JPH11143125A - Electrostatic charge image developing toner, production of electrostatic charge image developing toner, electrostatic charge image developer and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner having excellent electrification uniformity, electrification stability, image fixing property, image durability and shape controlling property. SOLUTION: This toner is obtd. by heating and melting either aggregated particles produced by aggregating resin particles in a dispersion liquid with dispersion of at least resin particles, or deposited particles produced by depositing fine particles on the aggregated particles in a fine particle dispersion liquid with dispersion of fine particles, and the toner has, on the surface thereof, an acid value carrying layer containing polar groups and having a crosslinked structure. The acid value measured by KOH titration is 5 to 40 mgKOH/g, and the apparent crosslinked density (ϕen) measured by dynamic viscoelasticity by sinusoidal wave vibration method is 1×10<-6> mol/cm<3> <=(ϕen)<=9×10<-9> mol/cm<3> . In this relation, ϕ is the front factor, e is the crosslinking rate and n is the apparent crosslinked density (mol/cm<3> ).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in charge uniformity, charge stability, image fixability, image durability, shape control, etc., and is preferably used for forming an image by electrophotography or the like. The present invention relates to a toner for image development, a method for efficiently producing the toner for electrostatic image development, and an electrostatic image developer and an image forming method using the toner for electrostatic image development.

[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, a charging step,
Forming an electrostatic image on the photoreceptor through an exposure step and the like, and developing the electrostatic image using a developer containing toner particles,
The electrostatic image is visualized through a transfer step, a fixing step, and the like.

As the developer, there are known a two-component developer containing toner particles and carrier particles, and a one-component developer containing magnetic toner particles or non-magnetic toner particles. ing. The toner particles in the developer are usually manufactured by a kneading and pulverizing method. In this kneading and pulverizing method, a thermoplastic resin or the like is melt-kneaded together with a pigment, a charge controlling agent, a release agent such as wax, and the like. After cooling, the melt-kneaded material is finely pulverized, and the resultant is classified to obtain desired toner particles. It is a manufacturing method. In addition, inorganic and / or organic fine particles may be further 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.

In the case of toner particles produced by the above-mentioned kneading and pulverizing method, the shape is usually irregular and the surface composition is not uniform. Although the shape and surface composition of the toner particles slightly change depending on the pulverizability of the materials used and the conditions of the pulverization process, it is difficult to intentionally control these to a desired degree. In the case of toner particles produced by the above-mentioned kneading and pulverizing method using a material having particularly high pulverizability, further pulverization or a change in the shape of the toner particles may be caused by various mechanical forces such as shearing force in a developing machine. Often happen. As a result, in the two-component developer, the finely divided toner particles adhere to the carrier surface to accelerate the charge deterioration of the developer, or in the one-component developer, the particle size distribution increases. , The pulverized toner particles are scattered, or the developing property is reduced due to the change in the toner shape,
There is a problem that the image quality is deteriorated.

When the shape of the toner particles is irregular, even if a fluidity aid is added, the fluidity is not sufficient, and the fine particles of the fluidity aid are removed by a mechanical force such as a shear force during use. There is a problem that the particles move to the concave portions of the particles and are buried in the concave portions, whereby the fluidity decreases over time, and the developability, transferability, cleaning performance, and the like deteriorate. Further, if such toner is collected by a cleaning process, returned to the developing device and reused, there is a problem that image quality is likely to deteriorate. In order to prevent these problems, it is conceivable to further increase the amount of the flow aid, but in this case,
There is a problem that black spots are generated on the photoreceptor and particles of the flow aid are scattered.

On the other hand, in the case of a toner in which a release agent such as wax is internally added, the release agent may be exposed on the surface of the toner particles depending on the combination with a thermoplastic resin. In particular, in the case of a toner obtained by combining a resin which is imparted with elasticity by a high molecular weight component and is hardly pulverized, and a brittle wax such as polyethylene, polyethylene is often exposed on the surface of the toner particles. Although such a toner is advantageous for the releasability at the time of fixing and cleaning of the untransferred toner from the photoreceptor, the polyethylene on the surface of the toner particles is affected by mechanical force such as shearing force in a developing machine. Since the toner particles are easily detached from the toner particles and easily transferred to a developing roll, a photoreceptor, a carrier, or the like, there is a problem that such contamination is likely to occur, and the reliability as a developer is reduced.

Under these circumstances, in recent years, as a means for producing a toner having a controlled particle shape and surface composition, for example, JP-A-63-282755 and JP-A-6-25.
No. 0439 proposes a method for producing a toner by an emulsion polymerization aggregation method. In the methods proposed in these publications, a resin particle dispersion is prepared by emulsion polymerization or the like, a colorant dispersion in which a colorant is dispersed in an aqueous medium (solvent) is prepared, and both are mixed. This is a method for producing toner by forming aggregated particles corresponding to the diameter and fusing them by heating.

However, in these methods, it is necessary to prepare a colorant dispersion in which a colorant is dispersed in an aqueous solvent in advance, but the average particle size of the colorant in the colorant dispersion is controlled. It is difficult to produce a toner having desired characteristics. In order to control the average particle size of the colorant in the colorant dispersion, the colorant is dispersed in an aqueous medium (solvent) to a desired particle size without agglomeration, sedimentation or precipitation, and A colorant dispersion liquid is required so that the colorants do not aggregate with each other even when the aggregated particles are formed together with the particles, but preparation of such a colorant dispersion liquid is not easy. That is, if the average particle size of the colorant in the colorant dispersion is large, the sedimentation or precipitation of the colorant, aggregation of the colorants with the nuclei of coarse particles, the formation of the colorant when forming the aggregated particles together with the resin particles. Various problems such as deterioration of chargeability due to liberation and exposure of the colorant to the toner surface and deterioration of light transmittance of the toner due to coarse particles occur. Further, when the average particle size of the colorant in the colorant dispersion is small, problems such as insufficient colorability of the obtained toner occur.

On the other hand, in recent years, the demand for higher image quality has increased,
In particular, in color image formation, in order to realize a high-definition image, the toner tends to have a smaller diameter and a uniform particle diameter. When an image is formed using a toner having a wide particle size distribution,
Due to the toner on the fine powder side in the particle size distribution, the problem of contamination of the developing roll, charging roll, charging blade, photoreceptor, carrier, etc. and toner scattering becomes remarkable, and it is difficult to realize high image quality and high reliability at the same time. is there. Further, such a toner having a wide particle size distribution has a problem that its reliability is poor even in a system having a cleaning function, a toner recycling function, and the like. In order to achieve high image quality and high reliability at the same time, it is necessary to sharpen the particle size distribution of the toner, to reduce the particle size, and to make the particle size uniform.

In order to solve these problems, for example, JP-A-62-73277 and JP-A-3-35660 propose a method of coating a so-called toner surface layer with a resin layer. However, with these methods,
Certainly, the influence of the colorant on the chargeability can be prevented, but it is difficult to contain a component having charge controllability, and it is difficult to improve the mechanical strength of the toner itself.

In order to solve this problem, Japanese Patent Laid-Open Publication No.
In Japanese Unexamined Patent Publication No. 2-73277, a charge control agent is added to the coating resin layer. In this case, as the number of copies is increased, the charge control agent is added similarly to the aforementioned colorant. The agent is likely to be exposed on the toner surface, which causes a problem in the durability of the toner. For this reason, a method of coating the surface of the toner particles in multiple stages has been proposed in JP-A-64-62666, JP-A-64-63035, and JP-B-58-57105. However, in these cases, there is a problem in balance between mechanical strength and chargeability, and there is a problem in that the process is complicated in manufacturing and disadvantageous in cost.

Further, a method for simultaneously satisfying both economy and chargeability has been proposed in Japanese Patent Application Laid-Open No. 8-286416. According to this method, although the manufacturability and charging performance are excellent, there is a problem that the inorganic dispersant is easily buried in the coating layer in the manufacturing method, so that the distribution of charged particles is large, and fog and scattering are caused. May cause In particular, when the number of printings is increased, the embedded inorganic dispersing material may be exposed, and this tendency becomes remarkable, especially under high temperature and high humidity.

In recent digital full-color copying machines and printers, color image originals are represented by B (blue),
(Red) and G (Green) after color separation, a latent image having a dot diameter of 20 to 70 μm corresponding to the original document is converted into Y (yellow), M (magenta), C (cyan), Using each developer of Bk (black), development is carried out by utilizing the subtractive color mixing action. In such a copying machine, it is necessary to transfer a large amount of developer compared to a conventional black and white machine, and it is necessary to correspond to a smaller dot diameter. Persistence, toner strength, and sharpness of particle size distribution are becoming increasingly important. Also, in view of the speeding up and energy saving of these copying machines, it is necessary to improve the low-temperature fixing property. From these points, a toner having a sharp particle size distribution and a small particle diameter is desired.

Further, in the case of a toner mounted on a full-color machine, a large amount of toner needs to be sufficiently mixed in color, so that improvement in color reproducibility and OHP transparency are essential. In the case of the toner, a polyolefin wax is generally added internally as a release agent component for the purpose of preventing low-temperature offset during fixing. In addition, a small amount of silicone oil is uniformly applied to the fixing roller to improve the high-temperature offset property. For this reason, a small amount of silicone oil adheres to the transfer material on which an image has been formed, and there is an unpleasant feeling of stickiness, which is not preferable. For this reason, Japanese Unexamined Patent Application Publication No.
In JP-A-61239 / 6, etc., an oil-less fixing toner in which a large amount of a release agent component is contained in a toner has been proposed, but none has been put to practical use yet.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention provides: 1. Various properties such as chargeability, developability, transferability, fixability, and cleaning property, in particular, charge uniformity, charge stability, image fixability, image durability, shape control, oilless fixation. It is an object of the present invention to provide a toner for developing an electrostatic image, which has excellent properties and the like, and satisfies high image quality and high reliability, and an electrostatic image developer using the toner for developing an electrostatic image. (2) An object of the present invention is to provide a toner for developing an electrostatic image which is suitable for a two-component electrostatic image developer having a high transfer efficiency, a small toner consumption and a long life. 3. An object of the present invention is to provide a method for producing an electrostatic image developing toner which can easily and simply produce an electrostatic image developing toner excellent in the above-mentioned characteristics without causing release of a colorant, a release agent, and the like. Aim. 4. An object of the present invention is to provide an image forming method capable of easily and easily forming a high-saturation full-color image on paper and OHP. 5 An object of the present invention is to provide an image forming method which is highly suitable for a so-called toner recycling system in which toner collected from a cleaner is reused and which can obtain high image quality.

