a colorant and a releasing agent, the releasing agent is disposed as a releasing agent layer along the surface of the toner. A dispersion of fine resin particles is mixed with a dispersion of a colorant to form aggregated particles. A dispersion of fine releasing agent particles is then added and mixed to stick the releasing agent particles to the surfaces of the aggregated particles. A dispersion of fine resin particles is further added and mixed to stick the fine resin particles to the surfaces of releasing agent layers on the aggregated particles. The resultant particles are heated to a temp. above the glass transition temp. of the fine resin particles to form a the objective toner particles by fusion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic image developing toner used for forming an image by electrophotography and the like, a method for producing the same, an electrostatic image developer, and an image forming method.

[0002]

2. Description of the Related Art Methods of visualizing image information via an electrostatic image, such as electrophotography, are currently widely used in various fields. In the electrophotographic method, an electrostatic image is developed on a photoreceptor through a charging step, an exposure step, and the like, and the electrostatic image is visualized through a transfer step, a fixing step, and the like.

[0003] Two-component developers containing toner particles and carrier particles and one-component developers containing only magnetic toner particles or non-magnetic toner particles are known as developers used in electrophotography. I have. The toner particles are usually manufactured by a kneading and pulverizing method. The kneading and pulverization method is a method in which a thermoplastic resin or the like is melt-kneaded with a pigment, a charge controlling agent, a release agent such as wax, and the like, and after cooling, the melt-kneaded material is finely pulverized.
This is a method of producing toner particles by classification. In addition, inorganic particles or organic particles may be added to the surface of the toner particles produced by the kneading and pulverizing method, if necessary, for the purpose of improving the fluidity and the cleaning property.

[0004] The toner particles produced by the kneading and pulverizing method are usually irregular in shape, and the surface composition cannot be adjusted uniformly. That is, the shape and surface composition of the toner particles slightly change depending on the pulverizability of the materials used, the conditions of the pulverization step, and the like, and it is difficult to intentionally control these. In particular, toner produced by a kneading and pulverization method using a material having high pulverizability is pulverized by receiving various shearing forces inside the developing machine,
It may be pulverized or its shape may change. In a two-component developer, finely divided toner particles adhere to the carrier surface,
Accelerates deterioration of developer charging performance. In addition, the one-component developer has a problem that the particle size distribution is enlarged, finely-divided toner particles are scattered, and the developing property is reduced due to a change in the toner shape, thereby causing a deterioration in image quality.

[0005] If the shape of the toner particles is irregular, even if a flow aid is added, the flowability of the toner particles cannot be sufficiently ensured. Further, inside the developing machine, the fine particles of the fluidity aid move to the concave portions of the toner particles due to shearing force,
There is a problem that, for example, the toner is buried inside the toner particles and the fluidity is reduced with time, so that the developing property, the transfer property, and the cleaning property are deteriorated. Further, if such a toner is collected in the cleaning process, returned to the developing device and reused, there is a problem that the image quality is easily deteriorated. In order to prevent these problems, it is conceivable to further increase the amount of the flow aid. However, when a large amount of the flow aid is used, black spots are generated on the photoreceptor or the flow aid is not used. There is a problem that fine particles are scattered.

On the other hand, in a toner to which a release agent such as wax is internally added, the release agent may move to and be exposed on the surface of the toner particles depending on the combination of the release agent and the thermoplastic resin. In particular, in the case of a toner in which a resin which is imparted with elasticity by a high molecular weight component and is hardly pulverized and a brittle wax such as polyethylene are combined, polyethylene is often exposed on the surface of the toner particles. A toner in which a release agent such as polyethylene is exposed on the surface is advantageous in terms of releasability at the time of fixing and cleaning property of untransferred toner on the surface of the photoreceptor.
The particles are detached from the surface of the toner particles by receiving a shearing force or the like in the developing machine, and easily migrate to a developing roll, a photoreceptor, a carrier, or the like and become contaminated. This contamination greatly reduces the reliability of the developer.

Therefore, in recent years, control of the shape and surface composition of the toner particles has been studied.
JP-A-3-282752 and JP-A-6-250439 propose an emulsion polymerization method. In this emulsion polymerization method, a resin fine particle dispersion is prepared by emulsion polymerization, while a colorant dispersion in which a colorant is dispersed in a solvent is prepared, and these are mixed to form aggregated particles corresponding to toner particles. ,
There is a method of obtaining toner particles by fusing by heating. In this method, the toner shape can be arbitrarily controlled from an irregular shape to a spherical shape by selecting a heating temperature.

However, according to the emulsion polymerization aggregation method, aggregated particles are formed in a uniform mixed state of fine resin particles and a colorant.
Due to the heat fusion, the composition becomes uniform from the inside of the toner particle toward the surface, and it is difficult to intentionally control the structure and composition of the toner particle surface. In particular, when a release agent is contained in the aggregated particles, the release agent is exposed on the surface of the fused toner particles to cause filming, or externally added to the toner surface for the purpose of imparting fluidity. The agent is coated with the release agent and buried inside the toner so that it cannot fulfill its purpose.

Further, a suspension polymerization method is proposed in JP-A-8-44111 and JP-A-8-286416. The suspension polymerization method is a method in which a polymerizable monomer is dispersed and suspended in an aqueous medium together with a colorant, a release agent, and the like, and then polymerized using the polymerizable monomer to obtain toner particles. According to the suspension polymerization method, toner particles having a multilayer structure in which, for example, wax as a release agent is coated with a binder resin can be obtained.

However, in this suspension polymerization method, it is necessary to adjust particles to an appropriate size in a suspended state. For this adjustment, it is necessary to stir the dispersion liquid at a high speed and at a high speed. However, it is generally very difficult to stir a liquid having a viscosity such as water uniformly at a high speed. If the mixing cannot be performed uniformly, the release agent is released, and a large amount of toner particles having a very small amount of the release agent or no toner at all are generated. As a result, the uneven distribution of the composition between the toner particles becomes remarkable, and it becomes impossible to sufficiently satisfy various characteristics such as fixing property and charging property required for the toner. At present, a technique for effectively preventing release of a release agent by a suspension polymerization method has not been established.

On the other hand, in recent years, there has been an increasing demand for higher image quality. In particular, in color image formation, in order to realize a highly fine image, it is strongly required to reduce the diameter of the toner and to make the particle diameter uniform. When an image is formed using a toner having a wide particle size distribution, the toner on the fine powder side contaminates a developing roll, a charging roll, a charging blade, a photoreceptor, a carrier, and the like, and scattering of the toner becomes remarkable. Therefore, it is difficult to simultaneously achieve high image quality and high reliability. In addition, such a toner having a wide particle size distribution naturally lowers the reliability of a system having a cleaning function, a toner recycling function, and the like.
In order to simultaneously achieve high image quality and high reliability, it is important to sharpen the particle size distribution of the toner and promote the reduction in the diameter and the uniformity of the particle size.

In order to satisfy the demand for higher image quality,
An important factor is to improve the fixability of the toner. In order to obtain sufficient toner fixing properties, it is necessary to expand the fixing temperature range. Conventionally, it is a general method to use a resin containing a plurality of types of resins having different molecular weights or a gel component as a binder resin to prevent offset on a high temperature side.

However, in the case of a color image in particular, if a resin containing plural kinds of resins having different molecular weights or a resin containing a gel component is used as a binder resin, the color mixing property of the fixed image, the smoothness of the image surface, and the transparency of the image are further improved. Properties are impaired, image quality is significantly degraded, especially when fixing images on film,
This effect is extremely large. Conversely, if the type of the resin is made one and the molecular weight is made constant or a resin containing no gel component is used, there are problems with the color mixing of the fixed image, the smoothness of the image surface, the transparency of the image, and the like. However, particularly when a large amount of a release agent is added, the viscosity of the toner is reduced and offset on the high temperature side is more likely to occur than before.

On the other hand, in forming a color image, when the toner is fixed on a paper surface or a film, it is necessary to improve the smoothness of the toner-fixed image to secure the color development and transparency of the image. For this reason, in the conventional method, it is general to maintain the releasing property and the smoothness of the fixing roll with respect to the toner by supplying an oil having a high releasing property such as silicone oil to the surface of the fixing roll. Was.

However, this method has a problem that the oil migrates to the paper surface or onto the film at the time of fixing, and the fixed image has a sticky feeling. In addition, when fixing is performed on paper, there is a problem that writing with a pen or the like becomes difficult on the paper on which the fixed image is formed because the oil reduces the surface energy of the paper. further,
When fixing on a film, there is a problem that the transparency of a fixed image is reduced by the oil remaining on the film.

Further, in the electrophotographic process, in order to stably maintain and exhibit the performance of the toner such as fluidity and chargeability under various mechanical stresses, it is necessary to expose a release agent to the surface of the toner particles. It needs to be suppressed. On the other hand, the release agent quickly oozes out to the toner particle surface when fixing the fixing roll, thereby increasing the releasability of the toner from the fixing roll. In consideration of the toner performance such as the above, it is desirable to suppress the use amount of the release agent and arrange the toner near the surface of the toner particles.

[0017]

SUMMARY OF THE INVENTION The present invention solves the problems of the conventional methods such as the kneading and pulverizing method, the suspension polymerization method and the emulsion polymerization agglutination method. An object of the present invention is to provide a manufacturing method, an electrostatic image developer and an image forming method.

A toner for developing an electrostatic image, which has excellent properties such as chargeability, developability, transferability, fixability, and cleaning properties, and is particularly excellent in smoothness, transparency, color mixing and color development in an image. Provided is an electrostatic image developer using an electrostatic image developing toner. A toner for developing an electrostatic charge image, which is excellent in fixability, chargeability, powder characteristics, and has high reliability while preventing exposure of the release agent to the toner surface and suppressing release of the release agent from the toner. Provided is an electrostatic image developer using a charge image developing toner. An electrostatic image developing toner suitable for a two-component electrostatic image developer having high transfer efficiency, low toner consumption, and long life.

It is an object of the present invention to provide a method for easily and simply producing a toner for developing an electrostatic image having the above-mentioned characteristics while keeping the amount of the releasing agent released extremely low. An image forming method for easily and easily forming a high-quality and highly reliable full-color image. Provided is an image forming method capable of obtaining high image quality in a so-called cleanerless system having no cleaning mechanism. Provided is an image forming method that is highly suitable for a so-called toner recycling system that reuses toner collected from a cleaner and that can obtain high image quality.

[0020]

The present invention has succeeded in solving the above problems by avoiding the following means. (1) An electrostatic image developing toner containing a resin, a colorant and a release agent, wherein the release agent is disposed in the toner as a release agent layer along the toner surface. Charge image developing toner. (2) The electrostatic image developing toner according to (1), wherein the core particles inside the release agent layer contain a resin, a colorant, and a release agent.

(3) The toner for developing an electrostatic image according to the above (1) or (2), wherein the surface of the release agent layer is coated with a resin. (4) The toner for developing an electrostatic image according to any one of (1) to (3), wherein a plurality of the release agent layers are arranged in the toner.

(5) The release agent layer has a thickness of 0.01 to 2.
The electrostatic image developing toner according to any one of the above (1) to (4), which is in a range of 0 μm. (6) The release agent layer is located between 0.01 and 3.0 from the toner surface.
The toner for developing an electrostatic image according to any one of the above (1) to (5), which is in a range of μm. (7) The content of the release agent is 0.5 to 0.5% of the toner weight.
(1) to (4), wherein the content is in the range of 50% by weight.
(6) The toner for developing an electrostatic image according to any one of the above (6).

(8) The shape factor SF1 of the toner is 100
≦ SF1 ≦ 140.
The toner for developing an electrostatic image according to any one of (1) to (7). (9) The electrostatic image developing toner according to any one of (1) to (8), wherein the toner has a volume average particle diameter (D ₅₀ ) in a range of 3 to 8 μm.

(10) Volume average particle size distribution index G of the toner
SDv (D _84V / D _16V) is an electrostatic image developing toner according to any one of above, wherein the at 1.26 or less (1) to (9).

(11) A dispersion of fine resin particles and a dispersion of colorant are mixed, and the fine resin particles and the colorant are aggregated to form aggregated particles. Added and mixed, the release agent fine particles were adhered to the surface of the aggregated particles, and further, a dispersion of resin fine particles was added and mixed, and the resin fine particles were adhered to the release agent layer surface of the aggregated particles. Thereafter, the electrostatic charge according to any one of (1) to (10), wherein the resin fine particles are heated to a temperature equal to or higher than the glass transition point to fuse and coalesce to form toner particles. A method for producing an image developing toner.

(12) The toner for developing an electrostatic image according to (11), wherein the aggregated particles are formed by making the polarity of the resin fine particle dispersion different from that of the colorant dispersion. Production method. (13) The (11) or (1) wherein the aggregated particles are formed by adding a surfactant having a polarity different from the polarity of the dispersion liquid obtained by mixing the resin fine particles and the colorant.
2) The method for producing a toner for developing an electrostatic image as described in 2).

(14) A release agent fine particle dispersion is adjusted to a polarity different from the polarity of the dispersion liquid in which the resin particles and the colorant are dispersed, and the release agent fine particle dispersion is dispersed in the aggregated particle dispersion. Adding to the liquid and mixing, wherein the release agent fine particles are attached to the surface of the aggregated particles (11)
(13) The method for producing a toner for developing an electrostatic image according to any one of (13) to (13). (15) The resin particles are dispersed in a solution containing an anionic surfactant, and the release agent particles are dispersed in a solution containing a cationic surfactant, wherein the (11) to (11) to ( 14. The method for producing a toner for developing an electrostatic image according to any one of 14).

(16) A dispersion of the resin fine particles and a dispersion of the colorant are mixed, and the resin fine particles and the colorant are aggregated using an inorganic metal salt having a charge of 2 or more to form aggregated particles. Forming, then adding and mixing a dispersion of release agent particles, adhering release agent particles to the surface of the aggregated particles, further adding and mixing a dispersion of resin particles, the aggregated particles After adhering the resin fine particles to the surface of the release agent layer, the resin particles are heated to a temperature equal to or higher than the glass transition point of the resin fine particles to fuse and coalesce, thereby forming toner particles. The method for producing a toner for developing an electrostatic image according to any one of (10) and (10). (17) The method for producing a toner for developing an electrostatic image according to (16), wherein the inorganic metal salt is a polymer.

(18) The dispersion of the release agent has an average particle size of 0.01 to 0.01 as measured by a scanning electron microscope (SEM).
The above (1), comprising a release agent of 2.0 μm.
1) The method for producing a toner for developing electrostatic images according to any one of 1) to 17). (19) the resin particles in the dispersion, the colorant and the average particle diameter of the release agent particles is 1μm or less
(11) The method for producing a toner for developing an electrostatic image according to any one of (18) to (18). (20) The method according to any one of (11) to (19), wherein the temperature at which the aggregated particles are fused is adjusted to a range of a temperature higher by 20 ° C. than the melting point Tm or the melting point of the release agent. The method for producing a toner for developing an electrostatic image according to the above.

(21) An electrostatic image developer containing a carrier and a toner, wherein the toner is the toner for developing an electrostatic image according to any one of (1) to (10). Electrostatic image developer. (22) The electrostatic image developer according to the above (21), wherein the carrier has a resin coating layer.

(23) a step of forming an electrostatic latent image on an electrostatic latent image carrier, a step of developing the electrostatic latent image with a developer on a developer carrier and forming a toner image, An image forming method including a transfer step of transferring an image onto a transfer body, and a cleaning step of removing an electrostatic image developing toner remaining on the electrostatic latent image carrier, wherein the developer is
An image forming method using the electrostatic image developer according to (21) or (22).