[0016]

Means for solving the above problems are as follows. That is, <1> agglomerated particles obtained by aggregating the resin particles in a dispersion liquid in which at least the resin particles are dispersed, and attaching the fine particles to the aggregated particles in a fine particle dispersion liquid in which at least the fine particles are dispersed. Is obtained by heating and fusing any of the adhered particles having an acid value-bearing layer containing a polar group and having a crosslinked structure on the surface, and having an acid value determined by KOH titration of 5 to 40 mgKOH / g. And the apparent crosslink density (φen) obtained from the measurement of dynamic viscoelasticity by the sinusoidal vibration method is 1 × 10 ⁻⁶ mol / cm ³ ≦ (φen)
≦ 9 × 10 ⁻⁹ mol / cm ^3, which is a toner for developing electrostatic images. Here, φ represents a front factor, e represents a crosslinking reaction rate, and n represents an apparent crosslinking density (mol / cm ³ ). <2> 5 to 30% by weight in a state where the low softening point substance is dispersed
The toner for developing an electrostatic image according to the above <1>. <3> The electrostatic image developing toner according to <2>, wherein the low-softening point substance has a median diameter measured by a transmission electron microscope (TEM) of 100 to 3000 nm. <4> The thickness of the acid value-supporting layer measured by a transmission electron microscope (TEM) of 50 to 1000 nm is <1>.
<3> The electrostatic image developing toner according to any one of <1> to <3>. <5> The electrostatic image developing toner according to any one of <1> to <4>, wherein the shape factor SF1 satisfies 100 ≦ SF1 ≦ 130. <6> The electrostatic image developing toner according to any one of <1> to <5>, wherein the volume average particle diameter is 2 to 9 μm. <7> The above <1> in which the charge amount is 10 to 40 μC / g.
To <6>. <8> an aggregation step of aggregating the resin particles in a dispersion liquid in which at least the resin particles are dispersed to form aggregated particles;
A fusion step of heating and aggregating the aggregated particles, and a layer forming step of forming an acid value-bearing layer on the surface of the particles obtained by the fusion step; A method for producing a toner for developing an electrostatic image, comprising producing the toner for developing an electrostatic image described above. <9> After the aggregation step and before the fusion step, a fine particle dispersion liquid in which fine particles are dispersed is added to and mixed with the aggregate particle dispersion liquid in which the aggregate particles are dispersed, and the fine particles are attached to the aggregate particles. The method for producing a toner for developing an electrostatic image according to <8>, further comprising an adhering step of forming adhering particles by heating the adhering particles in the fusing step. <10> The method according to <9>, wherein the layer forming step is performed by a swelling polymerization method. <11> The method according to any one of <8> to <10>, wherein the average particle size of the resin particles is 1 μm or less. <12> At least one of the aggregated particles and the attached particles is
The method for producing a toner for developing an electrostatic image according to any one of <9> to <11>, further comprising a colorant. <13> The method for producing a toner for developing an electrostatic image according to any one of <8> to <12>, wherein the layer forming step is performed using 0.1 to 2% by weight of a polyfunctional monomer. It is. <14> An electrostatic image developer containing a carrier and a toner, wherein the toner is the electrostatic image developing toner according to any one of <1> to <7>. It is a developer. <15> The above-mentioned <1 wherein the carrier has a resin coating layer.
4>. <16> a step of forming an electrostatic latent image on the electrostatic latent image carrier, a step of developing the electrostatic latent image with a developer layer on the developer carrier, and forming a toner image; In an image forming method including a transfer step of transferring onto a transfer body and a cleaning step of removing an electrostatic image developing toner remaining on an electrostatic latent image carrier, the developer layer may be configured such that the above-mentioned <
An image forming method comprising the electrostatic image developing toner according to any one of <1> to <7>. <17> The image forming method according to <16>, wherein in the cleaning step, the removed toner for developing an electrostatic image is transferred to a developer layer.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The toner for developing an electrostatic image of the present invention has an acid value-bearing layer containing a polar group and having a crosslinked structure on the surface, and has an acid value determined by KOH titration of 5-4.
0 mgKOH / g and apparent crosslink density (φen) determined from the measurement of dynamic viscoelasticity by the sinusoidal vibration method
Is 1 × 10 ⁻⁶ mol / cm ³ ≦ (φen) ≦ 9 × 10
^-9 mol / cm ³ . The toner for developing an electrostatic image of the present invention is an agglomerated particle obtained by aggregating the resin particles in a dispersion liquid in which at least resin particles are dispersed, and the fine particles are dispersed in a fine particle dispersion liquid in which at least fine particles are dispersed. Any of the adhered particles adhered to the aggregated particles is obtained by heating and fusing, and can be suitably produced by the method for producing a toner for developing an electrostatic image of the present invention.

The method for producing a toner for developing an electrostatic charge image according to the present invention comprises an aggregating step of aggregating the resin particles in a dispersion in which at least the resin particles are dispersed to form agglomerated particles, and heating the agglomerated particles. Fusing step for fusing, including at least a layer forming step of forming an acid value supporting layer on the surface of the particles obtained by the fusing step, and may further include other steps as needed, for example, After the aggregating step and before the fusing step, in the agglomerated particle dispersion in which the agglomerated particles are dispersed, a fine particle dispersion in which fine particles are dispersed is added and mixed, and the fine particles are attached to the agglomerated particles. The method may suitably include an attachment step of forming attached particles by causing the particles to adhere. Hereinafter, the toner for developing an electrostatic image of the present invention,
The details will be clarified through the description of the method for manufacturing the electrostatic image developing toner of the present invention.

(Aggregating Step) The aggregating step is a step of forming agglomerated particles by aggregating the resin particles in a dispersion in which at least the resin particles are dispersed. In the dispersion,
In addition to the resin particles, colorant particles, release agent particles, and other particles may be dispersed. The dispersion is prepared by, for example, appropriately adding and mixing the resin particles, the colorant particles, the release agent particles, and the other particles in a dispersion medium such as a surfactant. Or a resin particle dispersion in which the resin particles are dispersed,
The colorant dispersion liquid in which the colorant particles are dispersed, the release agent particle dispersion liquid in which the release agent particles are dispersed, and the other particle dispersion liquid in which the other particles are dispersed are appropriately added. It may be prepared by mixing.

-Resin particles- The resin in the resin particles includes, for example, a thermoplastic binder resin, and specifically, homopolymers of styrenes such as styrene, parachlorostyrene and α-methylstyrene. Or a copolymer (styrene resin); methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid Homopolymers or copolymers (vinyl resins) of esters having a vinyl group such as n-propyl, lauryl methacrylate, 2-ethylhexyl methacrylate; homopolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile; Copolymer (vinyl resin); vinyl methyl ether, vinyl ether Homopolymers or copolymers of vinyl ethers such as butyl ether (vinyl resins); Homopolymers or copolymers of vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone (vinyl resins); ethylene , Homopolymers or copolymers of olefins such as propylene, butadiene and isoprene (olefin resins); non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins and polyether resins; And graft polymers of these non-vinyl condensation resins and vinyl monomers. 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 prepared by emulsion polymerization or seed polymerization using an ionic surfactant or the like.

As the vinyl monomer, for example,
Monomers that serve as raw materials for vinyl polymer acids and vinyl polymer bases such as acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, ethylene imine, vinyl pyridine, and vinyl amine. In the present invention, the resin particles preferably contain the vinyl-based 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. Acid, a dissociable vinyl monomer having a carboxyl group such as fumaric acid as a dissociating group,
It is particularly preferable in terms of controlling the degree of polymerization and the glass transition point.

The concentration of the dissociating group in the dissociable vinyl monomer may be 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 surface to the inside of the particles can be determined by the above method and the like.

The average particle size of the resin particles is usually
It is at most 1 μm (1 μm or less), and 0.01 to 1 μm.
It is preferably μm. If the average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image becomes wider or free particles are generated, which tends to lower the performance and reliability. On the other hand, when the average particle size is within the above range, there is no such defect, and uneven distribution between toners is reduced,
This is advantageous in that the dispersion in the toner becomes good and the dispersion in performance and reliability is reduced. The average particle size is
For example, it can be measured using a microtrack or the like.

-Colorant Particles- The colorant in the colorant particles is not particularly limited, and known pigments and dyes can be used. Examples of the pigment include a black pigment, a yellow pigment, an orange pigment, a red pigment, a blue pigment, a violet pigment, a green pigment, a white pigment, an extender, and the like.

Examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, non-magnetic ferrite, magnetite and the like.

The yellow pigments include, for example, graphite, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hanza yellow, Hanza yellow 10G, benzidine yellow G, benzidine yellow GR, slen yellow, quinoline yellow, and palme yellow. Nent Yellow NCG and the like.

Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indaslen brilliant orange RK, and indaslen brilliant orange GK.

As the red pigment, for example, red iron red, cadmium red, lead red, mercury sulfide, watch young red, permanent red 4R, lithol red,
Brilliant Carmine 3B, Brilliant Carmine 6
B, DuPont Oil Red, Pyrazolone Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Eoxin Red, Alizarin Lake and the like.

Examples of the blue pigment include navy blue, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, and indaslen blue.
BC, aniline blue, ultramarine blue, chalco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate and the like.

Examples of the purple pigment include manganese purple, fast violet B, methyl violet lake and the like. Examples of the green pigment include chromium oxide, chrome green, pigment green, phthalocyanine green, malachite green lake, and final yellow green G.

Examples of the white pigment include zinc white,
Examples include titanium oxide, antimony white, and zinc sulfide.
Examples of the extender include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

Examples of the dyes include various dyes such as basic, acidic, disperse, and direct dyes, such as acridine, xanthene, azo, benzoquinone, azine, anthraquinone, dioxazine, and thiazine.
Azomethine-based, indico-based, thioindico-based, phthalocyanine-based, aniline black-based, polymethine-based, triphenylmethane-based, diphenylmethane-based, thiazine-based, thiazole-based, xanthene-based dyes, and more specifically, nigrosine, methylene blue, Rose Bengal,
Quinoline yellow, ultramarine blue and the like.

These colorants may be used alone or in combination of two or more, and may be used in the form of a solid solution. When two or more kinds are used in combination, the color of the toner can be arbitrarily adjusted by changing the kind and the mixing ratio of the colorant (pigment).

The colorant is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, OHP permeability, and dispersibility in a toner. The amount of the colorant in the toner is:
It is 1 to 20% by weight based on the toner particles. In addition,
When a magnetic material is used as the black colorant, the toner particles are different from the other colorant particles by 30 to 70%.
% By weight.

The average particle size of the colorant particles is usually at most 1 μm (1 μm or less),
It is preferably about 1 μm. If the average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image becomes wider or free particles are generated, which tends to lower the performance and reliability. On the other hand, when the average particle size is in the above range, the above-mentioned disadvantages are not only eliminated, but uneven distribution between toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are advantageously reduced. The average particle size can be measured using, for example, a microtrack or the like.

-Release Agent Particles (Low Softening Point Substance)-As the release agent in the release agent particles, ASTM D
The main maximum peak measured according to 3418-8 is 5
Materials at 0-140 ° C are preferred. If the main maximum peak is less than 50 ° C., offset tends to occur during fixing, and if it exceeds 140 ° C., the fixing temperature becomes high, and the smoothness of the surface of the fixed image cannot be obtained, thus impairing the glossiness. In the present invention, such a release agent may be referred to as a “low softening point substance”.

For the measurement of the main maximum peak, a known measuring device can be used, for example, D-manufactured by Shimadzu Corporation.
SC-50 can be used. As the measurement conditions, the melting point of indium and zinc is used for temperature correction of the detection unit of the device, the heat of fusion of indium is used for correction of the amount of heat, an aluminum pan is used for the sample, The measurement conditions in which an empty pan is set for use and the temperature rise rate is 10 ° C./min can be adopted.

Examples of the release agent (low softening point substance) include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicones having a softening point upon heating; oleamide, erucamide, and ricinoleamide. And fatty acid amides such as stearic acid amide; vegetable waxes such as carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil;
Animal waxes such as beeswax; mineral and petroleum waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax; and modified products thereof. These release agents (low softening point substances) may be used alone or in combination of two or more.
Among these release agents (low softening point substances), those used in Examples described later are preferable.

The content of the release agent particles in the toner for developing an electrostatic image is preferably 5 to 30% by weight, and more preferably 8 to 30% by weight.
-25% by weight is more preferred. The content is 5% by weight.
If it is less than 30%, the releasability 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. If it exceeds 30% by weight, the toner becomes brittle, and In any case, the toner particles are easily crushed by stirring, and the fluidity, durability, chargeability, blocking property, and the like are reduced. 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 the storability of the toner.

The average particle size of the release agent particles is usually at most 1 μm (1 μm or less), and 0.01 μm or less.
It is preferably about 1 μm. If the average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image becomes wider or free particles are generated, which tends to lower the performance and reliability. On the other hand, when the average particle size is in the above range, the above-mentioned disadvantages are not only eliminated, but uneven distribution between toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are advantageously reduced. The average particle size can be measured using, for example, a microtrack or the like.

In the present invention, the release agent particles (low softening point substance) are preferably contained in the toner for developing an electrostatic image in a dispersed state. The softening point material) preferably has a median diameter of 100 to 3000 nm, more preferably 160 to 2500 nm, measured by a transmission electron microscope (TEM). When the median diameter is within the numerical range,
This is advantageous in that the obtained toner for developing an electrostatic image can be improved in oil-less fixability, chargeability, image durability and the like. On the other hand, if the median diameter is less than 100 nm, it tends to migrate to the toner surface during fixing, and
If it exceeds m, the transparency of the OHP tends to decrease.

The above-mentioned release agent is dispersed in an aqueous medium such as water together with a polymer electrolyte such as an ionic surfactant, a polymer acid or a polymer base, heated to a temperature higher than the melting point, and subjected to a strong shearing force. When it is processed using a homogenizer or a pressure discharge type disperser to which is applied, fine particles of 1 μm or less can be easily prepared.

-Other Particles- Examples of the other particles include internal additives, charge control agents, inorganic particles, organic particles, lubricants, abrasives, magnetic powders, and the like.

Examples of the internal additives include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, 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, aluminum,
Dyes composed of a complex such as iron and chromium, and triphenylmethane pigments are exemplified. As the charge control agent in the present invention, a material which is hardly soluble in water is preferable from the viewpoint of controlling ionic strength which affects stability at the time of aggregation and fusion and reducing wastewater contamination.

Examples of the inorganic particles include silica,
All particles usually used as an external additive on the surface of a toner, such as alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide, may be mentioned. Examples of the organic particles include all particles usually used as an external additive on the surface of a toner, such as a vinyl resin, a polyester resin, and a silicone resin. In addition, these inorganic particles and organic particles can be used as a flow aid, a cleaning aid, and the like.

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

Examples of the magnetic powder include substances that are magnetized in a magnetic field, such as ferromagnetic powders such as iron, cobalt, and nickel, and compounds such as ferrite and magnetite. When the magnetic powder is used, it is necessary to pay attention to the transfer property of the magnetic substance to an aqueous layer, and it is preferable that the magnetic substance is subjected to a surface modification such as a hydrophobic treatment.

The average particle size of the other particles is usually at most 1 μm (ie, 1 μm or less),
It is preferably from 1 to 1 μm. The average particle size is 1 μm
When the ratio exceeds, the particle size distribution of the finally obtained toner for developing an electrostatic image is widened, or free particles are generated, so that the performance and reliability are likely to be lowered. On the other hand, when the average particle size is in the above range, the above-mentioned disadvantages are not only eliminated, but uneven distribution between toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are advantageously reduced. The average particle size can be measured using, for example, a microtrack or the like.

When the dispersion contains not only the resin particles but also the colorant particles, the type of the colorant particles combined with the resin particles is not particularly limited. Can be selected freely as appropriate.

—Dispersion Medium— Examples of the dispersion medium in the dispersion include an aqueous medium. Examples of the aqueous medium include water such as distilled water and ion-exchanged water, and alcohols. These may be used alone or in combination of two or more.

In the present invention, it is preferable to add and mix a surfactant to the aqueous medium. Examples of the surfactant include anionic surfactants such as sulfate, sulfonate, phosphate, and soap; cationic surfactants such as amine salt and quaternary ammonium salt; polyethylene. Preferable examples include nonionic surfactants such as glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Of these, ionic surfactants are preferred, and anionic surfactants and cationic surfactants are more preferred.

The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic 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; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonylphenyl ether sulfate. Lauryl sulfonate, dodecyl sulfonate, dodecyl benzene sulfonate, sodium alkyl naphthalene sulfonate such as triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric amide sulfonate, olein Sulfonates such as acid amide sulfonates; lauryl phosphate, isopropyl Dialkyl sodium sulfosuccinates, such as sodium dioctyl sulfosuccinate, lauryl disodium sulfosuccinate; Sufeto, phosphoric acid esters such as nonyl phenyl ether phosphate
Sulfosuccinates, such as disodium lauryl polyoxyethylene sulfosuccinate; and the like.

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; and the like.

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;
Alkylamines 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 monopalmitate, polyoxyethylene Nso sorbitan monostearate,
Sorbitan ester ethers such as polyoxyethylene sorbitan monooleate; and the like.

In the case where the dispersion is prepared by mixing a resin particle dispersion in which the resin particles are dispersed and a colorant particle dispersion in which the colorant particles are dispersed, the resin in the dispersion is prepared by mixing The content of the particles may be 40% by weight or less, preferably about 2 to 20% by weight, and the content of the colorant may be 50% by weight or less, and 2 to 40% by weight. % Is preferable, and the content of the other components (particles) may be such that the object of the present invention is not impaired, and is generally extremely small. 0.01-5% by weight
And preferably about 0.5 to 2% by weight.

The method for preparing the dispersion or the resin particle dispersion is not particularly limited, and a method appropriately selected according to the purpose can be adopted. For example, the method can be prepared as follows. . When the resin in the resin particles is a homopolymer or copolymer (vinyl resin) of a vinyl monomer such as the ester having a vinyl group, the vinyl nitrile, the vinyl ether, or the vinyl ketone. The resin particles made of a homopolymer or copolymer (vinyl resin) of the vinyl monomer by subjecting the vinyl monomer to emulsion polymerization or seed polymerization in an ionic surfactant. A dispersion obtained by dispersing in an ionic surfactant can be prepared.

When the resin in the resin particles is a resin other than the homopolymer or copolymer of the vinyl monomer, the resin is dissolved in an oily solvent having a relatively low solubility in water. If, dissolve the resin in the oily solvent,
The solution is added to water together with the ionic surfactant and the polymer electrolyte, dispersed in fine particles using a disperser such as a homogenizer, and then prepared by evaporating the oily solvent by heating or reducing the pressure. can do.

The colorant particle dispersion can be prepared, for example, by dispersing the colorant in an aqueous medium such as the surfactant. The release agent particle dispersion is dispersed in water together with, for example, an ionic surfactant or a polymer electrolyte such as a polymer acid or a polymer base. This can be prepared by subjecting the release agent to fine particles by subjecting it to strong shearing using a homogenizer or a pressure discharge type disperser while heating the release agent to a temperature equal to or higher than the melting point of the release agent. The other particle dispersion can be prepared, for example, by dispersing other particles such as inorganic particles in an aqueous medium such as the surfactant.

When the dispersion or the resin particles dispersed in the resin particle dispersion are composite particles containing components other than the resin particles, the dispersion obtained by dispersing these composite particles is as follows: For example, it can be prepared as follows. For example, a method of dissolving and dispersing each component of the composite particles in a solvent, dispersing in water with an appropriate dispersant as described above, and removing the solvent by heating or reducing the pressure, emulsion polymerization, or the like. Alternatively, it can be prepared by performing mechanical shearing or electric adsorption on the surface of a latex prepared by seed polymerization or seed polymerization and immobilizing the resultant. When the composite particles include, for example, the resin and the colorant, it is advantageous in that the release of the colorant and the dependence of the chargeability of the toner on the colorant can be improved.

The dispersing means is not particularly limited, and examples thereof include a dispersing apparatus known per se such as a rotary shearing homogenizer, a ball mill having a media, a sand mill, and a dyno mill.

-Formation of agglomerated particles- The agglomerated particles are prepared, for example, as follows. To a first dispersion (resin particle dispersion) containing an aqueous medium to which the ionic surfactant is added and mixed, an ionic surfactant () having a polarity opposite to that of the ionic surfactant, or a mixture thereof is added. Aqueous medium () or a second dispersion containing the aqueous medium (resin particle dispersion, colorant particle dispersion, release agent particle dispersion,
(Other particle dispersions) are mixed.

When this mixed solution is stirred using a stirring means, the resin particles and the like are aggregated in the dispersion by the action of the ionic surfactant to form aggregated particles of the resin particles and the like. Is prepared. The stirring means is not particularly limited, and can be appropriately selected from known stirring devices and the like according to the purpose. The mixing is preferably performed at a temperature equal to or lower than the glass transition point of the resin of the resin particles contained in the liquid mixture. When the mixing is performed under this temperature condition, the aggregation can be performed in a stable state.

In the above case, aggregated particles formed by aggregating at least one of the resin particles dispersed in the first dispersion are formed. In the above case, agglomerated particles formed by aggregating at least one kind of resin particles and the like dispersed in the second dispersion and at least one kind of resin particles dispersed in the first dispersion are It is formed.

The agglomerated particles are formed by heteroaggregation or the like. For example, the balance between the polarity and the amount of the ionic surfactant contained in the dispersion to be added and the dispersion to be added is shifted in advance. It is formed by adding a polar / amount of an ionic surfactant so as to compensate for the deviation in balance. Specifically, the ionic surfactant contained in the dispersion to be added and the ionic surfactant contained in the side to be added are set to opposite polarities, and the balance of the polarities is previously shifted. It is preferable to compensate for this deviation in balance. That is, it is preferable to add the ionic surfactant contained in the liquid to be added to the ionic surfactant contained in the liquid to be added so as to compensate for this deviation in balance.