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The toner for developing an electrostatic image of the present invention is provided with a release agent layer near the toner surface and a resin coating on the toner surface, so that the toner is released when passing through a fixing roll. Facilitates the exudation of the release agent onto the toner surface, improves the anti-offset properties, and at the same time, reduces the amount of the release agent remaining inside the toner at the time of fixing, thereby avoiding the inconvenience caused by mixing the release agent into the toner image. In particular, it is possible to improve the transparency, color mixture, color development, smoothness, and the like of a color image. In addition, since the release agent is not substantially exposed on the toner surface before passing through the fixing roll, a large amount of the release agent can be added as compared with the kneading and pulverizing method, and the toner powder Body fluidity can be maintained. In addition, since the contamination of the carrier, the photoconductor and the like by the release agent can be avoided, the influence on the chargeability, the developability and the like can be suppressed. Further, since the colorant is mainly disposed on the aggregated particles corresponding to the core portion of the toner and is not exposed on the toner surface, it is possible to suppress the fluctuation of the charge of the toner due to the exposure of the colorant. When a plurality of colorants are used as described above, it is possible to prevent a difference in chargeability due to the colorants between toners.

Hereinafter, the toner for developing an electrostatic image of the present invention will be described in accordance with the manufacturing procedure. The method for producing a toner for developing an electrostatic image of the present invention is characterized in that a dispersion of resin fine particles obtained by dispersing at least resin fine particles and a dispersion of a colorant obtained by dispersing a colorant are mixed and colored with resin fine particles. To prepare a dispersion of aggregated particles for dispersing the aggregated particles (hereinafter sometimes referred to as “aggregation step of mother aggregated particles”). Is added and mixed, and the release agent is attached to the surface of the aggregated particles to form a release agent layer (hereinafter referred to as a “release agent attachment step”). Further, a dispersion liquid of resin fine particles or the like is added to adhere the resin fine particles for resin coating on the surface of the adhered particles (hereinafter, may be referred to as “adhesion step of resin fine particles for resin coating”). The dispersion of the obtained aggregated particles is subjected to glass transition of the resin fine particles. And coalescence of the adhered particles by heating at a temperature above to form toner particles (hereinafter sometimes referred to as "fusion step").

In the above-described method for producing a toner for developing an electrostatic image, a releasing agent dispersion may be added to the mother aggregated particle step to incorporate the release agent into the mother aggregated particles. A plurality of release agent layers may be arranged in the toner by repeating the above-described step of attaching the release agent and the step of attaching the resin fine particles for the resin film. Also,
It is also possible to change the composition of the layer by adding it to the aggregated particle dispersion while changing the mixing ratio of the fine particles dispersed when forming the adhesion layer.

In the step of aggregating the mother agglomerated particles and / or the step of adhering various fine particles, the type and amount of the ionic surfactant for adjusting the polarity of the dispersion liquid are selected to control the degree of agglutination and / or adhesion. can do. For example, by dispersing resin fine particles in a solution containing an anionic surfactant, dispersing a colorant in a solution containing a cationic surfactant, and by mixing both, the resin fine particles and the colorant are aggregated. Can be done.

The balance between the polarity and the amount of the ionic surfactant contained in the dispersion to be mixed is shifted in advance, and an ionic surfactant having a polarity and an amount that compensates for the shift in the balance is used. Aggregation and / or adhesion can also be performed by adding.

The aggregation of the mother aggregated particles is performed by a method in which a dispersion of resin fine particles having different polarities and a colorant dispersion are mixed to form aggregated particles, or a dispersion obtained by mixing resin fine particles and a colorant. A method of adding a surfactant having a polarity different from that of the dispersion to form aggregated particles can be employed.

In order to attach fine particles such as a release agent to the mother aggregated particles, the release agent fine particles previously adjusted to have a different polarity from the dispersion liquid of the mother aggregated particles composed of the resin fine particles and the colorant are used. Fine particles such as a release agent can be attached to the surface of the mother aggregated particles by adding and mixing the dispersion liquid, and a layer of the fine particle component can be formed through a subsequent fusion step.

In the fusion step, although the resin and the release agent in the final adhered particles are melted, the resin particles and the release agent have low or no compatibility with each other. The release agent fine particle layer existing near the surface in the adhered particles fuses with each other to form a release agent layer in the toner. At that time, the colorant particles are taken into the fused body of the resin fine particles in the mother aggregated particles to form toner particles for electrostatic image development.

In the attaching step, a fine particle dispersion such as a release agent is added to the mother aggregated particle dispersion, and if necessary, repeated two or more times to add the fine particles uniformly to the surface of the mother aggregated particles. Further, a resin fine particle dispersion for a resin coating is additionally mixed to adhere resin fine particles to the surface of the adhered particles, and the adhesion of the fine particles is formed by hetero-aggregation or the like. In the fusion step, the resin fine particles and the release agent in the adhered particles are both melted, but generally the resin fine particles and the release agent have low compatibility or are not compatible at all. A release agent layer is formed on the surface of a core portion composed of a resin and a coloring agent corresponding to the aggregated particles, and a resin film is further formed thereon, thereby forming toner particles for electrostatic image development as a whole.

Another method for producing a toner for developing an electrostatic image of the present invention is the method of producing a toner for developing an electrostatic image described above, wherein, in the step of aggregating the mother aggregated particles, an inorganic material having at least two charges is used as an aggregating means. The method is characterized in that a polymer of a metal salt is used, and the other steps are a method for forming toner particles by employing the same method as the above-mentioned method for producing a toner for developing an electrostatic image. According to this method, the preparation of the aggregated particles is facilitated, and the amount of the surfactant used can be significantly reduced. Therefore, it is possible to prevent the influence of the surfactant from being mixed into the toner on the chargeability of the toner. As a result, the charge control of the toner can be easily and reliably performed. Further, the washing step for removing the surfactant from the toner particles obtained in the fusing step can be greatly shortened.

Examples of the resin used in the resin fine particle dispersion include thermoplastic resins, and specifically, homopolymers of styrenes such as styrene, parachlorostyrene, α-methylstyrene, and the like. Copolymer (styrene-based resin); methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate,
Lauryl acrylate, 2-ethylhexyl acrylate,
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, and other homopolymers or copolymers (vinyl resins) of esters having a vinyl group; acrylonitrile, methacrylonitrile Homopolymers or copolymers of vinyl nitriles such as vinyl (vinyl resin); Homopolymers or copolymers of vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether (vinyl resin); vinyl methyl ketone, vinyl ethyl Homopolymers or copolymers of ketones and vinyl isopropenyl ketones (vinyl resins); Homopolymers or copolymers of olefins such as ethylene, propylene, butadiene and isoprene (olefin resins); epoxy resins and polyesters Resin, polyurethane resin, poly Bromide resin, cellulose resin, non-vinyl condensation resin of polyether resin and the like, and the like graft polymer of these non-vinyl condensation resin and a vinyl monomer and the like. These resins may be used alone or in combination of two or more.

Of these resins, vinyl resins are particularly preferred. A vinyl resin is advantageous in that a resin particle dispersion can be easily adjusted by emulsion polymerization or seed polymerization using an ionic surfactant or the like. Examples of the vinyl monomer include acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinylsulfonic acid,
Examples of the monomer include a raw material for a vinyl polymer acid or a vinyl polymer base such as ethyleneimine, vinylpyridine, and vinylamine. In the present invention, the resin fine particles preferably contain the vinyl monomer as a monomer component. In the present invention, among these vinyl monomers, a vinyl polymer acid is more preferable in terms of easiness of a reaction for forming a vinyl resin, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, and cinnamic acid. And a dissociable vinyl monomer having a carboxyl group as a dissociating group, such as fumaric acid, is particularly preferred in terms of controlling the degree of polymerization and the glass transition point.

The concentration of the dissociating group in the dissociable vinyl monomer is determined, for example, by dissolving particles such as toner particles from the surface as described in Polymer Latex Chemistry (Polymer Publishing Association). It can be determined by a quantification method or the like. In addition, the molecular weight and glass transition point of the resin from the particle surface to the inside can also be determined by the above method and the like.

The average particle size of the fine resin particles in the dispersion is 1
μm or less, preferably in the range of 0.01 to 1 μm is appropriate. When the average particle size exceeds 1 μm, the particle size distribution of toner particles obtained by aggregation and fusion is widened, or free particles are generated, which tends to cause deterioration in toner performance and reliability. In the present invention, by adjusting the average particle size to the above range, the dispersion of the resin fine particles in the aggregated particles can be improved, and the uneven distribution of the composition between the toner particles can be suppressed. There is an advantage that variation can be kept low. The average particle size can be measured by, for example, a laser diffraction type particle size distribution analyzer or a Coulter counter.

Examples of the coloring agent include carbon black, chrome yellow, Hansa yellow, benzidine yellow, slen yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliant carmine 3B, Brilliant Carmine 6B, Dupont Oil Red, Pyrazolone Red, Risor Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride,
Various pigments such as phthalocyanine blue, phthalocyanine green, malachite green oxalate; acridine, xanthene, azo, benzoquinone, azine, anthraquinone, dioxazine, thiazine, azomethine, indigo, thioindigo, phthalocyanine And aniline black, polymethine, triphenylmethane, diphenylmethane, thiazole and xanthene dyes. These colorants may be used alone or
Two or more kinds may be used in combination.

The colorant has an average particle size of 1 μm or less, preferably 0.5 μm, more preferably 0.01 to 0.5 μm.
Is appropriate. If the average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic charge image is widened, or free particles are easily generated, and the performance and reliability of the toner are liable to be reduced. In the present invention, by adjusting the average particle diameter to the above range, the dispersion of the colorant in the aggregated particles is improved, and the uneven distribution of the composition among the toner particles can be suppressed, and the performance and reliability of the toner can be improved. There is an advantage that variation can be reduced. And the average particle size is 0.5μ
m or less, the color developability, color reproducibility, O
HP permeability and the like can be further improved. The average particle size can be measured using, for example, a laser diffraction type particle size distribution analyzer. The content of the colorant in the aggregated particles is 50% by weight or less, preferably 2 to
A range of 40% by weight is suitable.

It is preferable that the release agent generally has poor compatibility with the binder resin of the toner. If a release agent having high compatibility with the binder resin is used, the release agent dissolves into the binder resin and promotes plasticization of the binder resin, lowers the viscosity of the toner during high-temperature fixing, and easily causes offset. . And
Part of the release agent particles existing near the toner surface due to plasticization of the binder resin move to the resin side of the toner center (core portion), and the effect of the release agent that can be exhibited only when present near the surface Or by plasticizing with the resin particles present on the toner surface, the glass transition point of the resin layer on the toner surface is lowered, and the fluidity of the toner is deteriorated. The release effect is related to the distance between the dispersion unit of the release agent contained in the toner particles and the distance from the toner surface. In general, the larger the dispersion unit of the release agent is, the longer the distance of the release agent is from the toner surface. The smaller the is, the greater the effect.

In the method for producing a toner for developing an electrostatic image of the present invention, since the aggregated particles are produced by aggregating the fine particles, the position of the release agent layer can be relatively easily controlled. At this time, even during the growth of the particle diameter of the aggregated particles, the position of the release agent present in the vicinity of the surface of the aggregated particles is maintained unchanged even during the aggregation because of the small stress.
Further, under the stress, even if the materials having high compatibility between the resin and the release agent are mutually compatible, the compatibility does not easily progress, so that the toner obtained by the method for producing the electrostatic image developing toner of the present invention may Can exhibit a sufficient release effect even if the release agent contained therein is highly compatible with the resin particles. As described above, the production method of the present invention is particularly advantageous because it can use a material that cannot be applied to the melt kneading method or the like since the stress is much smaller than the melt kneading method or the like.

Specific examples of the release agent include low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; silicones having a softening point upon heating; oleamide, erucamide, ricinoleamide, and the like.
Fatty acid amides such as stearic acid amide; plant waxes such as carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline Mineral and petroleum waxes such as wax and Fischer-Tropsch wax; ester waxes of higher fatty acids such as stearyl stearate and behenyl behenate and higher alcohols; butyl stearate, propyl oleate, monostearate glyceride, glyceride distearate; Ester waxes of higher fatty acids such as pentaerythritol tetrabehenate and unit prices or polyhydric lower alcohols;
Ester waxes comprising higher fatty acids such as diethylene glycol monostearate, dipropylene glycol distearate, diglyceride distearate, triglyceride tetrastearate and polyhydric alcohols; sorbitan higher fatty acid ester waxes such as sorbitan monostearate; Cholesteryl stearate and other cholesterol higher fatty acid ester waxes can be mentioned. These release agents may be used alone or in combination of two or more.

The melting point of the release agent is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher, from the viewpoint of ensuring the storage stability of the toner. In addition, from the viewpoint of securing the toner fixing property, the temperature is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and particularly preferably 130 ° C. or lower. When the melting point is lower than 30 ° C., the exudation of wax on the surface of the fixed image is liable to occur, and the fixed image becomes sticky. On the other hand, when the temperature exceeds 150 ° C., the release agent is hardly dissolved in the toner, so that the release effect is reduced.

In the present invention, since the location of the release agent is controlled near the surface of the toner, the content of the release agent in the toner can be suppressed to a small amount. The effect of can be fully exhibited. The content of the release agent in the toner is 0.1 to 50% by weight.
Is preferable, the range of 0.5 to 40% by weight is more preferable, and the range of 1 to 30% by weight is particularly preferable. When the content of the release agent is less than 0.1% by weight, the releasing effect is not sufficient, so that the toner adheres to the fixing roll at the time of high-temperature fixing, so-called offset tends to occur. The release agent sometimes released increases or the toner becomes brittle, and the toner particles are easily stirred by being stirred in the developing machine.

The average particle size of the release agent in the dispersion is preferably 2 μm or less, more preferably 0.1 to 2 μm. When the average particle size exceeds 2 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image is widened, or free particles are easily generated, and the performance and reliability of the toner are easily reduced. By adjusting the average particle diameter within the above range, uneven distribution of the composition between toner particles can be suppressed, and there is an advantage that variations in toner performance and reliability can be reduced. The average particle size can be measured using, for example, a laser diffraction type particle size distribution measuring device, a centrifugal type particle size distribution measuring device, or the like.

The waxes used as the release agent include:
A homogenizer or a pressure discharge type disperser that can be dispersed in an aqueous medium such as water with a polymer electrolyte such as an ionic surfactant, a polymer acid, or a polymer base and heated to a temperature equal to or higher than the melting point to apply a strong shearing force. Can be easily dispersed in release agent fine particles of 2 μm or less. There is no particular limitation on the combination of the resin of the resin fine particles, the colorant, and the release agent, and they can be appropriately selected and used depending on the purpose.

In the present invention, if necessary, fine particles such as an internal additive, a charge controlling agent, inorganic fine particles, organic fine particles, a lubricant, and an abrasive may be added to the resin fine particle dispersion, the colorant dispersion, and the release agent dispersion. Can be added. The addition method may be such that the fine particles may be dispersed in a fine resin particle dispersion, a colorant dispersion, or a release agent dispersion, or a resin fine particle dispersion, a colorant dispersion, a release agent dispersion, or the like may be mixed. In the mixture consisting of
A dispersion obtained by dispersing the fine particles may be added and mixed.

Examples of the internal additives include metals such as ferrite, magnetite, reduced iron, cobalt, manganese, and nickel, alloys, and magnetic substances such as compounds containing these metals.