In general, depending on the type of the resin of the resin particles, the polarity thereof, and the like, aggregation may be difficult, and specific material particles may be released during aggregation, and a desired toner composition may not be obtained. When the release agent or the like is released, the inherent properties of the toner are impaired, and the released release agent overflows from the developing device during development and contaminates the inside of the developing device. The mechanical stress may cause problems such as destruction or coalescence and filming on the developing sleeve. However, when the aggregated particles are formed as described above, such a problem does not occur, for example,
Even if the polarity of the resin and the colorant in the resin particles is the same, by adding a surfactant of the opposite polarity, it is possible to easily form uniform aggregated particles by the resin particles and the colorant. This is advantageous in that it can be performed.

The average particle diameter of the aggregated particles formed in this aggregation step is not particularly limited, but is usually controlled so as to be substantially the same as the average particle diameter of the toner for developing an electrostatic image to be obtained. You. The control can be easily performed, for example, by appropriately setting and changing the temperature and the mixing / stirring conditions.

By the above-described aggregation step, the resin particles dispersion liquid mixed with each other, the resin particles dispersed in the colorant particle dispersion, the colorant particles, the release agent particles, and the like are aggregated to form aggregated particles. Then, an aggregated particle dispersion obtained by dispersing the aggregated particles is prepared. The agglomerated particles have an average particle size that is substantially the same as the average particle size of the electrostatic image developing toner. The content of the aggregated particles in the aggregated particle dispersion is usually 40
% By weight or less. In the present invention, the aggregated particles may be referred to as “base particles”, and it is preferable that the aggregated particles include the resin particles, the colorant particles, and the release agent particles.

(Adhering Step) The adhering step can be carried out as needed. A fine particle dispersion liquid in which fine particles are dispersed is added to the agglomerated particle dispersion liquid, and the fine particles are adhered to the agglomerated particles. This is a step of forming adhered particles.

In the adhering step, the agglomerated particles are used as the base particles, and the fine particles in the fine particle dispersion liquid added and mixed in the agglomerated particle dispersion liquid uniformly adhere to the surface thereof to form the adhered particles. . The adhered particles are formed by hetero-aggregation or the like. For example, the balance between the polarity and the amount of the ionic surfactant contained in the dispersion to be added and the dispersion to be added is shifted in advance, and the shift in the balance is performed. Is formed by adding a polar / amount of an ionic surfactant to make up for the ionic surfactant.

As the fine particles, for example,
Examples of the fine particles include resin fine particles made of the resin particles, colorant fine particles made of the colorant particles, release agent fine particles made of the release agent particles, and other fine particles made of the other particles. As the fine particle dispersion, a resin fine particle dispersion in which the resin fine particles are dispersed, a colorant fine particle dispersion in which the colorant fine particles are dispersed, a release agent fine particle dispersion in which the release agent fine particles are dispersed, Other fine particle dispersions in which other fine particles are dispersed are exemplified. These fine particle dispersions may be used alone or in combination of two or more.

Fine particles such as the resin fine particles are uniformly adhered to the surface of the aggregated particles to form adhered particles, and the adhered particles are heated and fused in a fusion step described later. In the case where an agent or the like is contained, these surfaces are covered with the material of the fine particles (a shell is formed), so that it is possible to effectively prevent the release agent and the like from being exposed from the toner particles. it can.

In the attaching step, for example, in the case of producing a multicolor electrostatic image developing toner, if the resin fine particles are used, a layer of the resin fine particles is formed on the surface of the aggregated particles. The effect of the coloring agent contained in the aggregated particles on the charging behavior can be minimized, and the difference in charging characteristics depending on the type of the coloring agent can be reduced. Further, if a resin having a high glass transition point is selected as the resin in the resin fine particles, a toner for developing an electrostatic charge image having both good heat preservability and fixability and excellent chargeability can be manufactured.

In the attaching step, the above-mentioned fine particle dispersion liquid is added and mixed, and then the fine particle dispersion liquid in which a resin or inorganic particles having a high hardness is dispersed as the fine particles is added and mixed. A shell made of a resin or inorganic particles having high hardness can be formed near the surface of the particles. In this case, the wax can effectively act as a release agent at the time of fixing while suppressing the exposure of the wax. As described above, for example, the surface of the aggregated particles can be coated with a resin or a charge control agent, and a colorant and a release agent can be present near the surface of the toner particles.

The average particle size of the fine particles is usually at most 1 μm (that is, 1 μm or less), and is 0.01 to 1 μm.
It is preferably μm. If the average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image becomes wider or free particles are generated, which tends to lower the performance and reliability. On the other hand, when the average particle size is within the above range, the above-mentioned disadvantages are not obtained, and it is advantageous in that a layer structure of fine particles is formed. The average particle size can be measured using, for example, a microtrack or the like.

The volume of the fine particles depends on the volume fraction of the toner for developing an electrostatic image, and is preferably 50% or less of the volume of the toner for developing an electrostatic image. When the volume of the fine particles exceeds 50% of the volume of the obtained toner for developing an electrostatic image, the fine particles do not adhere to or aggregate with the aggregated particles, and new aggregated particles are formed by the fine particles. The composition distribution and the particle size distribution of the toner for developing an electrostatic image may fluctuate significantly, and desired performance may not be obtained.

In the fine particle dispersion, one kind of these fine particles may be dispersed alone to prepare a fine particle dispersion, or two or more kinds of fine particles may be used in combination to prepare a fine particle dispersion. You may. In the latter case, the combination of the fine particles used in combination is not particularly limited, and can be appropriately selected depending on the purpose.

Examples of the dispersion medium in the fine particle dispersion include the above-mentioned aqueous medium. In the present invention, it is preferable that at least one of the above-mentioned surfactants is added to and mixed with the aqueous medium.

The content of the fine particles in the fine particle dispersion is usually 5 to 60% by weight, preferably 10 to 40% by weight. If the content is outside the above range, the control of the structure and composition from the inside to the surface of the toner for developing an electrostatic image may not be sufficient.

The fine particle dispersion is prepared, for example, by dispersing at least one kind of the fine particles in an aqueous medium to which an ionic surfactant or the like is added and mixed. Further, it can be prepared by mechanically shearing or electrically adsorbing and immobilizing on a latex surface prepared by emulsion polymerization or seed polymerization.

In this attaching step, the fine particles are attached to the surface of the agglomerated particles to form attached particles. Since the fine particles correspond to newly added particles as viewed from the aggregated particles, they may be referred to as “additional particles” in the present invention.

The method of adding and mixing the fine particle dispersion liquid in the adhering step is not particularly limited. For example, the method may be performed gradually and continuously, or may be performed in a plurality of steps and stepwise. Is also good. Thus, by adding and mixing the fine particles (additional particles), the generation of fine particles can be suppressed, and the particle size distribution of the obtained toner for developing an electrostatic image can be sharpened. Further, the composition and physical properties from the surface to the inside of the obtained electrostatic image developing toner can be changed stepwise, and the structure of the electrostatic image developing toner can be easily controlled.

In the above, when the resin in the resin particles and the fine particles is selected so that the glass transition point of the resin existing outside the toner is higher than the glass transition point of the resin existing inside the toner, It is possible to achieve both the storage stability and fluidity of the toner and the minimum fixing temperature. Further, by increasing the molecular weight of the resin on the polymer side and increasing the elasticity in the molten state, offset to the heat roll at a high temperature can be prevented. This effect is an extremely effective means especially when oil application is not performed.

Further, when the molecular weight of the resin existing outside the toner (ie, the resin in the fine particles) is selected to be smaller than the molecular weight of the resin existing inside the toner (ie, the resin in the aggregated particles). Since the smoothness of the surface of the obtained toner particles is increased, the fluidity and transfer performance are easily improved. However, when the agglomerated particles are not formed of one type of resin fine particles, that is, when two or more types of resin particles are agglomerated, the resin existing inside the toner (that is, The molecular weight of the (resin) means the average value of the molecular weights of all the resins contained in the aggregated particles.

The molecular weight of the resin existing outside the toner,
If the molecular weight of the resin present inside the toner is extremely different, the resulting toner particles may have a low adhesive strength between the core and the coating layer portion. When a mechanical stress such as stirring or mixing with a carrier is applied, the toner particles may be destroyed. Therefore, when attaching the fine particles to the aggregated particles, first, resin fine particles having an intermediate molecular weight and / or a glass transition point between the resin existing inside the toner and the resin existing inside the toner are used. The resin particles can be attached to the aggregated particles, and then the selected resin fine particles can be attached.

When the fine particle dispersion liquid is divided into a plurality of times and added and mixed stepwise into the aggregated particle dispersion liquid, a layer of the fine particles is layered stepwise on the surface of the aggregated particles to form an electrostatic charge image. A structural change or composition gradient can be imparted from the inside to the outside of the particles of the developing toner, physical properties can be changed, the surface hardness of the particles can be improved, and at the time of fusing in a fusing step described later. In addition to maintaining the particle size distribution and suppressing its fluctuation, the addition of a surfactant or a stabilizer such as a base or an acid for enhancing the stability at the time of fusion becomes unnecessary, and the amount of these additives is minimized. This is advantageous in that it can be suppressed to the limit, and cost reduction and quality improvement can be achieved.

The conditions for adhering the fine particles to the agglomerated particles are as follows. That is, the temperature is not higher than the glass transition point of the resin in the resin particles in the aggregating step, and is preferably about room temperature. When heating is performed at a temperature equal to or lower than the glass transition point, the aggregated particles and the fine particles easily adhere to each other, and as a result, the formed adhered particles are easily stabilized. Since the treatment time depends on the temperature, it cannot be specified unconditionally, but is usually about 5 minutes to 2 hours. In addition, at the time of the adhesion, the dispersion liquid 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 case is advantageous in that uniform adhered particles are easily formed.

In the present invention, the number of times this adhesion step is performed may be one or a plurality of times. In the former case, only one layer of the fine particles (additional particles) is formed on the surface of the aggregated particles,
In the latter case, if two or more kinds of fine particle dispersions are prepared, a layer of fine particles (additional particles) contained in these fine particle dispersions is formed on the surface of the aggregated particles. The latter case is advantageous in that a toner for developing an electrostatic image having a complicated and precise hierarchical structure can be obtained, and a desired function can be imparted to the toner for developing an electrostatic image.

When the attaching step is performed a plurality of times, the fine particles (additional particles) to be attached first and the fine particles (additional particles) to be attached subsequently to the aggregated particles (base particles) may be in any combination. It may be appropriately selected depending on the use of the electrostatic image developing toner and the like.

When the adhering step is performed a plurality of times, each time the fine particles are added and mixed, the dispersion liquid containing the fine particles and the agglomerated particles is changed to a temperature below the glass transition point of the resin in the resin particles in the aggregating step. A mode in which heating is performed at a temperature is preferable, and a mode in which the heating temperature is increased stepwise is more preferable. This is advantageous in that the attached particles can be stabilized and the generation of free particles can be suppressed.