Examples of the charge control agent include a quaternary ammonium salt compound, a nigrosine compound, a dye composed of a complex of aluminum, iron, chromium and the like, and a triphenylmethane pigment. In the present invention, the charge control agent is added for the purpose of controlling the ionic strength which affects the stability at the time of aggregation, adhesion, fusion, and the like, and for the purpose of reducing wastewater contamination. The charge control agent is preferably of a material that is hardly soluble in water.

As the inorganic fine particles, for example, external additives on the surface of the toner, such as silica, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide, can be used. As the organic fine particles, for example, an external additive on the surface of the toner, such as a vinyl resin, a polyester resin, and a silicone resin, can be used. In addition, these inorganic fine particles and organic fine particles can be used as a flow aid, a cleaning aid, and the like.

Examples of the lubricant include fatty acid amides such as ethylene bisstearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate. Examples of the abrasive include silica, alumina, cerium oxide, and the like.

The above-mentioned internal additives, charge controlling agents, inorganic fine particles,
The average particle size of fine particles such as organic fine particles, lubricants and abrasives is 1
μm or less, preferably in the range of 0.01 to 1 μm. If the average particle size exceeds 1 μm, the particle size distribution of the toner for developing an electrostatic image finally obtained becomes wide, or free particles are generated, and the performance and reliability of the toner tend to be deteriorated. By adjusting the average particle diameter within the above range, uneven distribution of components between toners is reduced, the dispersion in the toner is improved, and variations in the performance and reliability of the toner can be suppressed. The average particle size can be measured using, for example, a laser diffraction type particle size distribution measuring device, a centrifugal type particle size distribution measuring device, or the like. The above-mentioned other fine particles can be appropriately added as long as the object of the present invention is not impaired, but is generally very small, specifically in the range of 0.01 to 5% by weight, Preferably 0.5 to 2
A weight percent range is appropriate.

The dispersion medium used for the dispersion liquid of the resin fine particles, the colorant dispersion liquid, the release agent dispersion liquid and the other fine particle dispersion liquids is as follows.
For example, an aqueous medium can be used. Examples of the aqueous medium include water such as distilled water and ion-exchanged water, and alcohol. These may be used alone or in combination of two or more.

The aqueous medium is preferably used by adding and mixing a surfactant in advance. This surfactant stabilizes the resin fine particles, the colorant, the release agent fine particles, etc. in an aqueous medium, improves the storage stability of the dispersion, and stabilizes the aggregated particles in the aggregation step and the adhesion in the adhesion step. It also contributes to the stability of the particles.

Examples of the surfactant include anionic surfactants such as sulfate ester type, sulfonate type, phosphate ester type and soap type; and cationic surfactants such as amine salt type and quaternary ammonium salt type. Nonionic surfactants such as polyethylene glycol-based, alkylphenol-ethylene oxide adduct-based and polyhydric alcohol-based surfactants. Of these, ionic surfactants are preferred, and anionic surfactants and cationic surfactants are more preferred.

In the method for producing a toner for developing an electrostatic image of the present invention, there is no problem even if the polarities of the surfactants used in the resin fine particle dispersion, the colorant dispersion and the release agent dispersion are the same. By reducing the polarity of the surfactant contained in the resin fine particle dispersion and the colorant dispersion and the polarity of the surfactant contained in the release agent dispersion, the free release agent is reduced. And it is advantageous because free particles can be reduced in the subsequent deposition step.

In general, an anionic surfactant has a strong dispersing power and is excellent in dispersing resin fine particles and a colorant. Therefore, a cationic surfactant is used as a surfactant for dispersing a release agent. Is more advantageous. The anionic surfactant or the cationic surfactant is preferably used in combination with a nonionic surfactant. The surfactants may be used alone or in combination of two or more.

Specific examples of the anionic surfactant include fatty acid soaps such as potassium laurate, sodium oleate and castor oil sodium; and sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonylphenyl ether sulfate. , Sodium alkylnaphthalenesulfonate such as laurylsulfonate, dodecylbenzenesulfonate, triisopropylnaphthalenesulfonate, dibutylnaphthalenesulfonate, naphthalenesulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric amide sulfonate, oleic acid amide Sulfonates such as sulfonates; lauryl phosphate, isopropyl phosphate, nonyl Phosphoric acid esters such as E alkenyl ether phosphates; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate, such as sulfosuccinate salts such as sodium lauryl sulfosuccinate 2.

Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride,
Amine salts such as oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate; lauryltrimethylammonium chloride, dilauryldimethylammonium chloride, distearylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleyl Quaternary ammonium salts such as bispolyoxyethylene methylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulfate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzenedimethylammonium chloride and alkyltrimethylammonium chloride.

Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl Ethers, alkylphenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene laurate, polyoxyethylene stearate,
Alkyl esters such as polyoxyethylene oleate;
Alkyl amines such as polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene tallow amino ether; polyoxyethylene lauric amide, polyoxyethylene Alkyl amides such as stearic acid amide and polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide and the like Alkanolamides: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmiate, polyoxyethylene Nso sorbitan monostearate,
And sorbitan ester ethers such as polyoxyethylene sorbitan monooleate.

The content of the surfactant in each dispersion can be appropriately selected as long as it does not impair the present invention, but is generally small. Specifically 0.0
1 to 10% by weight, preferably 0.05 to 5% by weight
And more preferably in the range of 0.1 to 2% by weight. If the content is less than 0.01% by weight, the dispersion of the resin fine particle dispersion, the colorant dispersion, and the release agent dispersion loses the stability and causes agglomeration. Therefore, there is a problem that release of specific particles occurs. On the other hand, if the content exceeds 10% by weight, the particle size distribution of the particles becomes wide, and the control of the particle size becomes unfavorable.

The method for preparing the resin fine particle dispersion is not particularly limited, and can be appropriately selected according to the purpose. For example, it is prepared as follows. When the resin constituting the resin fine particles is a homopolymer or a copolymer (vinyl resin) of a vinyl monomer such as an ester having a vinyl group, a vinyl nitrile, a vinyl ether, or a vinyl ketone, Emulsion polymerization or seed polymerization of a vinyl monomer in an ionic surfactant can be used to convert resin particles of a homopolymer or copolymer (vinyl resin) of the vinyl monomer into an ionic surfactant. Can be prepared.

When the resin constituting the resin fine particles is a resin other than a homopolymer or a copolymer of a vinyl monomer, the resin is soluble in an oily solvent having a relatively low solubility in water. If it is dissolved in the oily solvent, the dissolved product is added to water together with the ionic surfactant and the polymer electrolyte, and dispersed in fine particles using a disperser such as a homogenizer, and then heated or reduced in pressure. The oily solvent is evaporated to prepare a resin fine particle dispersion.

The colorant dispersion can be prepared, for example, by dispersing the colorant in an aqueous medium such as the surfactant. The release agent dispersion, for example, the release agent is dispersed in water together with the ionic surfactant, a polymer acid, a polymer electrolyte such as a polymer base, and while heating this above the melting point, a homogenizer or By applying a strong shearing force using a pressure discharge type dispersing machine, the release agent can be finely divided to prepare a dispersion. The dispersion obtained by dispersing the fine particles of the other components can be prepared, for example, by dispersing the fine particles in an aqueous medium such as the surfactant.

When preparing a dispersion of composite particles by adding fine particles of other components to the resin fine particle dispersion, the colorant dispersion, the release agent dispersion, etc., for example, the components of the composite particles are added After dissolving and dispersing in a solvent, it is dispersed in water together with an appropriate dispersant, and a method of evaporating the solvent by heating or depressurizing, or applying a mechanical shearing force or electric force to a latex surface produced by emulsion polymerization or seed polymerization. The composite particles can be prepared by immobilization with a suction force. These methods are effective in suppressing the release of the colorant and the like, and in improving the colorant dependence of the chargeability of the electrostatic image developing toner.

The dispersing means is not particularly limited. For example, a known dispersing apparatus such as a rotary shearing homogenizer, a ball mill having a medium, a sand mill, and a dyno mill can be used.

The aggregated particles according to the third aspect of the present invention are prepared, for example, as follows. A first dispersion (a resin fine particle dispersion and a colorant dispersion, and if necessary, at least one kind of release agent dispersion) containing an aqueous medium to which an ionic surfactant is added and mixed, is mixed with the ionic surfactant. A method of adding and aggregating an ionic surfactant of the opposite polarity to the agent, in the above method, a method of adding and aggregating an ionic surfactant of the opposite polarity as a solution, anionic and cationic in each solution In this method, resin fine particles and a colorant are dispersed and aggregated. When this mixed liquid is stirred using a stirring means, resin particles and the like are aggregated in the dispersion liquid by the action of the ionic surfactant to form aggregated particles, and an aggregated particle dispersion liquid is obtained. In addition, the said stirring means is not specifically limited, It can select suitably from well-known stirring apparatuses according to the objective.

In this aggregated particle dispersion, a release agent dispersion,
Alternatively, when a dispersion containing a release agent and resin fine particles is added, a release agent fine particle layer or a resin fine particle layer containing release agent fine particles is formed on the surface of the aggregated particles. As the ionic surfactant of the dispersion containing the release agent, an ionic surfactant having an opposite polarity is used.

When forming aggregated particles, the polarity of the ionic surfactant contained in the dispersion to be added and the polarity of the ionic surfactant contained in the dispersion to be added are set to be opposite to each other, and It is preferable to shift the balance in advance, and to compensate for this shift in balance to cause aggregation. In general, depending on the type of the resin constituting the resin fine particles, the colorant, the release agent, the polarity, and the like, aggregation and adhesion may be difficult, and specific material particles may be released at the time of aggregation or adhesion, A desired toner composition may not be obtained.

More specifically, polyolefin-based release agents such as polyethylene and polypropylene used in ordinary toners have low polarity and extremely poor compatibility with fine resin particles. When the mold agent particles adhere, the release agent particles are easily released. If the amount of the released release agent is increased, the inherent properties of the toner are impaired, and the released release agent overflows from the developing machine during development, thereby contaminating the inside of the developing machine, or causing the released release agent inside the developing machine. Therefore, there is a possibility that a problem such as breakage due to mechanical stress or filming of the developing sleeve may occur.

However, since aggregation occurs due to the difference in polarity (anion / cation) of the surfactant, if the difference in polarity disappears, it is not possible to attach fine particles added later. Therefore, in the aggregation stage, the polarity balance is shifted, thereby facilitating the attachment of the particles added later.
The above problem can be avoided by forming the aggregated particles and attaching the additional fine particles as described above. For example, even if the polarity of the resin fine particle dispersion and the colorant dispersion is the same, aggregated particles containing the resin fine particles and the colorant uniformly can be obtained by adding a surfactant of the opposite polarity.

The aggregated particles according to the fourth aspect of the present invention are prepared, for example, as follows. That is, a first dispersion containing a water-based medium to which an ionic surfactant is added and mixed (a resin fine particle dispersion and a colorant dispersion, if necessary,
This is a method in which an inorganic metal salt having a charge of at least two valences is added to at least one type of release agent dispersion liquid) to cause aggregation to obtain an aggregated particle dispersion liquid.

The aggregating agent used in the aggregating step may be a polymer of an inorganic metal salt having a charge of 2 or more, which can be dissolved in the dispersion of the aggregating step.
The metal elements constituting the inorganic metal salt are 2A, 3A, 4A, 5A, 6A, 7A in the periodic table (long-period table).
It has two or more valence charges belonging to groups A, 8, 1B, 2B, and 3B. Specifically, metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; and inorganic metal polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide And so on. Among them, aluminum salts and their polymers are preferred. Generally, in order to obtain a sharper particle size distribution, the valency of the inorganic metal salt is 2 or more than monovalent.
The polymerization type inorganic metal salt polymer is more suitable when the valence is trivalent or more than divalent and the same valence.

The amount of the coagulant to be added is not particularly limited as long as it does not impair the present invention. 0.05 to 5% by weight, more preferably 0.1 to 2% by weight. When the amount added is less than 0.01% by weight,
Dispersions such as resin fine particle dispersions, colorant dispersions, and release agent dispersions become unstable. There are problems such as liberation. On the other hand, if it exceeds 10% by weight, the particle size distribution of the agglomerated particles becomes wide, and it becomes difficult to control the particle size.

The average particle size of the aggregated particles formed in the above-mentioned aggregation step is not particularly limited, but is usually controlled so as to be approximately the same as the average particle size of the final toner for developing an electrostatic image. Is good. This particle size control can be easily performed, for example, by appropriately selecting the aggregation temperature and the polymerization and stirring conditions. In this way, aggregated particles having substantially the same average particle size as the toner for developing an electrostatic image are formed, and an aggregated particle dispersion obtained by dispersing the aggregated particles is obtained. The content of the aggregated particles in the aggregated particle dispersion is 40.
% By weight or less is appropriate. Note that the aggregated particles may be referred to as “parent aggregated particles”.

In the step of adhering the release agent fine particles and the like, the release agent dispersion liquid obtained by dispersing the release agent fine particles in the aggregated particle dispersion liquid and / or the release agent dispersion liquid and various fine particles are mixed. This is an adhesion step in which a release agent layer is formed by adding and mixing the dispersed fine particle dispersion and adhering release agent fine particles, various fine particles, and the like to the surface of the aggregated particles. Examples of the fine particles include the resin fine particles, the colorant fine particles, and other fine particles, and a dispersion in which these fine particles are dispersed may be used alone or in combination of two or more. May be used.

The adhesion of the release agent fine particles to the surface of the aggregated particles is carried out by adding and mixing the fine particle dispersion to the aggregated particle dispersion. The method of addition and mixing is not particularly limited. It may be added and mixed continuously, or may be divided into a plurality of steps and performed stepwise. The additional addition and mixing of the fine particles as described above not only suppresses the generation of fine particles, but also simultaneously releases the released fine particles among the already added release agent fine particles on the surface of the aggregated particles. And the particle size distribution of the obtained toner can be sharpened. It is also possible to change the composition and physical properties stepwise from the toner surface toward the inside. In particular, it is also possible to change the position and layer thickness of the release agent layer inside the toner, and to change the structure of the toner. Can be easily controlled.

The release agent layer is formed by adding a release agent dispersion obtained by dispersing a release agent such as wax to the aggregated particle dispersion at least once and mixing the release agent fine particles on the aggregated particle surface. After that, a resin fine particle dispersion is added and mixed to adhere resin fine particles for a resin coating to form a release agent layer under the resin coating, and the release agent dispersion and the resin fine particle dispersion are mixed. By alternately adding and mixing, it is also possible to adhere two or more layers of the release agent fine particle layer to the surface of the aggregated particles. Alternatively, two or more release agent layers can be formed. As a result, exposure of the release agent to the toner surface can be suppressed, and the release function can be effectively exerted at the time of fixing.

The thickness of the release agent layer of the toner that has undergone the fusing step depends on the particle size and amount of the release agent fine particles to be added.
The thickness is approximately の of the theoretical release agent fine particle layer formed at the time of addition. This thickness can be easily measured by cross-sectional analysis of the toner using a transmission electron microscope (TEM) or the like. The thickness of the release agent layer is 0.01 to 2 μm.
The range of m, preferably in the range of 0.05 to 1 μm, more preferably in the range of 0.1 to 0.5 μm is effective in achieving the effects of the present invention. If the thickness of the release agent layer is less than 0.01 μm, the amount of the release agent that oozes onto the surface of the fixed image during fixing is insufficient, and the release effect cannot be sufficiently exerted. Also,
If it exceeds 2 μm, the amount of the release agent attached to the aggregated particles becomes large, so that the adhesion to the surface of the aggregated particles becomes insufficient, and the amount of the released release agent increases. Further, since the amount of the release agent contained in the toner becomes too large, there is a problem in the storability, durability and the like of the fixed image, which is not preferable.

The depth of the release agent layer from the toner particle surface (the depth to the outermost surface of the release agent layer) is determined by the thickness of the resin film on the toner particle surface. As the particle size of the resin fine particles added to form the resin film increases and as the amount of addition increases, the thickness of the resin film increases and the depth of the release agent layer also increases. The measurement of the depth is performed by a transmission electron microscope (TE
M) can be easily measured by cross-sectional observation.
The release agent layer is 0.01 to 3 μm from the toner surface, preferably 0.05 to 1 μm, more preferably 0.1 to 0.7 μm.
The range of μm is effective for exhibiting the effects of the present invention. If the thickness is less than 0.01 μm, an external additive such as a fluidity-imparting agent is embedded in the release agent near the toner surface, and the function of the external additive such as the fluidity of the toner is reduced. On the other hand, when the thickness exceeds 3 μm, the release agent hardly seeps into the toner surface during fixing, and offset tends to occur particularly at high temperatures. In addition, the average value of the values obtained by cross-sectional observation using a transmission electron microscope (TEM) or the like is used as the depth of the release agent.

In the step of attaching the resin fine particles for forming the resin film, the release agent fine particles and the like are attached to the surface of the aggregated particles to form a release agent layer, and then the adhered particles (aggregated particles having the release agent layer formed thereon) A resin fine particle dispersion is added to and mixed with the dispersion liquid to further adhere the resin fine particles to the surface of the adhered particles, and is formed by heating and fusing in a later-described fusing step to form a resin film (shell) on the toner particle surfaces. It is. The method of the addition and mixing is not particularly limited. For example, the addition and mixing may be performed gradually and continuously, or may be performed in a plurality of divided steps. By adding and mixing in this way,
Suppressing the generation of fine particles, among the particle size distribution particles already added, also has the effect of simultaneously adhering free release agent particles to the release agent layer surface of the aggregated particles,
The particle size distribution of the toner can be sharpened. Further, in the obtained electrostatic image developing toner, the composition and physical properties from the surface to the inside can be changed stepwise. In particular, the position and thickness of the release agent layer inside the toner can be changed, and the structure of the toner can be easily controlled.

This resin film can prevent the colorant, the release agent and the like from being exposed on the surface of the toner particles. As a result, the release agent seeps out of the toner surface at the time of fixing, and the release function can be effectively exhibited. Further, although the colorant affects the chargeability, the resin film prevents exposure to the surface of the toner particles and is substantially disposed in the aggregated particles, so that the charge fluctuation due to the colorant can be suppressed. . This can prevent a difference in the charging characteristics of the toner depending on the type of the colorant when the multicolor electrostatic image developing toner is manufactured. In addition, by selecting a resin having a high glass transition point as a resin constituting the resin film, it is possible to produce a toner for developing an electrostatic charge image having both excellent heat preservability and fixability and excellent chargeability. can do.

The average particle diameter of the resin fine particles for forming a resin film is 1 μm or less, and preferably in the range of 0.01 to 1 μm. When the average particle size exceeds 1 μm, the particle size distribution of the toner for developing an electrostatic image finally obtained is widened, free particles are generated, and reliability and performance are likely to be deteriorated. Fine particles within the above-mentioned range of the average particle size do not have the above-mentioned drawbacks and are free to form a layer structure by the fine particles. The average particle size can be measured with a microtrack or the like.

The proportion (volume) of the resin fine particles for forming the resin film in the toner depends on the volume fraction of the toner.
The volume is preferably 50% or less of the volume of the obtained electrostatic image developing toner. If it exceeds 50%, the particles do not adhere to the aggregated particles provided with the release agent layer, and new aggregated particles are generated by the fine particles, so that the composition distribution and the particle size distribution of the toner significantly fluctuate, and desired performance is obtained. Can not do.

In the above-mentioned dispersion of resin fine particles for forming a resin film, a dispersion in which one kind of resin fine particles are dispersed alone or a dispersion in which two or more kinds of fine particles are dispersed in combination may be used. As the resin fine particles, the resin fine particles used when generating the mother aggregated particles may be used. The fine particles used in combination are not particularly limited, but can be appropriately selected according to the purpose. As the dispersion medium of the fine particles, for example, the above-mentioned aqueous medium can be used, and it is preferable to add one or more surfactants in the same manner as described above.

The content of the fine particles in the dispersion is suitably in the range of 5 to 60% by weight, preferably 10 to 40% by weight. If the content is out of the range of 5 to 60% by weight, it may be difficult to control the structure and composition from the inside to the surface of the electrostatic image developing toner. The dispersion is prepared, for example, by adding and mixing an ionic surfactant or the like and dispersing at least one of the fine particles in an aqueous medium. Further, it can be adjusted by immobilizing it on the surface of a latex prepared by emulsion polymerization or seed polymerization by mechanical shearing or electric adsorption.

If the glass transition point of the resin constituting the resin film on the toner surface is selected to be higher than the glass transition point of the resin existing inside the toner, the storage stability and fluidity of the toner and the minimum fixing It is possible to balance both temperature and temperature. In addition, when the molecular weight of the resin of the resin coating on the polymer side is increased and the elasticity in the molten state is increased, it is possible to prevent offset to the heat roll at a high temperature. Therefore, this is an extremely effective means particularly in a fixing system in which oil is not applied to a heat roll.

When the molecular weight of the resin in the toner particle surface coating (outermost shell) is smaller than the molecular weight of the resin in the aggregated particles, the smoothness of the surface of the obtained toner particles is increased, and the fluidity and transferability are improved. This is advantageous in improving the quality. When two or more kinds of the fine particles are used in combination, it means the average value of the molecular weights of those resins.

When the molecular weight of the resin of the toner surface coating and the molecular weight of the resin of the agglomerated particles inside the toner are extremely different, the adhesive strength between the core resin and the coating resin may be low. When penetrating the release agent layer and directly bonding the resin of the core portion and the resin of the coating film, it is necessary to consider the above-mentioned adhesive force. Generally, toner is easily broken when it is agitated in a developing machine or mixed with a carrier and subjected to mechanical stress. Therefore, first, resin particles having a molecular weight and / or a glass transition point which are intermediate between the resin of the toner core portion and the resin of the resin film are attached to the aggregated particles, and then the resin particles for the resin film are attached. Accordingly, the destruction of the toner particles can be prevented.

When the fine particle dispersion including the release agent is divided into a plurality of portions and added stepwise, the layer of the fine particles is layered stepwise on the surface of the aggregated particles. The structure can be changed or a composition gradient can be provided. Moreover, when the fine particle dispersion is added and mixed a plurality of times, the particle size distribution can be kept sharp at the time of fusion, and the fluctuation of the particle size can be suppressed. In addition, it is possible to eliminate the need to add a surfactant such as a surfactant or a stabilizer such as a base or an acid to enhance the stability of the particles at the time of fusing, or to minimize the amount of these additives, thereby improving quality and Enables cost reduction.

The conditions for attaching the fine particles to the aggregated particles are as follows. The adhesion temperature is preferably lower than the glass transition point of the resin in the aggregated particles and up to room temperature. When heated to a temperature lower than the glass transition point, the aggregated particles and the fine particles are more likely to adhere, and the formed adhered particles are more easily stabilized.

The time for the adhesion treatment depends on the adhesion temperature and cannot be specified unconditionally, but is usually about 5 minutes to 2 hours. In the attaching operation, the dispersion containing the aggregated particles and the fine particles may be left standing, or may be gently stirred by a mixer or the like. The latter is advantageous because uniform adhered particles can be formed.

In the present invention, the attaching step may be performed once or plural times. In the former case, only one layer of the fine particles (additional particles) is formed on the surface of the aggregated particles, whereas in the latter case, if two or more types of fine particle dispersions are prepared, A layer of additional particles contained in these fine particle dispersions can be laminated on the surface, and a toner for developing an electrostatic image having a complicated and precise hierarchical structure can be obtained, and the toner has a desired function. can do.

When the adhering step is performed a plurality of times, fine particles (additional particles) to be first adhered to the above-mentioned mother aggregated particles
And the fine particles (additional particles) to be adhered thereafter may be in any combination, and can be appropriately selected according to the use of the toner for developing an electrostatic image. When the adhesion step is performed a plurality of times, each time the fine particle dispersion is added and mixed, heating is preferably performed at a temperature lower than the glass transition temperature of the resin in the aggregated particles, and the heating temperature is preferably increased stepwise. . By this heating, the attached particles can be stabilized, and the generation of free fine particles can be suppressed.

In the above adhering step, by appropriately selecting the fine particles, a toner for developing an electrostatic image having desired characteristics can be freely designed and manufactured. Note that the distribution of the colorant in the attached particles eventually becomes the distribution of the colorant in the toner particles. Therefore, the fine and uniform dispersion of the colorant in the attached particles improves the color development of the toner. Preferred for. For that purpose, it is desirable to add the coloring agent not only to the aggregated particles but also to the release agent layer.

The fusing step is a step of fusing and coalescing the adhered particles to form toner particles. The heating temperature in the fusion step needs to be a temperature higher than the glass transition point of the resin in the aggregated particles and the resin for the coating film added in the adhesion step, and it is necessary to heat at a temperature at which the release agent fuses. . Specifically, it is necessary to heat this heating temperature to a temperature lower than the melting point of the release agent by 20 ° C. or more, preferably to a temperature lower by 10 ° C. than the melting point of the release agent, more preferably It is desirable to heat the adhered particles at a temperature equal to or higher than the melting point of the molding agent. If the heating temperature is lower than the melting point of the release agent by 20 ° C. or more, the release agent particles cannot be effectively fused with each other, and a release agent layer cannot be formed. The upper limit of the heating temperature may be lower than the decomposition temperature of the resin. Therefore, the heating temperature varies depending on the type of the resin and cannot be specified unconditionally, but a temperature in a range from 20 ° C. lower than the glass transition temperature of the resin or the melting point of the release agent to 180 ° C. is appropriate. . By selecting the heating temperature, the shape of the obtained toner particles can be arbitrarily controlled from an irregular shape to a spherical shape. The heating can be performed using a heating device / apparatus known per se. The fusion time is short if the heating temperature is high, and long if the heating temperature is low, but is generally about 30 minutes to 10 hours.

The toner particles having undergone the fusion step of the present invention can be washed and dried under appropriate conditions. In addition, on the obtained toner surface, silica, alumina,
Inorganic fine particles such as titania and calcium carbonate, and fine resin particles such as a vinyl resin, a polyester resin and a silicone resin may be added by applying a shearing force in a dry state. These inorganic fine particles and resin fine particles function as external additives such as a flow aid and a cleaning aid.

According to the method for producing a toner for developing an electrostatic image of the present invention, fine powder is not generated during the production of the toner. Therefore, the operation of removing the fine powder in the kneading and pulverizing method or the suspension polymerization method is unnecessary, and the production process is simplified. Has the advantage of Also, the resin particles, the colorant and the release agent are aggregated in a uniformly dispersed state,
Since the toner can be attached and fused, the composition of the toner for developing an electrostatic image can be uniformly controlled. Further, since a highly hydrophobic material such as a release agent can be selectively present inside the toner particles, the amount of the release agent exposed on the surface of the toner particles can be significantly reduced.

The resin used in the present invention has a weight average molecular weight (M
w) and the number average molecular weight (Mn) were measured by gel permeation chromatography. Weight average molecular weight (Mw)
The molecular weight distribution represented by the ratio (Mw / Mn) of the number average molecular weight (Mn) is preferably 2 to 30, more preferably 2 to 20, and particularly preferably 2 to 15. The ratio (Mw / M
If the molecular weight distribution represented by n) exceeds 30, the transparency, smoothness and color mixing of the fixed image cannot be sufficiently ensured,
In particular, when a toner for developing an electrostatic image is developed and fixed on a film, an image projected by transmission of light becomes an unclear and dark image or an opaque and non-colored projected image. On the other hand, when the ratio (Mw / Mn) is less than 2, the viscosity of the toner at the time of high-temperature fixing is remarkably reduced, and offset tends to occur. On the other hand, the ratio (Mw / Mn)
When the molecular weight distribution represented by is adjusted within the above numerical range,
The transparency, smoothness, and color mixing of the fixed image can be ensured, and a decrease in the viscosity of the toner during high-temperature fixing can be suppressed, and the occurrence of offset can be effectively prevented.

The volume average particle diameter D ₅₀ of the toner of the present invention is 2 to 2.
9 μm, preferably 3 to 8 μm is suitable. When the average particle size is less than 2 μm, the chargeability tends to be insufficient, and the developability may be reduced. When the average particle size exceeds 9 μm, the resolution of an image may be reduced.

The charge amount of the toner for developing an electrostatic image of the present invention is in the range of 10 to 40 μC / g, preferably 15 to 35 μC / g.
The range of g is appropriate. If it is less than 10 μC / g, background stains are likely to occur, and if it is more than 40 μC / g, the image density tends to decrease. Summer (30 ° C, 90% RH)
Is preferably in the range of 0.5 to 1.5, and the ratio of the charge amount in winter to the charge amount in winter (10 ° C., 10% RH),
The range of 0.7 to 1.3 is more preferable. If this ratio is out of the above range, the toner becomes more environmentally dependent and the charging property becomes unstable, which is not practically preferable.

The toner for developing an electrostatic image obtained in this way has various properties such as chargeability, developability, transferability, fixability, and cleaning property, particularly smoothness, transparency, color mixing, and color development in an image. Is excellent, the influence of environmental conditions is small, and the above-mentioned characteristics can be exhibited stably, so that the reliability is high. Also, unlike the case where the toner for developing an electrostatic image is manufactured by a kneading and pulverizing method, it is manufactured by an agglomeration and fusion method, so that the average particle size can be reduced and the particle size distribution is sharpened. be able to.

The electrostatic image developer of the present invention is not particularly limited except that it contains the toner for developing an electrostatic image.
The component composition can be arbitrarily selected according to the purpose.
It may be used alone, and may be prepared as a one-component electrostatic image developer, or may be prepared as a two-component electrostatic image developer in combination with a carrier. The carrier used here is not particularly limited, and a carrier known per se can be used. For example, JP-A-62-39879
A known carrier such as a resin-coated carrier described in JP-A-56-11461 and the like can be used.

Next, a resin-coated carrier will be described as a specific example of the carrier. The core particles of the carrier, usual iron powder, ferrite, can be used, such as magnetite molding material, a volume average particle size D ₅₀ is preferably in the range of 30 to 200 [mu] m.

Examples of the coating resin for the core particles include styrenes such as styrene, parachlorostyrene and α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, acrylic acid 2 -Α-methylene fatty acid monocarboxylic acids such as ethylhexyl, methyl methacrylate, methacrylic acid, 2-ethylhexyl n-propyl methacrylate lauryl methacrylate; nitrogen-containing acrylics such as dimethylaminoethyl methacrylate; vinyl such as acrylonitrile and methacrylonitrile Nitriles, vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether;
Vinyl methyl ketone, vinyl ethyl ketone, vinyl ketones such as vinyl isopropenyl ketone, olefins such as ethylene and propylene, vinylidene fluoride, tetrafluoroethylene, homopolymers such as vinyl fluorine-containing monomers such as hexafluoroethylene, Or a copolymer comprising two or more monomers, methyl silicone, silicones such as methyl phenyl silicone, bisphenol,
Examples include polyesters containing glycol and the like, epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins, and the like. These resins may be used singly or may be used alone.
More than one species may be used in combination. The amount of the coating resin used is in the range of 0.1 to 10 parts by weight, preferably 0.5 to 3.0 parts by weight, based on 100 parts by weight of the core particles.