When the adhering step is performed a plurality of times, adhered particles formed by adhering the fine particles to the agglomerated particles prepared in the aggregating step a plurality of times are formed. Therefore,
In the attaching step, by appropriately selecting fine particles to the aggregated 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 finally becomes the distribution of the colorant in the toner particles. Therefore, the finer and more uniform the dispersion of the colorant in the attached particles, the more the resulting electrostatic image development becomes. The color development of the toner is improved.

(Fusing step) In the fusing step, the agglomerated particles are treated with the adhering particles when the adhering step is carried out.
This is a step of heating and fusing to form toner particles.

The heating temperature may be a temperature between the glass transition temperature of the resin contained in the agglomerated particles and the glass transition temperature of the resin contained in the adhered particles in the case of performing the adhering step, to the decomposition temperature of the resin. Good. Accordingly, the heating temperature varies depending on the type of the resin of the resin particles (and the fine particles), and cannot be specified unconditionally. When performed, the glass transition temperature of the resin contained in the adhered particles is 180 ° C. By appropriately 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.

As the fusion time, a short time is sufficient if the heating temperature is high, and a long time is necessary if the heating temperature is low. That is, the fusion time depends on the heating temperature and cannot be specified unconditionally, but is generally 30 minutes to 10 hours.

By the above-described fusion step, the aggregated particles (base particles) are fused, and when the adhesion step is performed, the fine particles (additional particles) are adhered to the surface of the aggregated particles, The adhered particles prepared in the attaching step are fused.

(Layer Forming Step) The layer forming step is a step of forming an acid value-carrying layer on the surface of the particles obtained by the fusing step. The formation of the acid value-carrying layer can be carried out by using, for example, swelling polymerization, emulsion polymerization, hetero-aggregation, etc. In the present invention, among these, it is particularly preferable to carry out swelling polymerization. In the case of the swelling polymerization,
In the layer forming step, an appropriate amount of a specific polar resin and a reactive diluent containing a specific cross-linking agent (cross-linking structure forming agent) are added to the agglomerated particle dispersion and swelled for a desired time. Thereafter, the acid value supporting layer is formed on the surface of the aggregated particles by heating.

-Polar resin- The polar resin is an acid value-imparting component added to the reactive diluent described above, and is preferably a polymer or copolymer having a polar group. In the layer forming step, the polar resin is usually dissolved by adding 1 to 30 parts by weight to 100 parts by weight of the reactive diluent. The polymer or copolymer having these polar groups gathers in the vicinity of the surface of the aggregated particles (base particles) in water due to its polarity in water and forms a shell. The surface can be replaced with any resin component. For this reason, plasticization generally occurring when the layer formed by swelling polymerization is a thin layer is suppressed, and excellent characteristics in both chargeability and toner strength are obtained. The amount of the polar resin is more preferably 5 to 20 parts by weight. When the addition amount is less than 1 part by weight, it becomes difficult to form the acid value-carrying layer, and there is a problem in production stability. When the addition amount exceeds 30 parts by weight, the solution viscosity during swelling polymerization is reduced. Too high,
It is not preferable because of poor film formability.

The acid value of the polar resin is preferably from 5 to 40 mgKOH, as determined by KOH titration, from the viewpoint of preventing the plasticization of the acid value-bearing layer and improving the chargeability. More preferably, it is 25 mg KOH. If the acid value determined by the KOH titration is less than 5 mgKOH, it is difficult to form an acid value-supporting layer on the surface of the particles obtained in the fusion step, and if it exceeds 40 mgKOH, it is difficult to swell during swelling polymerization. However, it is not preferable because the film formability is poor. On the other hand, when the acid value obtained by the KOH titration is within the above numerical range, the above problem does not occur, and the generation of plasticity due to the formation of the dissolved mixed layer during the formation of the acid value supporting layer is effectively suppressed. This is advantageous in that the acid value supporting layer can be efficiently formed.

Representative examples of the polar resin include methacrylic acid-acrylic acid copolymer, ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,4-butane. Dihydric alcohols such as diol, neopentyl glycol, 1,4-butenediol, 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol A, oxyethylenated bisphenol A, and terephthalic acid, maleic acid, Polyesters comprising phthalic acid, isophthalic acid, succinic acid, adipic acid, malonic acid, etc., and anhydrides, esters of these with lower alcohols, and derivatives thereof, are preferred.

—Crosslinking Agent (Crosslinking Structure-Forming Agent) — The crosslinking agent (crosslinking structure-forming agent) is not particularly limited as long as it is a polyfunctional monomer, but a bifunctional monomer is preferably used. The difunctional monomer is not particularly limited, but includes, for example, divinylbenzene, diethylaminopropyl methacrylate, diglycidyl methacrylate, ethylene dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and dimethacrylic acid. Examples include decaethylene glycol, pentaethylene glycol dimethacrylate, pentacontactor dimethacrylate, allyl methacrylate, 1,3-butylene ethylene glycol dimethacrylate, diethylene glycol dimethacrylate phthalate, and diallyl terephthalate.

The amount of the crosslinking agent (crosslinking structure forming agent) added to the aggregated particle dispersion is preferably 0.1 to 2% by weight, more preferably 0.3 to 1.0% by weight. When the addition amount is less than 0.1% by weight, the chargeability is improved, but a crosslinked structure is hardly obtained, and the image durability is hardly improved. Both are not preferred because they impair. On the other hand, when the addition amount is within the numerical range, the crosslinking agent (crosslinking structure forming agent)
Is advantageous in that the chargeability of the obtained electrostatic image developing toner can be further improved.

-Reactive diluent-The reactive diluent is not particularly limited and may be appropriately selected from known ones according to the purpose.
For example, styrene monomers such as styrene, parachlorostyrene, α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, and n-acrylate
Esters having a vinyl group such as butyl, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, acrylonitrile, methacrylonitrile, etc. Vinyl nitriles, vinyl methyl ethers, vinyl ethers such as vinyl isobutyl ether, vinyl methyl ketones, vinyl ethyl ketones, vinyl ketones such as vinyl isopropenyl ketone, and monomers such as ethylene, propylene, butadiene, and polyolefins. Can be

These may be used alone, or
Two or more kinds may be used in combination. Among these, a hydrophobic monomer is preferable, and styrene and a styrene derivative are particularly preferable. In the present invention, using one of these alone or in combination of two or more enhances the adsorptivity to the aggregated particles, In addition, it is preferable in that durability can be enhanced.

In the layer forming step, the amount of the reactive diluent and the reaction (swelling) time are appropriately selected according to the desired layer thickness, shape, and the like. From the point, the shape factor SF1 is 100 ≦ SF1 ≦ 1
Preferably, it is selected to be 30. The average value of the shape coefficients (square of perimeter / projected area) is calculated by, for example, the following method. That is, an optical microscope image of the toner scattered on the slide glass is taken into a Luzex image analyzer through a video camera, and the square of the perimeter of 50 or more toners / projected area (ML ² / A) is calculated, and the average value is calculated. Is calculated.

In the layer forming step, a polymerization initiator can be suitably used. The polymerization initiator is not particularly limited. Examples of the water-soluble initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, and hydrogen peroxide. In addition, examples of the oil-soluble initiator include known azo-based initiators, azide-based initiators, and peroxide-based initiators. For example, 2,2-
Azobis- (2,4-divaleronitrile), 2,2-azobis (cyclohexane-1-carbonitrile), 2,
Azo or diazo initiators such as 2-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxy carbonate, cumene hydroperoxide, Peroxide initiators such as 1,4-dichlorobenzoyl peroxide and lauroyl peroxide. These may be used alone or in combination of two or more.

The amount of the polymerization initiator to be added is usually 0.1 to 20 parts by weight, and 0.5 to 5 parts by weight based on 100 parts by weight of the total of the reactive diluent and the polar resin. Parts are preferred. If the amount is less than 0.1 part by weight, a sufficient reaction cannot be obtained. If the amount exceeds 20 parts by weight, not only is it economically disadvantageous, but also self-emulsifying particles increase, so that the stability of the swelling polymerization system is increased. Is impaired.

By the layer forming step, an acid value carrying layer containing a polar group and having a crosslinked structure is formed on the surface of the particles obtained by the fusing step. After completion of the layer forming step (swelling polymerization), the particles are washed, separated into solid and liquid, and dried to obtain a desired toner for developing an electrostatic image. It is preferable that the washing be sufficiently performed by replacement washing with ion exchanged water from the viewpoint of chargeability. The solid-liquid separation,
Although there is no particular limitation, suction filtration, pressure filtration and the like are preferred from the viewpoint of productivity. The drying is not particularly limited in the method,
From the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration type fluidized drying and the like are preferred.

In the above-mentioned 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 particles. There is no need to remove the generated fine powder, which is advantageous in that the process can be simplified. Further, since at least the resin particles and the colorant are uniformly dispersed or fused to form aggregates aggregated in an intentionally localized state, toner particles are formed. Can be controlled uniformly or intentionally. 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 on the surface of the toner particles can be reduced.

The toner for developing an electrostatic image of the present invention obtained as described above has an acid value carrying layer containing a polar group and having a crosslinked structure on the surface, and has an acid value determined by KOH titration of 5 to 5. 40 mgKOH / g, and the apparent crosslink density (φ
en) is 1 × 10 ⁻⁶ mol / cm ³ ≦ (φen) ≦ 9
× 10 ⁻⁹ mol / cm ³ . The electrostatic image developing toner of the present invention that satisfies these requirements is excellent in uniform chargeability, charge stability, image quality durability, image fixability, and the like, and can control the shape factor SF1 to 100 ≦ SF1 ≦ 130. Excellent controllability.

In order to verify the crosslinked structure, measurement and calculation of storage elastic modulus G ′, loss elastic modulus G ″, and loss tangent tan δ by dynamic viscoelasticity measurement (temperature dispersion measurement) according to a sinusoidal vibration method. Is preferably used.

In the measurement of the dynamic viscoelasticity, usually, the toner for developing an electrostatic image is formed into a tablet, set on a parallel plate having a diameter of 8 mm, the normal force is set to 0, and the vibration frequency is 6.28 rad / sec. To give vibration.
The measurement starts at 40 ° C and lasts up to 200 ° C. The measurement time interval is 120 seconds, and the temperature rise rate after the start of the measurement is 1 ° C./min. During the measurement, the amount of strain is appropriately maintained at each measurement temperature, and adjusted appropriately so as to obtain an appropriate measurement value.

When a rubber-like flat area (plateau area) was observed, the apparent crosslink density was calculated from the following equation using the value of the storage elastic modulus G 'at the center temperature, and this was used as the value in the present invention. Crosslink density.