For the production of the carrier, a heating type kneader, a heating type Henschel mixer, a UM mixer and the like can be used. Can be. The mixing ratio of the toner and the carrier in the electrostatic image developer of the present invention is not particularly limited, and can be appropriately selected depending on the purpose.

The image forming method of the present invention includes an electrostatic latent image forming step, a toner image forming step, a transfer step, and a cleaning step, and can further add a recycling step as needed. The recycling step is to return the toner collected in the cleaning step to the toner image forming step. The image forming method including the recycling step can be carried out using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. Further, the present invention can be applied to a recycling system in which the cleaning step is omitted and the toner is collected simultaneously with the development. Each of the above steps is a general step per se, for example, as described in JP-A-56-40868 and JP-A-49-912.
No. 31, for example. The image forming method of the present invention can be applied to known image forming apparatuses such as a copying machine and a facsimile machine.

[0116]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
In the following description, “parts” means parts by weight.

The average particle size D ₅₀ and the volume average particle size distribution index GSDv (D _{84 V} / D _{16 V} ) of the toner were measured using a Coulter counter (TA2 type, manufactured by Coulter Co., Ltd.). The average particle size of the resin fine particles, the colorant fine particles, and the release agent fine particles was measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.). The resin in the aggregated particles and the molecular weight and molecular weight distribution of the resin for the resin coating were measured by gel permeation chromatography (HLC-81, manufactured by Tosoh Corporation).
20 GPC).

The glass transition point of the fine resin particles was measured using a differential scanning calorimeter (DSC-50, manufactured by Shimadzu Corporation) at a temperature rising rate of 3 ° C./min. Evaluation of toner cross section
Transmission electron microscope TEM (JEOL Ltd., JE
OL1010), the thickness of the release agent layer and the depth of the release agent layer from the toner surface were measured based on the magnification. The shape factor SF1 of the toner was measured using a Luzex image analyzer (LUZEXIII, manufactured by Nicole).

Further, the evaluation of the electrostatic image developer was carried out by forming an image using a modified VIVACE400 manufactured by Fuji Xerox Co., Ltd., and determining the image quality of the obtained image (related to the color mixing of the image), the background stain, (Related to the smoothness of the image) and transparency were visually evaluated. Note that the above-described color developability is obtained by evaluating the color of an image fixed on paper with cyan toner on a document, and the transparency is obtained by evaluating the color of an image fixed on a transparent film with cyan toner with respect to an original. . These evaluation results are summarized in Table 1.

—Preparation of Resin Fine Particle Dispersion (1) — Styrene 360 parts Butyl acrylate 40 parts Acrylic acid 8 parts Dodecylmercaptan 10 parts Carbon tetrabromide 4 parts The above components (all manufactured by Wako Pure Chemical Industries, Ltd.) are mixed in advance. 8 parts of a nonionic surfactant (manufactured by Sanyo Chemical Co., Nonipol 8.5) and 7 parts of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) Is dissolved in 585 parts of ion-exchanged water in a flask, and the solution is charged into the flask, dispersed, emulsified, and slowly mixed for 10 minutes while further mixing with ammonium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.). 50 parts of ion-exchanged water in which 3 parts were dissolved was added, and after purging with nitrogen, the contents were heated in an oil bath until the temperature of the flask reached 70 ° C. while stirring the inside of the flask. The reduction polymerization was continued. afterwards,
The reaction solution is cooled to room temperature, and the resin fine particle dispersion (1)
Was prepared. Next, a part of the resin fine particle dispersion (1) was left in an oven at 80 ° C. to remove water, and the properties of the residue were measured. The average particle diameter was 150 nm, the glass transition point was 58 ° C. The weight average molecular weight was 23,000.

—Preparation of Resin Fine Particle Dispersion (2) — Styrene 340 parts Butyl acrylate 40 parts Methyl acrylate 20 parts Acrylic acid 8 parts Dodecylmercaptan 8 parts Carbon tetrabromide 4 parts The above components (all were Wako Pure Chemical Industries, Ltd.) Was previously mixed and dissolved to prepare a solution, and 2 parts of a nonionic surfactant (manufactured by Sanyo Chemical Co., Nonipol 8.5) and an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Neogen RK) was placed in a flask containing a surfactant solution in which 2 parts of neogen RK were dissolved in 586 parts of ion-exchanged water. The solution was poured into the flask, dispersed and emulsified, and slowly mixed with ammonium persulfate (10 minutes). 50 parts of ion-exchanged water in which 2.5 parts of Wako Pure Chemical Co., Ltd. were dissolved, nitrogen replacement was carried out, and then the contents of the flask were stirred until the contents reached 70 ° C. Heated in vinegar, and emulsion polymerization is continued for 6 hours. Thereafter, the reaction liquid was cooled to room temperature to prepare a resin fine particle dispersion liquid (2). Next, a part of the resin fine particle dispersion (1) was left in an oven at 80 ° C. to remove water, and the characteristics of the residue were measured.
0 nm, glass transition point is 60 ° C., weight average molecular weight is 2
It was 7,000.

—Preparation of Resin Fine Particle Dispersion (3) — 330 parts of styrene 70 parts of butyl acrylate 8 parts of dodecyl mercaptan 4 parts of carbon tetrabromide 4 parts The above components (all manufactured by Wako Pure Chemical Industries, Ltd.) are mixed in advance. Then, the solution was adjusted, and 8 parts of a nonionic surfactant (Emulgen 840, manufactured by Kao Corporation) and 7 parts of an anionic surfactant (Nurex Paste H, manufactured by NOF Corporation) were ion-exchanged. A surfactant solution dissolved in 585 parts of water is placed in a flask, and the solution is poured into the flask, dispersed and emulsified, and slowly mixed for 10 minutes, and further mixed with 1 part of ammonium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.). 50 parts of ion-exchanged water in which was dissolved was added, and after purging with nitrogen, the contents were heated in an oil bath until the temperature of the flask reached 70 ° C. while stirring the inside of the flask. Between emulsion polymerization was continued. Thereafter, the reaction solution was cooled to room temperature to prepare a resin fine particle dispersion (3). Then, a part of the resin fine particle dispersion (3) was left in an oven at 80 ° C. to remove water, and the characteristics of the residue were measured.
0 nm, glass transition point 55 ° C, weight average molecular weight 4
It was 4,000.

—Preparation of Resin Fine Particle Dispersion (4) — Polyester 200 parts (Glass transition point 61 ° C., molecular weight 26,000, manufactured by Sanyo Chemical Co., Ltd.) Tetrahydrofuran (manufactured by Wako Pure Chemical Industries) 400 parts Polyethylene glycol (Wako Pure Chemical Industries, Ltd.) 20 parts Ion-exchanged water 500 parts The above components were mixed and dissolved, and the solution was adjusted.
Dispersed by a stator type homogenizer (Ultra Turrax, manufactured by IKA) for 15 minutes, then heated and left at 80 ° C. for 4 hours, cooled, and cooled to an average particle size of 2
A resin fine particle dispersion (4) was prepared by dispersing 20 nm of resin fine particles.

—Preparation of Colorant Dispersion (1) — Phthalocyanine Pigment (PVFASTBLUE, manufactured by Dainichi Seika Co., Ltd.) 60 parts Anionic surfactant (manufactured by Wako Pure Chemical Industries, Ltd.) 2 parts Ion-exchanged water 300 parts After dissolving in a homogenizer (I
(Ultra Turrax, manufactured by KA Corporation) to prepare a colorant dispersion (1) in which a colorant (phthalocyanine pigment) having an average particle size of 150 nm is dispersed.

—Preparation of Release Agent Particle Dispersion Solution (1) — 100 parts of paraffin wax (HNP0190, manufactured by Nippon Seiro, melting point 90 ° C.) Anion surfactant (Ripearl 860K, manufactured by Lion Corporation) 3 parts Ion-exchanged water After mixing and dissolving 500 parts of the above components, a homogenizer (I
After dispersing using an Ultra Turrax (manufactured by KA Co., Ltd.), dispersion treatment is performed with a pressure discharge type homogenizer, and release agent fine particle dispersion liquid (paraffin wax) having an average particle diameter of 190 nm is dispersed. 1) was prepared.

—Preparation of Release Agent Fine Particle Dispersion (2) — 100 parts of polyethylene wax (Polywax 655, melting point 93 ° C., manufactured by Toyo Petrolite Co.) Anionic surfactant (Pionin A-45-D, manufactured by Takemoto Yushi Co., Ltd.) 2 parts 500 parts of ion-exchanged water After mixing and dissolving the above components, a homogenizer (I
(Ultra Turrax manufactured by KA Co., Ltd.), and then subjected to dispersion treatment with a pressure discharge type homogenizer to disperse release agent fine particles (polyethylene wax) having an average particle size of 320 nm (polyethylene wax). 2) was prepared.

—Preparation of Release Agent Particle Dispersion (3) — 100 parts of glycerin monostearate (manufactured by Nikko Chemicals Co., melting point: 75 ° C.) 3 parts of anionic surfactant (manufactured by Daiichi Kogyo Seiyaku, Neogen SC) 500 parts of exchanged water After mixing and dissolving the above components, a homogenizer (I
After dispersing using KA company, Ultra Turrax),
Dispersion treatment with a pressure discharge type homogenizer, average particle size of 4
A release agent fine particle dispersion (3) prepared by dispersing release agent fine particles (glycerin monostearate ester wax) of 00 nm was prepared.

(Example 1) -Preparation of agglomerated particles- Resin fine particle dispersion (1) 300 parts Colorant dispersion (1) 15 parts Cationic surfactant (Sanisol B50, manufactured by Kao Corporation) 3 parts Ion-exchanged water 500 parts The above components were placed in a round stainless steel flask and homogenized (Ultra Turrax T50, manufactured by IKA).
Then, the mixture was dispersed in a heating oil bath while being heated to 47 ° C. with stirring, and kept at 47 ° C. for 30 minutes to form aggregated particles. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 4.4 μm.

-Attachment of release agent fine particles-30 parts of a release agent fine particle dispersion (1) is gently added to the aggregated particle dispersion, and the mixture is heated and stirred at 47 ° C for 30 minutes to form a surface of the aggregated particles. Release agent fine particles were adhered. When a part of the obtained adhered particles was observed with an optical microscope, the release agent-adhered particles having an average particle size of about 4.8 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the release agent-attached particle dispersion, gently add 70 parts of the resin fine particle dispersion (1), and raise the temperature of the heating oil bath to 48 ° C. After holding for 1 hour, resin fine particles were adhered to the surface of the release agent-adhered particles. When a part of the obtained adhered particles was observed with an optical microscope, the average particle diameter was about 5.0.
Resin fine particle-adhered particles of 4 μm were formed.

-Fusion of adhered particles- Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen S)
C) An aqueous solution of an anionic surfactant in which 6 parts were dissolved in 24 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the dispersion liquid of fine resin particle-adhered particles. C. and maintained for 5 hours to fuse the adhered particles. Then, the reaction product is filtered,
After being sufficiently washed with ion-exchanged water, it was dried using a vacuum drier to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 5.
4 μm, and the release agent content in the toner was 3.3% by weight. Further, when the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.1 μm was formed at a depth of about 0.2 μm from the toner surface on average. In addition, the volume average particle size distribution index GSDv of the toner
( _D84V / _D16V ) is 1.23, and the shape factor SF1 is 1
28. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was −24 μC / g, and the charge amount in a low-temperature and low-humidity environment was −28 μC / g. One part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts of the obtained toner particles, and mixed with a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of an electrostatic image developer- Ferrite particles (manufactured by Powder Tech, average particle size 50 μm)
m) 100 parts of methyl methacrylate resin (manufactured by Mitsubishi Rayon Co., Ltd., molecular weight 95,000) was mixed with 1.5 parts of toluene 50
0 parts together with a pressure-type kneader, stirred and mixed at room temperature for 15 minutes, heated to 70 ° C. while mixing under reduced pressure to distill off toluene, then cooled and classified using a 105 μm sieve to coat the resin. A ferrite carrier was obtained. This resin-coated ferrite carrier and the toner for developing an electrostatic image were mixed to prepare a two-component electrostatic image developer having a toner concentration of 7% by weight. An image was formed using the electrostatic image developer as described above, and the image quality was evaluated. The results are shown in Table 1.

(Example 2) -Preparation of aggregated particles- Resin fine particle dispersion (1) 150 parts Colorant dispersion (1) 15 parts Cationic surfactant (Sanisol B50, manufactured by Kao Corporation) 2 parts Ion-exchanged water 500 parts The above-mentioned components were placed in a round stainless steel flask, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used.
Then, the mixture was dispersed in a heating oil bath while being heated to 49 ° C. with stirring, and kept at 49 ° C. for 30 minutes to form aggregated particles. When a part of the aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 4.6 μm.

-Attachment of release agent fine particles-80 parts of the release agent fine particle dispersion (1) is gently added to the above-mentioned aggregated particle dispersion, and the mixture is further heated and stirred at 49 ° C for 30 minutes, and the surface of the aggregated particles is maintained. The release agent fine particles were adhered to the sample.
Observation of a part of the adhered particles with an optical microscope revealed that the release agent-adhered particles having an average particle size of about 5.2 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, 150 parts of the resin fine particle dispersion (1) was gently added, and the temperature of the heating oil bath was set at 51 ° C. And kept for 2 hours to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 5.
7 μm resin adhered particles were formed.

-Fusion of adhered particles- Anionic surfactant (Neogen S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C) An aqueous solution of an anionic surfactant in which 10 parts were dissolved in 40 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the adhered particle dispersion, and heated to 92 ° C. while stirring was continued. And held for 5 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 6.
0 μm, and the content of the release agent in the toner was 9.0% by weight. Further, when the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.8 μm was formed at a depth of about 1.1 μm from the toner surface on average. In addition, the volume average particle size distribution index GSDv of the toner
( _D84V / _D16V ) is 1.24 and the shape factor SF1 is 1
04. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was −22 μC / g, and the charge amount in a low-temperature and low-humidity environment was −24 μC / g. One part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts of the obtained toner particles, and mixed with a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 1 using the electrostatic image developing toner. The image quality was evaluated in the same manner as in Example 1 using this electrostatic image developer, and the results are shown in Table 1.

(Example 3) -Preparation of agglomerated particles- Resin fine particle dispersion (1) 280 parts Colorant dispersion (1) 15 parts Cationic surfactant (Sanisol B50, manufactured by Kao Corporation) 4 parts 500 parts of ion-exchanged water The above-mentioned components were accommodated in a round stainless steel flask, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used.
Then, the mixture was dispersed in a heating oil bath while being heated to 44 ° C. with stirring, and kept at 44 ° C. for 40 minutes to form aggregated particles. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 5.0 μm.

-Attachment of release agent fine particles-To the aggregated particle dispersion, gently add 40 parts of the release agent fine particle dispersion (1), and further heat and stir at 44 ° C for 30 minutes to obtain a surface of the aggregated particle. The release agent fine particles were adhered to the sample.
When a part of the obtained adhered particles was observed with an optical microscope, the release agent adhered particles having an average particle size of about 5.6 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, 50 parts of a resin fine particle dispersion (2) was gently added, and the temperature of the heating oil bath was raised to 45 ° C. And held for 1 hour to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 5.6.
Resin fine particle-adhered particles of μm were formed.

-Fusion of adhered particles- Anionic surfactant (Neogen S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C) An aqueous solution of an anionic surfactant in which 10 parts were dissolved in 40 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the adhered particle dispersion, and heated to 85 ° C. while stirring was continued. And held for 9 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 3.
4 μm, and the content of the release agent in the toner was 4.5% by weight. Further, when the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.8 μm was formed at a depth of about 0.5 μm from the toner surface on average. In addition, the volume average particle size distribution index GSDv of the toner
( _D84V / _D16V ) is 1.20 and the shape factor SF1 is 1
It was 31. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was −18 μC / g, and the charge amount in a low-temperature and low-humidity environment was −21 μC / g. To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 1 using the electrostatic image developing toner. The image quality was evaluated in the same manner as in Example 1 using this electrostatic image developer, and the results are shown in Table 1.

(Example 4) -Preparation of aggregated particles- Resin fine particle dispersion (1) 260 parts Colorant dispersion (1) 15 parts Cationic surfactant (Catinal LTC-35A, manufactured by Toho Chemical Co., Ltd.) 4 parts 500 parts of ion-exchanged water The above-mentioned components were accommodated in a round stainless steel flask, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used.
Then, the mixture was dispersed in a heating oil bath while stirring to 52 ° C., and kept at 52 ° C. for 40 minutes to form aggregated particles. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 4.9 μm.

-Attachment of release agent fine particles-To the agglomerated particle dispersion, slowly add 10 parts of a release agent fine particle dispersion (2), and further stir at 49 ° C for 60 minutes while heating and stirring the surface of the agglomerated particles. Release agent fine particles were adhered. When a part of the obtained adhered particles was observed with an optical microscope,
Release agent-adhered particles having an average particle size of about 5.7 μm were formed.

—Adhesion of Resin Fine Particles for Surface Coating— 135 parts of resin fine particle dispersion (1) was gently added to the obtained release agent-adhered particle dispersion, and the temperature of the heating oil bath was set to 53 ° C. And kept for 2 hours to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 6.
Resin fine particle-adhered particles of 2 μm were formed.

-Fusion of Adhered Particles- An aqueous solution of anionic surfactant in which 10 parts of an anionic surfactant (manufactured by NOF CORPORATION, NUREX®) was dissolved in 40 parts of ion-exchanged water was prepared, and the dispersion of the adhered particles was performed The surfactant aqueous solution was gently added to the solution, and the solution was heated to 90 ° C. and kept for 7 hours while continuing stirring to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 7.
The toner had a release agent content of 1.1% by weight and a surfactant content of 1% by weight.
When the cross section of the toner particles was observed by TEM,
A release agent layer having an average thickness of 0.12 μm was formed at a depth of about 2.8 μm from the toner surface on average. In addition, the volume average particle size distribution index GSDv (D _84V / D
_16V ) was 1.19 and the shape factor SF1 was 132. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was ─26 μC / g, and the charge amount in a low-temperature and low-humidity environment was -29 μC / g.
To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 1 using the electrostatic image developing toner. The image quality was evaluated in the same manner as in Example 1 using this electrostatic image developer, and the results are shown in Table 1.

(Example 5) -Preparation of agglomerated particles- Resin fine particle dispersion (2) 260 parts Colorant dispersion (1) 20 parts Cationic surfactant (Sanisol B50, manufactured by Kao Corporation) 3 parts Ion-exchanged water 500 parts The above-mentioned components were placed in a round stainless steel flask, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used.
Then, the mixture was dispersed in a heating oil bath while being heated to 44 ° C. with stirring, and kept at 44 ° C. for 60 minutes to form aggregated particles. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 3.9 μm.

-Attachment of release agent fine particles-80 parts of a release agent fine particle dispersion (3) is gently added to the aggregated particle dispersion, and the mixture is further heated and stirred at 44 ° C for 80 minutes to form a surface of the aggregated particles. Release agent fine particles were adhered. When a part of the obtained adhered particles was observed with an optical microscope,
Release agent-adhered particles having an average particle size of about 4.2 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, 80 parts of a resin fine particle dispersion (2) was gently added, and the temperature of the heating oil bath was raised to 45 ° C. And held for 1 hour to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 4.8.
Resin fine particle-adhered particles of μm were formed.

-Fusion of adhered particles- Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen S
C) An aqueous solution of an anionic surfactant in which 10 parts were dissolved in 30 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the adhered particle dispersion, and heated to 88 ° C. while stirring was continued. And held for 6 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 5.
5 μm, and the content of the release agent in the toner was 9.2% by weight. Further, when the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 2.8 μm was formed at a depth of about 0.5 μm from the toner surface on average. In addition, the volume average particle size distribution index GSDv of the toner
( _D84V / _D16V ) is 1.26 and the shape factor SF1 is 1
It was 40. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was −31 μC / g, and the charge amount in a low-temperature and low-humidity environment was −38 μC / g. To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of electrostatic image developer- Ferrite particles (manufactured by Powder Tech, average particle size 50 μm)
m) 100 parts and a silicone resin (SR2411, manufactured by Toray Dow Corning Silicone Co., Ltd., solid content 20%) 2
0 parts together with 500 parts of toluene in a pressure kneader,
After stirring and mixing at room temperature for 15 minutes, 70
The temperature was raised to ° C, and toluene was distilled off. Then, it was again placed in a kneader while stirring at 150 ° C. for 5 hours, cooled, and then classified using a 105 μm sieve to produce a resin-coated ferrite carrier. This resin-coated ferrite carrier and the toner for developing an electrostatic image were mixed to prepare a two-component electrostatic image developer having a toner concentration of 7% by weight. The image quality was evaluated in the same manner as in Example 1 using this electrostatic image developer, and the results are shown in Table 1.

(Example 6) -Preparation of aggregated particles- Resin fine particle dispersion (1) 100 parts Colorant dispersion (1) 15 parts Cationic surfactant (Sanisol B50, manufactured by Kao Corporation) 4 parts Ion-exchanged water 500 parts The above-mentioned components were placed in a round stainless steel flask, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used.
Then, the mixture was dispersed and heated in an oil bath for heating with stirring to 50 ° C., and kept at 50 ° C. for 40 minutes to form aggregated particles. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 3.8 μm.

First Adhesion of Release Agent Particles First, gently add 30 parts of the release agent particle dispersion (1) to the above-mentioned aggregated particle dispersion, and further heat and stir at 48 ° C. for 60 minutes. The release agent fine particles were adhered to the surface of the aggregated particles.
When a part of the obtained adhered particles was observed with an optical microscope, the release agent-adhered particles having an average particle size of about 4.0 μm were formed.

-Attachment of Resin Fine Particles-To the adhered particle dispersion, 50 parts of the resin fine particle dispersion (1) was gently added, and the mixture was further kept at 48 ° C for 1 hour. Resin fine particles were adhered. Observation of the obtained adhered particles with an optical microscope revealed that resin fine particle adhered particles having an average particle size of about 4.2 μm were formed.

Second Adhesion of Release Agent Fine Particles To the obtained resin fine particle adhered particle dispersion, gently add 20 parts of the release agent fine particle dispersion (1).
The release agent particles were adhered to the surface of the resin particle adhered particles while maintaining the heating and stirring for minutes. Observation of a part of the adhered particles with an optical microscope revealed that the release agent-adhered particles having an average particle diameter of about 4.3 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the release agent-attached particle dispersion, 70 parts of a resin fine particle dispersion (1) was gently added, and the oil bath was heated at 50 ° C to 2 parts. After holding for a time, resin fine particles were adhered to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that resin fine particle adhered particles having an average particle size of about 5.1 μm were formed.

-Fusion of adhered particles- Anionic surfactant (Neogen S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C) An aqueous solution of an anionic surfactant in which 10 parts were dissolved in 40 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the adhered particle dispersion, and heated to 85 ° C. while stirring was continued. And held for 9 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 5.
5 μm, and the content of the release agent in the toner was 6.0% by weight. Further, when the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.4 μm at a depth of about 0.2 μm from the toner surface and an average of about 0.5 μm from the toner surface were obtained. A release agent layer having an average thickness of 0.1 μm was formed at the depth. The volume average particle size distribution index GSDv ( _D84V / _D16V ) of the toner is 1.
22, and the shape factor SF1 was 138. Further, the toner particles were added to a high temperature and high humidity environment (28 ° C., 85% RH) and a low temperature and low humidity environment (10 ° C.
After being left at 30% RH for 12 hours, respectively, the charge amount (μC / g) was measured. The charge amount (Q / M) in a high temperature and high humidity environment was −33 μC / g, and the charge amount in a low temperature and low humidity environment was −. A good charging characteristic of 36 μC / g was exhibited. To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 5 using the electrostatic image developing toner. The image quality was evaluated in the same manner as in Example 5 using this electrostatic image developer, and the results are shown in Table 1.

(Example 7) -Preparation of aggregated particles- Resin fine particle dispersion (2) 280 parts Colorant dispersion (1) 15 parts Cationic surfactant (Sanisol B50, manufactured by Kao Corporation) 2 parts Ion-exchanged water 500 parts The above-mentioned components were placed in a round stainless steel flask, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used.
Then, the mixture was dispersed in a heating oil bath while being heated to 55 ° C. with stirring, and kept at 55 ° C. for 30 minutes to form aggregated particles. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 4.9 μm.

-Attachment of release agent fine particles-The release agent fine particle dispersion liquid (2) is gently added to the above-mentioned aggregated particle dispersion liquid by 70 parts, and further heated and stirred at 55 ° C for 30 minutes, and the surface of the aggregated particle surface is maintained. The release agent fine particles were adhered to the sample.
Observation of a part of the adhered particles with an optical microscope revealed that the release agent-adhered particles having an average particle size of about 5.9 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, gently add 50 parts of resin fine particle dispersion (2), and further heat the oil bath to 58 ° C. For 2 hours to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 6.1 μm.
Was formed.

-Fusion of adhered particles- Anionic surfactant (Neogen S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C) An aqueous solution of an anionic surfactant in which 15 parts were dissolved in 50 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the adhered particle dispersion, and heated to 80 ° C. while stirring was continued. And held for 20 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 6.
5 μm, and the release agent content in the toner was 8.0% by weight. Further, when the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.6 μm was formed at a depth of about 0.6 μm from the toner surface on average. In addition, the volume average particle size distribution index GSDv of the toner
( _D84V / _D16V ) is 1.21 and the shape factor SF1 is 1
34. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was -29 μC / g, and the charge amount in a low-temperature and low-humidity environment was -27 μC / g, indicating good charging characteristics. To 100 parts of the obtained toner particles, 1.5 parts of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 5 using the electrostatic image developing toner. The image quality was evaluated in the same manner as in Example 5 using this electrostatic image developer, and the results are shown in Table 1.

(Comparative Example 1) -Preparation of agglomerated particles- Resin fine particle dispersion liquid (1) 300 parts Release agent fine particle dispersion liquid (1) 30 parts Colorant dispersion liquid (1) 15 parts Cationic surfactant (Kao 3 parts Ion-exchanged water 500 parts The above-mentioned components were stored in a round stainless steel flask, and were homogenized (IKA, Ultra Turrax T50).
Then, the mixture was dispersed in a heating oil bath while stirring to 47 ° C., and kept at 47 ° C. for 30 minutes to form aggregated particles. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 4.6 μm.

-Attachment of Resin Fine Particles for Surface Coating-To this aggregated particle dispersion, 70 parts of resin fine particle dispersion (1) was gently added, and the oil bath was heated and kept at 48 ° C for 1 hour. Then, fine resin particles were attached to the surface of the aggregated particles. Observation of the obtained adhered particles with an optical microscope revealed that resin fine particle adhered particles having an average particle size of about 5.0 μm were formed.

-Fusion of adhered particles- Anionic surfactant (Neogen S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C) An aqueous solution of an anionic surfactant in which 6 parts were dissolved in 24 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the adhered particle dispersion, and heated to 92 ° C. while stirring was continued. And held for 5 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size of the obtained toner was 5.1 μm. When the cross section of the toner particles was observed by TEM, it was confirmed that the release agent fine particles were randomly dispersed in the cross section of the toner. The average particle diameter D ₅₀ of the obtained toner particles was 5.1 μm, and the content of the release agent in the toner was 3.4% by weight. When the cross section of the toner particles was observed by SEM, the release agent fine particles were randomly dispersed in the cross section of the toner. In addition, the volume average particle size distribution index GSDv ( _D84V / _D16V ) of the toner was 1.26, and the shape factor SF1 was 127. Further, the toner particles were added to a high-temperature and high-humidity environment (28 ° C, 85% R) without adding an external additive.
H) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours each, and the charge amount (μC / g) was measured. The charge amount (Q / M) in the high-temperature and high-humidity environment was −22 μm.
C / g, the charge amount in a low-temperature and low-humidity environment was -27 μC / g. To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 1 using the electrostatic image developing toner. The image quality was evaluated in the same manner as in Example 1 using this electrostatic image developer, and the results are shown in Table 1.

(Comparative Example 2) -Preparation of aggregated particles- Resin fine particle dispersion liquid (1) 300 parts Colorant dispersion liquid (1) 15 parts Cationic surfactant (Sanisol B50, manufactured by Kao Corporation) 3 parts Ion-exchanged water 500 parts The above-mentioned components were placed in a round stainless steel flask, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used.
Then, the mixture was dispersed in a heating oil bath while stirring to 47 ° C., and kept at 47 ° C. for 30 minutes to form aggregated particles. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 4.0 μm.

-Attachment of release agent fine particles-The release agent fine particle dispersion liquid (1) is gently added to the above-mentioned aggregated particle dispersion liquid by 3 parts, and the mixture is further heated and stirred at 47 ° C for 30 minutes, and the surface of the aggregated particle surface is maintained. The release agent fine particles were adhered to the sample. When a part of the obtained adhered particles was observed with an optical microscope,
Release agent-adhered particles having an average particle size of about 4.5 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-adhered particle dispersion, gently add 70 parts of the resin fine particle dispersion (1), and further heat the oil bath to 48 ° C. For 1 hour to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 5.2 μm.
Was formed.

-Fusion of adhering particles- Anionic surfactant (Neogen S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C) Prepare an aqueous solution of an anionic surfactant in which 6 parts are dissolved in 24 parts of ion-exchanged water, gently add the aqueous solution of the surfactant to the adhered particle dispersion, and heat to 97 ° C. while continuing stirring. And held for 10 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 5.
4 μm, and the release agent content in the toner was 0.33% by weight. When the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.008 μm was formed at a depth of about 0.01 μm from the toner surface on average. Further, the volume average particle size distribution index G of the toner
SDv (D _84V / D _16V) is 1.23, a shape factor SF
1 was 138. Further, the toner particles are added to a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) without adding an external additive.
After standing for a period of time, the charge amount (μC / g) was measured. The charge amount (Q / M) in a high-temperature and high-humidity environment was −9 μC / g.
The charge amount in a low-temperature and low-humidity environment was −18 μC / g. To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 1 using the electrostatic image developing toner. The image quality was evaluated in the same manner as in Example 1 using this electrostatic image developer, and the results are shown in Table 1.