Apparent crosslinking density (G′e) = 3φenRT φ: front factor, e: crosslinking reaction rate, n: apparent crosslinking density (mol / cm ³ ), R: gas constant (J / m)
ol), T: temperature (K), G'e: storage modulus of rubbery region (10 ^-5 N / cm ² )

The apparent crosslink density (φen) determined from the measurement of dynamic viscoelasticity by the sinusoidal vibration method described above is as follows:
1 × 10 ⁻⁶ mol / cm ³ ≦ (φen) ≦ 9 × 10 ^-9 m
ol / cm ³ is advantageous in that the strength and durability of the toner for developing an electrostatic image can be improved, and as a result, the image durability can be greatly improved.

The toner for developing an electrostatic image of the present invention has a structure in which the surface of the agglomerated particles is coated with the acid value-carrying layer. And the fine particles (additional particles) on the surface of the base particles.
Is formed, and the surface of the layer is coated with the acid value supporting layer. The layer of the fine particles (additional particles) may be a single layer or two or more layers. In general, the number of layers is determined by the amount of the adhesion in the method for producing the electrostatic image developing toner of the present invention. This is the same as the number of times the process has been performed.

The thickness of the acid value-carrying layer is 50 to 1000 nm from the surface of the electrostatic image developing toner particles as observed by a transmission electron microscope (TEM). If the thickness is less than 50 nm, plasticization is likely to occur due to mixing with the resin particles, and if it exceeds 1000 nm, swelling and adhesion failure is likely to occur.

The volume average particle diameter of the toner for developing electrostatic images is preferably 2 to 9 μm, more preferably 3 to 8 μm. When the volume average particle size is less than 2 μm, the chargeability is likely to be insufficient, and the developability may be reduced,
If it exceeds 9 μm, the resolution of the image may be reduced.
The volume average particle size can be measured using a known particle size measuring device, for example, Coulter Counter TA (manufactured by Nikkaki), Multisizer (manufactured by Nikkaki), or the like.

Further, the number average particle size index (GSDp) of the average particle size of the toner for developing an electrostatic image is preferably 1.25 or less. The number average particle size index (GSDp) and the volume average particle size distribution index (GSDv) are obtained by dividing a particle size distribution measured using the particle size measuring device into a volume, a number, In each case, the cumulative distribution is drawn from the smaller diameter side, and the particle size at which the cumulative value is 16% is defined as volume D16% or several 16%.
It is defined as 0% or the number D50%. Further, it is defined as a volume D84% or a number D84%. Using these, the volume average particle size distribution index (GSDv) is calculated as follows: volume D84% / volume D84
%, And the number average particle size index (GSDp) is
It is calculated from 84% / number D84%.

The charge amount of the toner for developing an electrostatic image is preferably 10 to 40 μC / g, and more preferably 15 to 35 μC / g.
g is more preferred. If the charge amount is less than 10 μC / g, background stains are likely to occur, and if it exceeds 40 μC / g, the image density tends to decrease. The ratio between the amount of charge in summer and the amount of charge in winter of the electrostatic image developing toner is preferably 0.5 to 1.5,
0.7-1.3 is preferred. If the ratio is out of the preferred range, the toner is highly dependent on the environment and lacks in charge stability, which may not be practically preferable.

In the toner for developing an electrostatic image of the present invention,
The molecular weight distribution represented by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured using gel permeation chromatography is 4 to 30.
Is preferable, 4-20 are more preferable, and 5-15 are especially preferable. When the molecular weight distribution represented by the ratio (Mw / Mn) exceeds 30, the light transmittance and coloring properties are not sufficient,
In particular, when a toner for developing an electrostatic image is developed or fixed on a film, an image projected by light transmission becomes a blurred and dark image or a projection image which is not transparent and does not develop a color. At the time of fixing, the viscosity of the toner is remarkably reduced, and offset tends to occur. On the other hand, when the molecular weight distribution represented by the ratio (Mw / Mn) is within the above numerical range, the light transmittance and the coloring property are sufficient, and the viscosity of the electrostatic image developing toner at the time of high-temperature fixing decreases. Can be prevented, and the occurrence of offset can be effectively suppressed.

An external additive can be used in the electrostatic image developing toner of the present invention. Examples of the external additive include a flow aid, a cleaning aid, and the like. Examples of the fluidity aid and the cleaning aid include silica, alumina, titania, inorganic particles such as calcium carbonate, vinyl resin, polyester, resin fine particles such as silicone, and the like. To the surface of the toner for developing an electrostatic image.

The toner for developing an electrostatic charge image of the present invention has various properties such as chargeability, developability, transferability, fixability and cleaning property, in particular, charge uniformity, charge stability, image fixability, image durability, and the like. Excellent shape controllability, oil-less fixability, etc. In addition, the above performances are stably exhibited without being affected by environmental conditions.
Maintain, high reliability. Since the electrostatic image developing toner is manufactured by the method of manufacturing an electrostatic image developing toner of the present invention, unlike the case of being manufactured by the kneading and pulverizing method, the average particle diameter is small, and The distribution is sharp.

The electrostatic image developer of the present invention is not particularly limited except that it contains the toner for developing an electrostatic image of the present invention, and can have an appropriate component composition according to the purpose. The electrostatic image developer of the present invention is prepared as a one-component electrostatic image developer by using the electrostatic image developing toner of the present invention alone, or a two-component electrostatic image developer by using in combination with a carrier. As an electrostatic image developer. The carrier is not particularly limited and includes a carrier known per se. 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. In the electrostatic image developer, as the mixing ratio of the electrostatic image developing toner of the present invention and a carrier,
There is no particular limitation, and it can be appropriately selected according to 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. Each of the above steps is a general step itself, for example, as described in JP-A-56-40868 and JP-A-
No. 9-91231. The image forming method of the present invention can be carried out by using a known image forming apparatus such as a copying machine or a facsimile machine.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier. The toner image forming step is a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the toner for developing an electrostatic image of the present invention. The transfer step is a step of transferring the toner image onto a transfer member. The cleaning step is a step of removing the electrostatic image developer remaining on the electrostatic latent image carrier.

In the image forming method of the present invention, it is preferable that the cleaning step further includes a toner recycling step of transferring the collected electrostatic image developing toner to the developer layer. The image forming method of the embodiment 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 at the same time as the development.

[0129]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited to these examples. In the following, the glass transition point of the resin in the resin particles and the toner particles was measured using a differential scanning calorimeter (DSC-50, manufactured by Shimadzu Corporation) under the condition of a heating rate of 3 ° C./min.

Example 1 Preparation of Resin Particle Dispersion (1) Styrene 370 g n-butyl acrylate 30 g acrylic acid 6 g dodecanethiol 24 g carbon tetrabromide 4 g or more 6 g of a nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and 10 g of anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
g was dissolved in 550 g of ion-exchanged water in a flask, dispersed in a flask, emulsified, and slowly mixed for 10 minutes. After purging with nitrogen, the contents in the flask were heated in an oil bath until the temperature of the flask reached 70 ° C. while stirring, and the emulsion polymerization was continued for 5 hours. Thereafter, the reaction solution was cooled to room temperature, and then left in an oven at 80 ° C. to remove water, whereby the average particle size was 155 nm, and the glass transition point was 59%.
A resin particle dispersion liquid (1) was prepared by dispersing resin particles having a weight average molecular weight (Mw) of 13,000 at 1 ° C.

Preparation of Resin Particle Dispersion (2) Styrene 280 g n-butyl acrylate 120 g Acrylic acid 8 g or more were mixed and dissolved, and 6 g of a nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.) (Neogen R)
In a flask prepared by dissolving 12 g of ion-exchanged water in 550 g, dispersed in a flask, emulsified, and slowly mixed for 10 minutes. Then, after purging with nitrogen, while stirring the inside of the flask, the content was heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued as it was for 5 hours. Thereafter, the reaction solution was cooled to room temperature, and then left on an oven at 80 ° C. to remove water, whereby the average particle size was 105 nm, the glass transition point was 53 ° C.,
A resin particle dispersion liquid (2) was prepared by dispersing resin particles having a weight average molecular weight (Mw) of 550,000.

-Preparation of Colorant Dispersion (1)-Carbon Black ... 50 g (Cabot Corporation: Mogar L) Nonionic surfactant ... 5 g (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) Ion-exchanged water: 200 g or more were mixed and dissolved, and a homogenizer (manufactured by IKA)
Colorant dispersion liquid (1) obtained by dispersing a colorant (magenta pigment) by dispersing for 10 minutes using (Ultra Tax).
Was prepared. The average particle size of the colorant in the colorant dispersion liquid (1) was 250 nm.

Preparation of Release Agent Dispersion (1) Paraffin Wax 50 g (HNP0190, manufactured by Nippon Seiro Co., Ltd., melting point 85 ° C.) Cationic surfactant 5 g (Kao Corporation: Sanisol B50) Ion-exchanged water 200 g or more are mixed and dissolved, and a homogenizer (manufactured by IKA,
(Ultratax) for 10 minutes to prepare a release agent dispersion liquid (1) in which a release agent (paraffin wax) is dispersed. The average particle size of the release agent in the release agent dispersion liquid (1) was 550 nm.

<Aggregating Step> Resin Particle Dispersion (1) ... 120 g Resin Particle Dispersion (2) ... 80 g Colorant Dispersion (1) ... 30 g Release agent dispersion (1) 40 g Cationic surfactant 1.5 g (Sanisol B50 manufactured by Kao Corporation) The above was placed in a round stainless steel flask, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and then heated to 48 ° C. in a heating oil bath. The obtained aggregated particles were measured using a Coulter counter (manufactured by Coulter, TA2 type) and found to be 5.5 μm.

<Adhesion Step> -Preparation of Adhered Particles- After keeping the aggregated particle dispersion at 48 ° C. for 30 minutes, the resin particle dispersion (1) as a resin fine particle dispersion was added to the aggregated particle dispersion. 60 g was gradually added, and the temperature of the oil bath for heating was further increased and maintained at 50 ° C. for 1 hour.
The obtained adhered particles were measured using a Coulter counter (TA2, manufactured by Coulter, Inc.) and found to be 5.8.
μm.

<Fusing Step> After adding 3 g of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen R), the mixture was heated to 97 ° C. while continuing stirring and maintained for 3 hours. Thereafter, the mixture was cooled, filtered, washed with ion-exchanged water, and dried using a vacuum drier to obtain aggregated particles.

When the obtained fused particles were measured using a Coulter counter (TA2, manufactured by Coulter Co.), the volume average particle size (D50%) was 5.7 μm.
The particle size distribution coefficient GSD was 1.24. Further, the shape factor S of the fused particles obtained from shape observation by Luzex
F1 was 134 and was observed to be potato-shaped. Further, from a cross-sectional image of the fused particles observed with a transmission electron microscope (TEM), it was confirmed that the low softening point substance was dispersed in the fused particles, and that the arithmetic average diameter was 160 nm.

<Layer forming step> -Preparation of polar resin solution- Styrene 82.5 g Butyl acrylate 17.5 g Divinylbenzene 0.6 g (manufactured by Wako Pure Chemical Industries) Terephthalic acid-PO-modified bisphenol A-trimellitic acid-based polyester (acid value: 11.5, manufactured by Sanyo Chemical Co., Ltd.) Stir, dissolve and mix in ³ beakers.

After the dispersion in which the fused particles obtained in the above-mentioned fusion step were dispersed was cooled to 25 ° C., the pH of the dispersion was adjusted to 10.0 with sodium carbonate. Then, 43.2 g of the polar resin solution was dropped at a speed of 1.49 g / min while stirring at a blade tip peripheral speed of 60 m / min. After stirring was continued for 10 minutes, 0.65 g of ammonium persulfate was added, the temperature was raised to 70 ° C at a rate of 1 ° C / min, and the mixture was heated at 70 ° C for 7 hours to react. As described above, an acid value supporting layer containing a polar group and having a crosslinked structure was formed on the surface of the fused particles.

After the completion of the above reaction, the reaction solution was cooled, filtered,
After sufficiently washing with ion-exchanged water, solid-liquid separation was performed by Nutsche suction filtration. This was further redispersed in 3 L of ion exchange water at 40 ° C., and stirred at 300 rpm for 15 minutes.
Washed. This operation was further repeated 5 times, and the pH of the filtrate was 6.54, the electric conductivity was 6.7 μS / cm, and the surface tension was 7
When the pressure reached 0.2 N / m, solid-liquid separation was performed by Nutsche suction filtration using No. 5A filter paper. Then
Vacuum drying was continued for 12 hours on the obtained toner particles for electrostatic image development.

-Characteristics of Toner for Developing an Electrostatic Image- When this toner for developing an electrostatic image was evaluated, the particle size measured by a Coulter counter was 6.32 μm, and the volume G
SD was 1.21, shape factor SF1 was 121, and it was observed that it was spherical. As a result of observing the toner for developing an electrostatic image using a transmission electron microscope (TEM), according to a cross-sectional image of the toner for developing an electrostatic image, a substance having a low softening point was found in the toner particles for developing an electrostatic image. It was dispersed, and it was confirmed that the arithmetic mean diameter was 320 nm.

The thickness of the acid value carrying layer of this toner for developing an electrostatic image was observed by a transmission electron microscope (TEM) to be 150 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RD.
AII (manufactured by Rheometric Co.), the toner for developing an electrostatic image was observed to have a rubber-like flat area, and the apparent crosslink density calculated from the storage modulus G ′ at 140 ° C. (Φen) is 6.4 × 10 ⁻⁷ mol /
cm ³ , and the acid value determined by KOH titration was 13.7 m.
gKOH.

Next, using this toner for developing an electrostatic image, the chargeability of the non-externally added toner was determined as Q / M, and the chargeability at 28 ° C. and the humidity of 8 was measured.
When evaluated under an environment of 5%, the evaluation was as good as −24 μC / g. When the chargeability was similarly evaluated in an environment at 10 ° C. and a humidity of 30%, it was -26 μC / g, and almost no environmental difference was recognized.

-Production of Electrostatic Image Developer- Hydrophobic silica (TS720: manufactured by Cabot) was added to 50 g of the electrostatic image developing toner, and blended in a sample mill. This blend was weighed to a ferrite carrier coated with 1% of methacrylate (manufactured by Soken Chemical Co., Ltd.) having an average particle size of 50 μm so that the toner concentration became 5%, and stirred and mixed with a ball mill for 5 minutes to develop an electrostatic image. An agent was prepared. The chargeability of the externally added toner was −27 μC / g in an environment of 23 ° C. and a humidity of 85%.

Using this electrostatic image developer, an image forming apparatus (Fuji Xerox Co., V500 remodeled machine) was used for 10,000
A running test was performed on zero sheets, and the chargeability, image, and toner morphology before and after running were evaluated. The chargeability was extremely stable at −26 μC / g even after running, showing excellent performance. In addition, the image has a clear image of 10,000 without any background dirt (fog) or scattering.
It was also obtained in the durability of the sheet. In addition, the humidity is 30
%, The chargeability was similarly evaluated.
C / g, and almost no environmental difference was recognized.

Further, when the fixing property was evaluated,
, Good fixing properties were obtained, and no occurrence of offset was observed even at 230 ° C. Further, a part of the toner before and after the endurance was sampled, and the morphology was observed with a scanning electron microscope. As a result, almost no change was observed, indicating good durability.

(Example 2) [0147] The same procedure as in Example 1 was carried out except that the aggregating step was changed as follows, and the adhering step was not performed.

<Aggregating Step> Resin Particle Dispersion (1) 180 g Resin Particle Dispersion (2) 80 g Colorant Dispersion (1) 30 g Release agent dispersion (1) 40 g Cationic surfactant 1.5 g (Sanisol B50 manufactured by Kao Corporation) The above was placed in a round stainless steel flask, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and then heated to 48 ° C. in a heating oil bath. Thereafter, the temperature of the heating oil bath was further increased and kept at 50 ° C. for 1 hour.

When the obtained fused particles were measured using a Coulter counter (TA2, manufactured by Coulter), the volume average particle size (D50%) was 5.9 μm.
The particle size distribution coefficient GSD was 1.23. Further, the shape factor S of the fused particles obtained from shape observation by Luzex
F1 was 137 and was observed to be potato-shaped.

When the electrostatic image developing toner obtained in Example 2 was evaluated, the average particle diameter measured with a Coulter counter was 6.44 μm, and the GSD
Was 1.22, the shape factor SF1 was 122, and it was observed that the particles were spherical. Transmission electron microscope (TE
Observation by M) confirmed that a low softening point substance was dispersed in the toner particles for electrostatic image development in the cross-sectional image of the toner for electrostatic image development, and that the arithmetic average diameter was 100 nm. .

The thickness of the acid value carrying layer in the toner for developing an electrostatic image was 100 nm as observed by a transmission electron microscope (TEM). The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sine wave vibration method is described by R
When the toner was developed using DA II (manufactured by Rheometrics), the toner for developing an electrostatic image was observed to have a rubbery flat area, and apparent cross-linking determined from the storage modulus G ′ at 140 ° C. The density (φen) is 6.1 × 10 ⁻⁷ mol /
cm ³ , and the acid value determined by KOH titration is 13.5 m.
gKOH was confirmed.

Next, the chargeability of the non-externally added toner using the toner for developing an electrostatic image was evaluated to be -23 μC / g when the O / M was evaluated at 28 ° C. and 85% humidity. Met. When the chargeability was similarly evaluated in an environment at 10 ° C. and a humidity of 30%, it was -27 μC / g, and almost no environmental difference was recognized. When an externally added toner was prepared using the toner for developing an electrostatic image in the same manner as in Example 1, the chargeability of the externally added toner was −28 μC / g in an environment of 23 ° C. and 85% humidity. .

An electrostatic image developer was prepared in the same manner as in Example 1, and this electrostatic image developer was manufactured by Fuji Xerox.
A running test was performed on 10,000 sheets using a 500-model remodeled machine, and evaluation was performed on the chargeability, image, and toner morphology before and after running.

As a result, the charging property was extremely stable at -26 μC / g even after running, and excellent performance was exhibited. As for the image, a clear image with no background stain (fogging) or scattering was obtained even at the durability of 10,000 sheets. When the chargeability was evaluated in an environment at 10 ° C. and a humidity of 30%, it was -28 μC / g, and almost no environmental difference was recognized. When the fixing property was evaluated, 130 ° C.
, Good fixing properties were obtained, and no occurrence of offset was observed even at 230 ° C. Further, when a part of the toner before and after the endurance was sampled and the form was observed with a scanning male microscope, almost no change was observed, and good durability was exhibited.

(Example 3) In Example 1, the dropping rate of the polar resin solution in the layer forming step was 0.64 g /
Except for minutes, the procedure was the same as in Example 1. PH of final filtrate
Was 6.57, the electric conductivity was 3.5 μS / cm, and the surface tension was 71.7 N / m. When the electrostatic image developing toner obtained in Example 3 was evaluated, the average particle diameter measured using a Coulter counter was 6.12 μm, the GSD was 1.20, and the shape factor SF1 was 130. And a potato shape was observed.

Next, in the cross-sectional image of the electrostatic image developing toner observed by a transmission electron microscope (TEM), a low softening point substance is dispersed in the electrostatic image developing toner particles.
The arithmetic mean diameter was 1100 nm, and the thickness of the acid value carrying layer was 130 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics),
The electrostatic image developing toner was observed to have a rubbery flat area, and the apparent crosslink density (φen) calculated from the storage elastic modulus G ′ at 140 ° C. was 1.3 × 10 ⁻⁸ mol / cm.
³ , and the acid value determined by KOH titration is 13.1 mgK.
OH.

The toner for developing an electrostatic image of Example 3 was used in a similar manner to Example 1 by using a modified X500 manufactured by Fuji Xerox Co., Ltd. under an environment of 28 ° C. and 10% humidity at 10%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the toner without external addition was −27 μC / g, and the toner after external addition was −27 μC / g.
It was as good as 27 μC / g. Furthermore, the durability was stable at −26 μC / g even after running, showing excellent performance. In addition, the image exhibited a sufficient image density, was free of background stain (fogging) and scattering, and was able to obtain a clear image even at the endurance of 10,000 sheets.
When the chargeability was evaluated under an environment of 10 ° C. and a humidity of 30%, it was -29 μC / g, and almost no environmental difference was recognized.

When the fixability was evaluated, good fixability was obtained at 130 ° C., and no occurrence of offset was observed even at 230 ° C. Further, a part of the toner before and after the endurance was sampled, and the morphology was observed with a scanning electron microscope. As a result, almost no change was observed, indicating good durability.

Example 4 Example 1 was the same as Example 1 except that the amount of the polar resin solution dropped in the layer forming step was 86.4 g, and that 1.29 g of ammonium persulfate was used. When the electrostatic image developing toner obtained in Example 4 was evaluated, the average particle diameter measured using a Coulter counter was 6.52 μm.
SD was 1.23, shape factor SF1 was 110.8, and it was observed that it was spherical.

Next, in the cross-sectional image of the toner for developing an electrostatic charge image observed by a transmission electron microscope (TEM), a substance having a low softening point is dispersed in the toner particles for developing an electrostatic charge image.
The arithmetic mean diameter was 480 nm, and the thickness of the acid value carrying layer was 990 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics), the toner for developing an electrostatic image was observed to have a rubber-like flat area, and the apparent crosslinking density (calculated from the storage modulus G ′ at 140 ° C.) φen) is 6.7 × 10 ⁻⁷ mol / cm ³
And the acid value determined by KOH titration is 15.0 mg KO.
H.