(Comparative Example 3) -Preparation of aggregated particles- Resin fine particle dispersion (2) 360 parts Colorant dispersion (1) 15 parts Cationic surfactant (Sanisol B50, manufactured by Kao Corporation) 3 parts Ion-exchanged water 500 parts The above-mentioned components were placed in a round stainless steel flask, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used.
Then, the mixture was dispersed in a heating oil bath while stirring to 47 ° C., and kept at 47 ° C. for 30 minutes to form aggregated particles. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 4.6 μm.

-Attachment of release agent fine particles-To the above aggregated particle dispersion, gently add 3 parts of the release agent fine particle dispersion (3), and further, while heating and stirring at 47 ° C for 30 minutes, to obtain aggregated particles. Release agent fine particles were adhered to the surface.
When a part of the obtained adhered particles was observed with an optical microscope, the release agent adhered particles having an average particle size of about 4.9 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, gently add 10 parts of resin fine particle dispersion (1), and further heat the oil bath to 48 ° C. For 1 hour to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 5.0 μm.
Was formed.

-Fusion of adhered particles- Anionic surfactant (Neogen S manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C) An aqueous solution of an anionic surfactant in which 22 parts were dissolved in 24 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the adhered particle dispersion, and heated to 88 ° C. while stirring was continued. And held for 5 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 6.
5 μm, and the content of the release agent in the toner was 0.33% by weight. Further, when the cross section of the toner particles was observed by TEM, a part of the release agent was exposed on the toner surface, and a release agent layer having an average thickness of 0.3 μm was formed near the toner surface. Further, the volume average particle size distribution index GS of the toner
Dv ( _D84V / _D16V ) is 1.25, and the shape factor SF1
Was 145. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. μC / g)
The charge (Q / M) in a high-temperature and high-humidity environment was −8 μC / g, and the charge in a low-temperature and low-humidity environment was −11 μC / g. To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 1 using the electrostatic image developing toner. The image quality was evaluated in the same manner as in Example 1 using this electrostatic image developer, and the results are shown in Table 1.

(Comparative Example 4) -Preparation of aggregated particles- Resin fine particle dispersion (1) 300 parts Colorant dispersion (1) 15 parts Cationic surfactant (Sanisol B50, manufactured by Kao Corporation) 3 parts Ion-exchanged water 500 parts The above-mentioned components were placed in a round stainless steel flask, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used.
Then, the mixture was dispersed in a heating oil bath while stirring to 47 ° C., and kept at 47 ° C. for 30 minutes to form aggregated particles. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 4.6 μm.

-Attachment of release agent fine particles-To the above aggregated particle dispersion, gently add 30 parts of the release agent fine particle dispersion (1), and further, while heating and stirring at 47 ° C for 30 minutes, keep the aggregated particle surface. The release agent fine particles were adhered to the sample.
When a part of the obtained adhered particles was observed with an optical microscope, the release agent adhered particles having an average particle size of about 4.9 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, gently add 70 parts of the resin fine particle dispersion (1), and further heat the oil bath to 48 ° C. For 1 hour to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 5.1 μm.
Was formed.

-Fusion of attached particles- Anionic surfactant (Neogen S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C) An aqueous solution of an anionic surfactant in which 6 parts were dissolved in 24 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the adhered particle dispersion, and heated to 66 ° C. while stirring was continued. And held for 30 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 5.
5 μm, and the release agent content in the toner was 3.3% by weight. When the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.2 μm was formed at a depth of about 0.2 μm from the toner surface on average. In addition, the volume average particle size distribution index GSDv of the toner
( _D84V / _D16V ) is 1.27 and the shape factor SF1 is 1
41. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was −19 μC / g, and the charge amount in a low-temperature and low-humidity environment was −23 μC / g. To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 1 using the toner for developing an electrostatic image. The image quality was evaluated in the same manner as in Example 1 using this electrostatic image developer, and the results are shown in Table 1.

(Embodiment 8) The toner was recovered from the cleaner section of a modified model of Fuji Xerox's VIVACE 400 used for evaluating the image quality in Example 1, and 10 parts of the recovered toner and 90 parts of the toner used in Example 1 were collected. The mixture was mixed to prepare a new toner, and a two-component electrostatic image developer was prepared in the same manner as in Example 1. An image was formed from this electrostatic image developer in the same manner as in Example 1, and the image quality was evaluated. The results are shown in Table 1.

Example 9 A cleaner brush and a cleaning blade were removed from the cleaner part of the modified model of VIVACE 400 manufactured by Fuji Xerox Co., Ltd. used for evaluating the image quality in Example 1, and the two-component static electricity was removed in the same manner as in Example 1. A charge image developer was prepared, an image was formed on the electrostatic image developer in the same manner as in Example 1, and the image quality was evaluated.
The results are shown in Table 1.

(Example 10) -Preparation of aggregated particles- Resin fine particle dispersion liquid (1) 300 parts Colorant dispersion liquid (1) 15 parts Zinc chloride 1 part Ion-exchanged water 500 parts The above components were placed in a round stainless steel flask. And a homogenizer (IKA, Ultra Turrax T50)
And then heated to 43 ° C. while stirring in an oil bath for heating, and kept at 43 ° C. for 30 minutes to form aggregated particles.

-Attachment of release agent fine particles-To the aggregated particle dispersion, 390 parts of a release agent fine particle dispersion (2) is gently added, and the mixture is further heated and stirred at 43 ° C for 30 minutes to form a surface of the aggregated particles. Release agent fine particles were adhered. When a part of the obtained adhered particles was observed with an optical microscope,
Release agent-adhered particles having an average particle size of about 4.8 μm were formed.

-Attachment of resin fine particles for surface coating-90 parts of resin fine particle dispersion liquid (1) was gently added to the release agent-adhered particle dispersion liquid, and the temperature of the heating oil bath was increased to 45 ° C. After holding for 1 hour, resin fine particles were adhered to the surface of the release agent-adhered particles. When a part of the obtained adhered particles was observed with an optical microscope, the average particle diameter was about 5.0.
Resin fine particle-adhered particles of 4 μm were formed.

-Fusion of adhered particles- Anionic surfactant (Neogen S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C) An aqueous solution of an anionic surfactant in which 6 parts were dissolved in 24 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the dispersion liquid of fine resin particle-adhered particles. C. and maintained for 5 hours to fuse the adhered particles. Then, the reaction product is filtered,
After being sufficiently washed with ion-exchanged water, it was dried using a vacuum drier to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 5.
4 μm, and the content of the release agent in the toner was 42.9% by weight. When the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 2.0 μm was formed at a depth of about 0.01 μm from the toner surface on average. Further, the volume average particle size distribution index GSD of the toner
v ( _D84V / _D16V ) was 1.26, and the shape factor SF1 was 140. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was 18 μC / g, and the charge amount in a low-temperature and low-humidity environment was 24 μC / g. One part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts of the obtained toner particles, and mixed with a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of electrostatic image developer- Ferrite particles (manufactured by Powder Tech, average particle size 50 μm)
m) 100 parts of methyl methacrylate resin (manufactured by Mitsubishi Rayon Co., Ltd., molecular weight 95,000) was mixed with 1.5 parts of toluene 50
0 parts together with a pressure-type kneader, stirred and mixed at room temperature for 15 minutes, heated to 70 ° C. while mixing under reduced pressure to distill off toluene, then cooled and classified using a 105 μm sieve to coat the resin. A ferrite carrier was obtained. This resin-coated ferrite carrier and the toner for developing an electrostatic image were mixed to prepare a two-component electrostatic image developer having a toner concentration of 7% by weight. An image was formed using the electrostatic image developer as described above, and the image quality was evaluated. The results are shown in Table 1.

(Example 11) -Preparation of agglomerated particles- Resin fine particle dispersion liquid (1) 150 parts Colorant dispersion liquid (1) 15 parts Zinc chloride 0.3 parts Deionized water 500 parts The above components were made of round stainless steel. Stored in a flask and homogenized (Ultra Turrax T50, manufactured by IKA)
Then, the mixture was dispersed in a heating oil bath while being heated to 49 ° C. with stirring, and kept at 49 ° C. for 30 minutes to form aggregated particles.

-Attachment of release agent fine particles-80 parts of the release agent fine particle dispersion (1) is gently added to the above-mentioned aggregated particle dispersion, and the mixture is further heated and stirred at 49 ° C for 30 minutes, and the surface of the aggregated particles is maintained. The release agent fine particles were adhered to the sample.
Observation of a part of the adhered particles with an optical microscope revealed that the release agent-adhered particles having an average particle size of about 5.2 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, 380 parts of the resin fine particle dispersion (1) was gently added, and the temperature of the heating oil bath was set at 51 ° C. And kept for 2 hours to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 5.
7 μm resin adhered particles were formed.

—Fusing of Adhered Particles— The pH of the dispersion liquid of resin fine particle adhered particles at 51 ° C. was measured to be 3.5. 1N N
After adjusting the pH at 51 ° C. to 6 by adding an aOH aqueous solution to stabilize the adhered particles, the mixture was heated to 92 ° C. while maintaining stirring and maintained for 5 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 6.
0 μm, and the content of the release agent in the toner was 9% by weight. Further, when the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.8 μm was formed at a depth of about 1.1 μm from the toner surface on average. Further, the volume average particle size distribution index GSDv (D _8
4V / _D16V ) is 1.24 and the shape factor SF1 is 124
Met. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was 19 μC / g, and the charge amount in a low-temperature and low-humidity environment was 26 μC / g. One part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts of the obtained toner particles, and mixed with a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 1 using the electrostatic image developing toner. The image quality was evaluated in the same manner as in Example 10 using this electrostatic image developer, and the results are shown in Table 1.

(Example 12) -Preparation of agglomerated particles- Resin fine particle dispersion (1) 280 parts Colorant dispersion (1) 15 parts Zinc chloride 0.1 part Ion-exchanged water 500 parts The above components were made of round stainless steel. Stored in a flask and homogenized (Ultra Turrax T50, manufactured by IKA)
Then, the mixture was dispersed in a heating oil bath while being heated to 48 ° C. with stirring, and kept at 48 ° C. for 40 minutes to form aggregated particles.

-Attachment of release agent fine particles-The release agent fine particle dispersion liquid (1) was gently added to the aggregated particle dispersion liquid by 40 parts, and the mixture was further heated and stirred at 48 ° C for 30 minutes. The release agent fine particles were adhered to the sample.
When a part of the obtained adhered particles was observed with an optical microscope, the release agent adhered particles having an average particle size of about 5.6 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, 50 parts of the resin fine particle dispersion (1) was gently added, and the temperature of the heating oil bath was set to 49 ° C. And held for 1 hour to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 5.6.
Resin fine particle-adhered particles of μm were formed.

-Fusion of Adhered Particles- The pH of the resin fine particle adhered particle dispersion at 49 ° C. was 3.5. 1N N
After adjusting the pH at 49 ° C. to 10 by adding an aOH aqueous solution and stabilizing the adhered particles, the mixture was heated to 97 ° C. and kept for 7 hours while continuing stirring to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 5.
9 μm, and the content of the release agent in the toner was 4.6% by weight. When the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.2 μm was formed at a depth of about 0.5 μm from the toner surface on average. In addition, the volume average particle size distribution index GSDv of the toner
( _D84V / _D16V ) is 1.24 and the shape factor SF1 is 1
03. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was −15 μC / g, and the charge amount in a low-temperature and low-humidity environment was −18 μC / g. One part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts of the obtained toner particles, and mixed with a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 10, except that the toner for developing an electrostatic image was used. The image quality was evaluated in the same manner as in Example 10 using this electrostatic image developer.
The results are shown in Table 1.

Example 13 Preparation of Aggregated Particles Resin Fine Particle Dispersion (1) 260 parts Colorant Dispersion (1) 15 parts Release Agent Dispersion (2) 20 parts Magnesium sulfate 0.2 part Ion exchange 500 parts of water The above-mentioned components are accommodated in a round stainless steel flask, and a homogenizer (IKA, Ultra Turrax T50) is used.
Then, the mixture was dispersed in a heating oil bath while stirring to 52 ° C., and kept at 52 ° C. for 40 minutes to form aggregated particles.

-Attachment of Release Agent Fine Particles-To the aggregated particle dispersion, gently add 30 parts of the release agent fine particle dispersion (1), and further, while heating and stirring at 49 ° C for 60 minutes, to the surface of the aggregated particles. Release agent fine particles were adhered. When a part of the obtained adhered particles was observed with an optical microscope,
Release agent-adhered particles having an average particle size of about 5.7 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, 150 parts of resin fine particle dispersion (2) was gently added, and the temperature of the oil bath for heating was set to 53 ° C. And kept for 2 hours to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 6.
Resin fine particle-adhered particles of 2 μm were formed.

-Fusion of Adhered Particles- The pH of the dispersion liquid of resin fine particle adhered particles at 53 ° C. was measured to be 3.5. 1N N
After adjusting the pH at 53 ° C. to 10 by adding an aOH aqueous solution to stabilize the adhered particles, the mixture was heated to 97 ° C. while maintaining stirring and maintained for 7 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 6.
5 μm, and the release agent content in the toner was 3.3% by weight. Further, when the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.09 μm was formed at a depth of about 0.4 μm from the toner surface on average. In addition, the volume average particle size distribution index GSDv of the toner
( _D84V / _D16V ) is 1.23, and the shape factor SF1 is 1
It was 17. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was −15 μC / g, and the charge amount in a low-temperature and low-humidity environment was −19 μC / g, indicating good charging characteristics. One part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts of the obtained toner particles, and mixed with a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 10 using the electrostatic image developing toner. The image quality was evaluated in the same manner as in Example 10 using this electrostatic image developer.
The results are shown in Table 1.

(Example 14) -Preparation of aggregated particles- Resin fine particle dispersion (1) 260 parts Colorant dispersion (1) 20 parts Ferric chloride 0.6 parts Ion-exchanged water 500 parts Housed in a stainless steel flask and homogenized (IKA, Ultra Turrax T50)
And then heated in an oil bath for heating with stirring to 42 ° C. and kept at 42 ° C. for 60 minutes to form aggregated particles.

-Attachment of Release Agent Fine Particles-To the aggregated particle dispersion, slowly add 50 parts of the release agent fine particle dispersion (2), and further, while heating and stirring at 42 ° C for 80 minutes, apply the mixture to the aggregated particle surface. Release agent fine particles were adhered. When a part of the obtained adhered particles was observed with an optical microscope,
Release agent-adhered particles having an average particle size of about 4.2 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, gently add 80 parts of the resin fine particle dispersion (1), and raise the temperature of the heating oil bath to 44 ° C. And held for 1 hour to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 4.8.
Resin fine particle-adhered particles of μm were formed.

—Fusing of Adhered Particles— The pH of the dispersion liquid of resin fine particle adhered particles at 45 ° C. was measured to be 3.5. 1N N
After the pH at 45 ° C. was adjusted to 10 by adding an aOH aqueous solution to stabilize the adhered particles, the mixture was heated to 88 ° C. while stirring and maintained for 10 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 3.
5 μm, and the content of the release agent in the toner was 5.6% by weight. When the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.2 μm was formed at an average depth of about 0.5 μm from the toner surface. In addition, the volume average particle size distribution index GSDv of the toner
( _D84V / _D16V ) is 1.25, and the shape factor SF1 is 1
23. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was −19 μC / g, and the charge amount in a low-temperature and low-humidity environment was −24 μC / g. To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of electrostatic image developer- Ferrite particles (manufactured by Powder Tech, average particle size 50 μm)
m) 100 parts and a silicone resin (SR2411, manufactured by Toray Dow Corning Silicone Co., Ltd., solid content 20%) 2
0 parts together with 500 parts of toluene in a pressure kneader,
After stirring and mixing at room temperature for 15 minutes, 70
The temperature was raised to ° C, and toluene was distilled off. Then, it was again placed in a kneader while stirring at 150 ° C. for 5 hours, cooled, and then classified using a 105 μm sieve to produce a resin-coated ferrite carrier. This resin-coated ferrite carrier and the toner for developing an electrostatic image were mixed to prepare a two-component electrostatic image developer having a toner concentration of 7% by weight. The image quality was evaluated in the same manner as in Example 10 using this electrostatic image developer, and the results are shown in Table 1.

(Example 15) -Preparation of agglomerated particles- Resin fine particle dispersion (1) 100 parts Colorant dispersion (1) 15 parts Aluminum sulfate 0.2 part Ion-exchanged water 500 parts The above components were made of round stainless steel. Stored in a flask and homogenized (Ultra Turrax T50, manufactured by IKA)
Then, the mixture was dispersed and heated in an oil bath for heating with stirring to 50 ° C., and kept at 50 ° C. for 40 minutes to form aggregated particles.

First Adhesion of Release Agent Particles First, 20 parts of a release agent particle dispersion (3) was gently added to the above-mentioned aggregated particle dispersion, and the mixture was further heated and stirred at 48 ° C. for 30 minutes. The release agent fine particles were adhered to the surface of the aggregated particles.
When a part of the obtained adhered particles was observed with an optical microscope, the release agent-adhered particles having an average particle size of about 4.0 μm were formed.

-Attachment of Resin Fine Particles-To the adhered particle dispersion, 50 parts of the resin fine particle dispersion (1) was gently added, and the mixture was further kept at 48 ° C for 1 hour. Resin fine particles were adhered. Observation of the obtained adhered particles with an optical microscope revealed that resin fine particle adhered particles having an average particle size of about 4.2 μm were formed.

-Second adhesion of release agent fine particles- Gently add 20 parts of release agent fine particle dispersion (2) to the obtained resin fine particle adhered particle dispersion, and further add 30 parts at 48 ° C.
The release agent particles were adhered to the surface of the resin particle adhered particles while maintaining the heating and stirring for minutes. Observation of a part of the adhered particles with an optical microscope revealed that the release agent-adhered particles having an average particle diameter of about 4.3 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the release agent-attached particle dispersion, gently add 70 parts of the resin fine particle dispersion (1), and further heat the oil bath to 50 ° C at 2 ° C. After holding for a time, resin fine particles were adhered to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that resin fine particle adhered particles having an average particle size of about 5.1 μm were formed.

—Fusing of Adhered Particles— The pH of the dispersion liquid of resin-adhered particles at 50 ° C. was measured to be 3.5. 1N N
After the pH at 50 ° C. was adjusted to 10 by adding an aOH aqueous solution to stabilize the attached particles, the mixture was heated to 85 ° C. while maintaining stirring and held for 9 hours to fuse the attached particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 5.
It was 5 μm, and the content of the release agent in the toner was 5% by weight. Further, when the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.1 μm at a depth of about 0.2 μm from the toner surface on average and a release agent layer having an average thickness of about 0.5 μm from the toner surface were obtained. The average thickness is 0.
A release agent layer of 1 μm was formed. Further, the volume average particle size distribution index GSDv ( _D84V / _D16V ) of the toner is 1.22.
And the shape factor SF1 was 126. Further, the toner particles are added to a high temperature and high humidity environment (28
° C, 85% RH) and low temperature and low humidity environment (10 ° C, 30%
RH) for 12 hours each, and then the charge amount (μC /
g), the charge amount (Q /
M) is −16 μC / g, and the charge amount in a low-temperature and low-humidity environment is −26.
A good charging characteristic of μC / g was exhibited. To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 14 using the toner for developing an electrostatic image. Using this electrostatic image developer, image quality was evaluated in the same manner as in Example 14,
The results are shown in Table 1.

(Example 16) -Preparation of aggregated particles- Resin fine particle dispersion (1) 280 parts Colorant dispersion (1) 15 parts Polyaluminum hydroxide 0.7 part Ion-exchanged water 500 parts Housed in a stainless steel flask and homogenized (IKA, Ultra Turrax T50)
Then, the mixture was dispersed in a heating oil bath while being heated to 55 ° C. with stirring, and kept at 55 ° C. for 30 minutes to form aggregated particles.

-Attachment of release agent fine particles-70 parts of a release agent fine particle dispersion (1) is gently added to the above-mentioned aggregated particle dispersion, and the mixture is further heated and stirred at 55 ° C for 30 minutes, and the surface of the aggregated particles is maintained. The release agent fine particles were adhered to the sample.
Observation of a part of the adhered particles with an optical microscope revealed that the release agent-adhered particles having an average particle size of about 5.9 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, gently add 50 parts of the resin fine particle dispersion (1), and further heat the oil bath to 58 ° C. For 2 hours to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 6.1 μm.
Was formed.

-Fusion of Adhered Particles- The pH of the dispersion liquid of resin fine particle adhered particles at 58 ° C. was measured to be 3.5. 1N N
After adjusting the pH at 58 ° C. to 10 by adding an aOH aqueous solution and stabilizing the adhered particles, the mixture was heated to 80 ° C. while maintaining stirring and maintained for 20 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 6.
5 μm, and the release agent content in the toner was 7.8% by weight. Further, when the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.6 μm was formed at a depth of about 0.6 μm from the toner surface on average. In addition, the volume average particle size distribution index GSDv of the toner
( _D84V / _D16V ) is 1.21 and the shape factor SF1 is 1
25. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge amount (Q / M) in a high-temperature and high-humidity environment was −16 μC / g, and the charge amount in a low-temperature and low-humidity environment was −25 μC / g. To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 14, except that the toner for developing an electrostatic image was used. Using this electrostatic image developer, image quality was evaluated in the same manner as in Example 14,
The results are shown in Table 1.

Comparative Example 5 Preparation of Aggregated Particles Resin Fine Particle Dispersion (1) 300 parts Colorant Dispersion (1) 15 parts Release Agent Fine Particle Dispersion (1) 30 parts Zinc chloride 1 part Ion-exchanged water 500 parts The above-mentioned components were placed in a round stainless steel flask, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used.
Then, the mixture was dispersed in a heating oil bath while stirring to 47 ° C., and kept at 47 ° C. for 30 minutes to form aggregated particles. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 4.6 μm.

-Attachment of release agent fine particles-400 parts of the release agent fine particle dispersion liquid (1) are gently added to the above-mentioned aggregated particle dispersion liquid, and the mixture is further heated and stirred at 47 ° C for 30 minutes, and the surface of the aggregated particle surface is maintained. The release agent fine particles were adhered to the sample. Observation of a part of the adhered particles with an optical microscope revealed that the release agent-adhered particles having an average particle size of about 5.9 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the aggregated particle dispersion, 10 parts of resin fine particle dispersion (1) was gently added, and the oil bath was heated and kept at 48 ° C for 1 hour. Then, fine resin particles were attached to the surface of the aggregated particles. Observation of the obtained adhered particles with an optical microscope revealed that resin fine particle adhered particles having an average particle size of about 5.0 μm were formed.

-Fusion of attached particles- Anionic surfactant (Neogen S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C) An aqueous solution of an anionic surfactant in which 6 parts were dissolved in 24 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the adhered particle dispersion, and heated to 92 ° C. while stirring was continued. And held for 5 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 5.
9 μm, and the content of the release agent in the toner is 45% by weight.
Met. Further, when the cross section of the toner particles was observed by TEM, it was confirmed that the release agent particles were randomly dispersed in the cross section of the toner. The volume average particle size distribution index GSDv ( _D84V / _D16V ) of the toner was 1.41 and the shape factor SF1 was 147. Further, the toner particles were added to a high temperature and high humidity environment (28 ° C.,
85% RH) and low-temperature, low-humidity environment (10 ° C, 30% R)
H) for 12 hours each, and then the charge amount (μC /
g), the charge amount (Q /
M) is -4 μC / g, and the charge in a low-temperature and low-humidity environment is -49 μC.
C / g. Colloidal silica (R97, manufactured by Nippon Aerosil Co., Ltd.) was used for 100 parts of the obtained toner particles.
2) 1 part was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 14, except that the toner for developing an electrostatic image was used. Using this electrostatic image developer, image quality was evaluated in the same manner as in Example 14,
The results are shown in Table 1.

(Comparative Example 6)-Preparation of aggregated particles-Resin fine particle dispersion liquid (1) 360 parts Colorant dispersion liquid (1) 15 parts Zinc chloride 1 part Ion-exchanged water 500 parts The above components were placed in a round stainless steel flask. And a homogenizer (IKA, Ultra Turrax T50)
Then, the mixture was dispersed in a heating oil bath while stirring to 47 ° C., and kept at 47 ° C. for 30 minutes to form aggregated particles.

-Attachment of release agent fine particles-To the above aggregated particle dispersion, gently add 4 parts of the release agent fine particle dispersion (1), and further heat and stir at 47 ° C for 30 minutes to obtain aggregated particles. Release agent fine particles were adhered to the surface.
When a part of the obtained adhered particles was observed with an optical microscope, the release agent adhered particles having an average particle size of about 4.9 μm were formed.

-Attachment of Resin Fine Particles for Surface Coating-To the obtained release agent-attached particle dispersion, gently add 10 parts of resin fine particle dispersion (1), and further heat the oil bath to 48 ° C. For 1 hour to adhere resin fine particles to the surface of the release agent-adhered particles. Observation of the obtained adhered particles with an optical microscope revealed that the average particle size was about 5.0 μm.
Was formed.

-Fusion of adhered particles- Anionic surfactant (Neogen S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C) An aqueous solution of an anionic surfactant in which 22 parts were dissolved in 24 parts of ion-exchanged water was prepared, and the aqueous solution of the surfactant was gently added to the adhered particle dispersion, and heated to 88 ° C. while stirring was continued. And held for 5 hours to fuse the adhered particles. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

The average particle size D ₅₀ of the obtained toner particles is 6.
5 μm, and the content of the release agent in the toner was 0.45% by weight. In addition, when the cross section of the toner particles was observed by TEM, a release agent layer having an average thickness of 0.01 μm was formed at a depth of about 3.1 μm from the toner surface on average. In addition, the volume average particle size distribution index GSDv of the toner
( _D84V / _D16V ) is 1.23, and the shape factor SF1 is 1
37. Further, the toner particles were left in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 30% RH) for 12 hours without adding an external additive. As a result, the charge (Q / M) in a high-temperature and high-humidity environment was −11 μC / g, and the charge in a low-temperature and low-humidity environment was −70 μC / g. To 100 parts of the obtained toner particles, 1 part of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Henschel mixer to obtain a toner for developing an electrostatic image.

-Preparation of Electrostatic Image Developer- A two-component electrostatic image developer was prepared in the same manner as in Example 14 using the electrostatic image developing toner. Using this electrostatic image developer, image quality was evaluated in the same manner as in Example 14,
The results are shown in Table 1.

[0253]

[Table 1]

As is clear from Table 1, Examples 1 to 16
The electrostatic image developer containing the electrostatic image developing toner of the present invention is superior in the anti-offset property and hardly causes the ground fogging compared to the electrostatic image developer containing the electrostatic developing toner of Comparative Examples 1 to 6. I understand. Further, with respect to the color developing properties and transparency required as color toners, the electrostatic image developers containing the electrostatic developing toners of Examples 1 to 16 are different from the electrostatic image developers containing the electrostatic developing toners of Comparative Examples 1 to 6. It can be seen that it is better than the developer.

[0255]

According to the present invention, by adopting the above structure, the amount of the release agent contained in the toner can be reduced, and the toner surface is covered with the resin film. The release can be greatly suppressed, and as a result, the release of the release agent can be prevented from adhering to the surface of the toner particles. In addition, it is possible to reliably prevent a decrease in color development and transparency due to light scattering of the release agent.
Further, even when the amount of the release agent added in color applications is increased, a high-quality copy image can be stably formed.

According to the present invention, it has become possible to provide a two-component electrostatic charge developer having a high transfer efficiency, a small toner consumption and a long service life. Further, according to the present invention, it is possible to form high-quality images in a cleanerless system having no cleaning mechanism and in a so-called toner recycling system in which toner collected from a cleaner is reused. In particular, the present invention is advantageous for forming a high-quality and reliable full-color image.

Further, according to the present invention, it is possible to provide a method for easily and simply producing a toner for electrostatic charge development excellent in the above-mentioned various properties. In the production of the electrostatic image developing toner of the present invention, in the step of preparing aggregated particles,
By adding an inorganic metal salt having a charge of at least two valences to perform aggregation, the amount of surfactant used can be significantly reduced, and the preparation of aggregated particles is simplified, and fusion and coalescence can be achieved. The washing for removing the surfactant from the toner particles obtained in the process is greatly shortened, and the influence of the surfactant on the chargeability of the toner can be prevented, so that the charge amount of the toner can be easily controlled.

As described above, according to the present invention, by adopting the above-mentioned constitution, the charging property, the developing property, the transferring property, the powder property,
It is possible to provide an electrostatic charge developing toner excellent in various properties such as cleaning properties and an electrostatic charge developer using the toner, and particularly, smoothness, transparency, color mixing property in an image,
This makes it possible to provide a highly reliable toner for developing an electrostatic image having excellent coloring properties and an electrostatic image developer using the toner for developing an electrostatic image, and is particularly suitable for a color toner.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takeshi Shoko 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Atsuhiko Eguchi 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Hideo Maehata 1600 Takematsu, Minamiashigara, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd.

Claims (5)

[Claims] 1. An electrostatic image developing toner containing a resin, a colorant and a release agent, wherein the release agent is arranged in the toner as a release agent layer along the toner surface. For developing electrostatic images. 2. A dispersion of resin fine particles and a dispersion of colorant are mixed, and the resin fine particles and the colorant are aggregated to form aggregated particles. Then, a dispersion of release agent fine particles is added. After mixing and releasing the release agent fine particles on the surface of the aggregated particles, further adding and mixing a dispersion of resin fine particles, after adhering the resin fine particles to the release agent layer surface of the aggregated particles 2. The method for producing a toner for developing an electrostatic image according to claim 1, wherein the resin particles are heated to a temperature equal to or higher than the glass transition point to fuse and coalesce to form toner particles. 3. A dispersion of resin fine particles and a dispersion of colorant are mixed, and the resin fine particles and the colorant are aggregated using an inorganic metal salt having a charge of two or more to form aggregated particles. Then, a dispersion liquid of the release agent particles is added and mixed, and the release agent particles are attached to the surface of the aggregated particles,
Further, a dispersion liquid of the resin fine particles is added and mixed, and the resin fine particles are adhered to the surface of the release agent layer of the agglomerated particles, and then heated to a temperature equal to or higher than the glass transition point of the resin fine particles to fuse and coalesce. 2. The method according to claim 1, wherein the toner particles are formed. 4. An electrostatic image developer containing a carrier and a toner, wherein the toner is the toner for developing an electrostatic image according to claim 1. 5. A step of forming an electrostatic latent image on an electrostatic latent image carrier, a step of developing the electrostatic latent image with a developer on a developer carrier to form a toner image, and 5. The method according to claim 4, wherein the image forming method includes a transfer step of transferring the toner onto a transfer body, and a cleaning step of removing an electrostatic image developing toner remaining on the electrostatic latent image carrier. An image forming method using a charge image developer.