The toner for developing an electrostatic image of Example 4 was used in a similar manner to Example 1 by using a modified X500 manufactured by Fuji Xerox Co., Ltd. under the environment of 28 ° C. and 10% humidity at 10%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the toner with no external addition was −30 μC / g, and the toner after external addition was −30 μC / g.
It was as good as 29 μC / g. Furthermore, the durability was stable at −31 μC / g even after running, showing excellent performance. In addition, the image exhibited a sufficient image density, was free of background stain (fogging) and scattering, and was able to obtain a clear image even at the endurance of 10,000 sheets.
When the chargeability was evaluated in an environment at 10 ° C. and a humidity of 30%, it was -30 μC / g, and almost no environmental difference was recognized.

When the fixing property was evaluated, good fixing property was obtained at 130 ° C., and no occurrence of offset was observed even at 240 ° C. Further, a part of the toner before and after the endurance was sampled, and the morphology was observed with a scanning electron microscope. As a result, almost no change was observed, indicating good durability.

Example 5 The procedure was the same as that of Example 1 except that the amount of divinylbenzene in the polar resin solution in the layer forming step was changed to 2.0 g. When the electrostatic image developing toner obtained in Example 5 was evaluated, the average particle diameter measured using a Coulter counter was 6.39 μm, the GSD was 1.23, and the shape factor SF1 was 117. .9, and was observed to be spherical.

Next, in the cross-sectional image of the toner for developing an electrostatic charge image observed by a transmission electron microscope (TEM), a substance having a low softening point is dispersed in the toner particles for developing an electrostatic charge image.
The arithmetic mean diameter was 720 nm, and the thickness of the acid value carrying layer was 780 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics), the toner for developing an electrostatic image was observed to have a rubber-like flat area, and the apparent crosslinking density (calculated from the storage modulus G ′ at 140 ° C.) φen) is 2.4 × 10 ⁻⁶ mol / cm ³
And an acid value determined by KOH titration of 13.3 mg KO
H.

The toner for developing an electrostatic charge image of Example 5 was used in the same manner as in Example 1 by using a modified X500 manufactured by Fuji Xerox Co., Ltd. at a temperature of 28 ° C. and a humidity of 85% for an environment of 10.0%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the unexternally added toner was −29 μC / g, and the externally added toner was −29 μC / g.
It was as good as 29 μC / g. Furthermore, the durability was stable at -32 [mu] C / g even after running, showing excellent performance. In addition, the image exhibited a sufficient image density, was free of background stain (fogging) and scattering, and was able to obtain a clear image even at the endurance of 10,000 sheets.
When the chargeability was evaluated under an environment of 10 ° C. and a humidity of 30%, it was -29 μC / g, and almost no environmental difference was recognized.

When the fixability was evaluated, good fixability was obtained at 130 ° C., and no occurrence of offset was observed even at 240 ° C. Further, a part of the toner before and after the endurance was sampled, and the morphology was observed with a scanning electron microscope. As a result, almost no change was observed, indicating good durability.

Example 6 Example 1 was the same as Example 1 except that the amount of divinylbenzene in the polar resin solution in the layer forming step was changed to 0.1 g. When the electrostatic image developing toner obtained in Example 6 was evaluated, the average particle diameter measured using a Coulter counter was 6.28 μm, the GSD was 1.21, and the shape factor SF1 was 118. .6, and was observed to be spherical.

Next, in the cross-sectional image of the electrostatic image developing toner observed by a transmission electron microscope (TEM), a low softening point substance is dispersed in the electrostatic image developing toner particles.
The arithmetic mean diameter was 570 nm, and the thickness of the acid value carrying layer was 150 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics), the toner for developing an electrostatic image was observed to have a rubber-like flat area, and the apparent crosslinking density (calculated from the storage modulus G ′ at 140 ° C.) φen) is 3.2 × 10 ⁻⁹ mol / cm ³
And the acid value determined by KOH titration was 13.9 mg KO.
H.

The electrostatic image developing toner of Example 6 was subjected to the same procedure as in Example 1 by using a modified X500 made by Fuji Xerox Co., Ltd. at 10,000 ° C. under an environment of 28 ° C. and 85% humidity.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the toner without external addition was −24 μC / g, and the toner after external addition was −24 μC / g.
It was as good as 27 μC / g. Furthermore, the durability was stable at −25 μC / g even after running, showing excellent performance. In addition, the image exhibited a sufficient image density, was free of background stain (fogging) and scattering, and was able to obtain a clear image even at the endurance of 10,000 sheets.
When the chargeability was evaluated under an environment of 10 ° C. and a humidity of 30%, it was -27 μC / g, and almost no environmental difference was recognized.

When the fixability was evaluated, good fixability was obtained at 130 ° C., and no occurrence of offset was observed even at 220 ° C. Further, a part of the toner before and after the endurance was sampled, and the morphology was observed with a scanning electron microscope. As a result, almost no change was observed, indicating good durability.

Example 7 The procedure of Example 1 was repeated, except that the polar resin solution in the layer forming step was replaced with the following polar resin solution. -Preparation of polar resin solution- Styrene 82.5 g Butyl acrylate 17.5 g Divinylbenzene 0.6 g (Wako Pure Chemical Industries) Acrylic acid-methacrylic acid-based polyester (acid value: 5) 10.0 g

The acrylic acid-methacrylic polyester was prepared by mixing 20 parts by weight of acrylic acid and 80 parts by weight of methacrylic acid, and then adding and dissolving 0.2 pph of lauroyl peroxide. This is 1mm
Was poured into two glass cells having a gap thickness of, and polymerized in a 90 ° C. water bath for 8 hours, and then the reaction product was mechanically pulverized.

When the toner for developing an electrostatic charge image obtained in Example 7 was evaluated, the average particle diameter measured using a Coulter counter was 6.55 μm.
Was 1.25, the shape factor SF1 was 120.3, and it was observed that the particles were spherical.

Next, in the cross-sectional image of the toner for developing an electrostatic charge image observed by a transmission electron microscope (TEM), a substance having a low softening point is dispersed in the toner particles for developing an electrostatic charge image.
The arithmetic average diameter was 770 nm, and the thickness of the acid value carrying layer was 690 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics), the toner for developing an electrostatic image was observed to have a rubber-like flat area, and the apparent crosslinking density (calculated from the storage modulus G ′ at 140 ° C.) φen) is 5.6 × 10 ⁻⁹ mol / cm ³
And the acid value determined by KOH titration is 9.7 mg KOH.
Met.

The electrostatic image developing toner of Example 7 was subjected to the same procedure as in Example 1 by using a modified X500 manufactured by Fuji Xerox Co., Ltd. under the environment of 28 ° C. and 85% humidity and a humidity of 10.0%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the charging property, the toner with no external addition was −22 μC / g, and the toner after external addition was −22 μC / g.
It was as good as 25 μC / g. Furthermore, the durability was stable at −24 μC / g even after running, showing excellent performance. In addition, the image exhibited a sufficient image density, was free of background stain (fogging) and scattering, and was able to obtain a clear image even at the endurance of 10,000 sheets.
When the chargeability was evaluated under an environment of 10 ° C. and a humidity of 30%, it was -23 μC / g, and almost no environmental difference was recognized.

When the fixability was evaluated, good fixability was obtained at 130 ° C., and no occurrence of offset was observed even at 220 ° C. Further, a part of the toner before and after the endurance was sampled, and the morphology was observed with a scanning electron microscope. As a result, almost no change was observed, indicating good durability.

Example 8 The procedure of Example 1 was repeated, except that the amount of the polar resin solution dropped in the layer forming step was changed to 10.6 g. When the electrostatic image developing toner obtained in Example 8 was evaluated, the average particle diameter measured with a Coulter counter was 6.01.
μm, the GSD is 1.21, and the shape factor SF1
Was 129.3 and was observed to be potato-shaped.

Next, in the cross-sectional image of the toner for developing an electrostatic image in a transmission electron microscope (TEM) observation, a substance having a low softening point is dispersed in the toner particles for developing an electrostatic image.
The arithmetic mean diameter was 180 nm, and the thickness of the acid value carrying layer was 120 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics), the toner for developing an electrostatic image was observed to have a rubber-like flat area, and the apparent crosslinking density (calculated from the storage modulus G ′ at 140 ° C.) φen) is 7.9 × 10 ⁻⁸ mol / cm ³
Has an acid value of 11.5 mg KO determined by KOH titration.
H.

The toner for developing an electrostatic image of Example 8 was used in the same manner as in Example 1 by using a modified X500 manufactured by Fuji Xerox Co., Ltd. under the environment of 28 ° C. and 85% humidity and a humidity of 10.0%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the toner without external addition was −24 μC / g, and the toner after external addition was −24 μC / g.
It was as good as 27 μC / g. Furthermore, the durability was stable at −26 μC / g even after running, showing excellent performance. In addition, the image exhibited a sufficient image density, was free of background stain (fogging) and scattering, and was able to obtain a clear image even at the endurance of 10,000 sheets.
When the chargeability was evaluated under an environment of 10 ° C. and a humidity of 30%, it was -25 μC / g, and almost no environmental difference was recognized.

When the fixing property was evaluated, good fixing property was obtained at 130 ° C., and no occurrence of offset was observed even at 220 ° C. Further, a part of the toner before and after the endurance was sampled, and the morphology was observed with a scanning electron microscope. As a result, almost no change was observed, indicating good durability.

Example 9 The procedure of Example 7 was repeated except that the acid value of the polar resin was changed from 5 to 40. When the electrostatic image developing toner obtained in Example 9 was evaluated, the average particle diameter measured using a Coulter counter was 6.13 μm, and the GSD was 1.2.
1, the shape factor SF1 was 118.6, and it was observed that the particles were spherical.

Next, in a cross-sectional image of the electrostatic image developing toner observed by a transmission electron microscope (TEM), a low softening point substance is dispersed in the electrostatic image developing toner particles.
The arithmetic average diameter was 670 nm, and the thickness of the acid value carrying layer was 1000 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics),
The electrostatic image developing toner was observed to have a rubbery flat area, and the apparent crosslink density (φen) calculated from the storage elastic modulus G ′ at 140 ° C. was 8.9 × 10 ⁻⁶ mol / cm.
³ , and the acid value determined by KOH titration is 51.2 mgK.
OH.

The toner for developing an electrostatic image of Example 9 was used in a similar manner to Example 7 by using a modified X500 manufactured by Fuji Xerox Co., Ltd. under an environment of 28 ° C. and 85% humidity and a humidity of 10.0%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the value of the unexternally added toner was −31 μC / g,
It was as good as 30 μC / g. Furthermore, the durability was stable at -32 [mu] C / g even after running, showing excellent performance. In addition, the image exhibited a sufficient image density, was free of background stain (fogging) and scattering, and was able to obtain a clear image even at the endurance of 10,000 sheets.
When the chargeability was evaluated in an environment of 10 ° C. and a humidity of 30%, it was −36 μC / g, and almost no environmental difference was recognized.

When the fixing property was evaluated, good fixing property was obtained at 130 ° C., and no occurrence of offset was observed even at 230 ° C. Further, a part of the toner before and after the endurance was sampled, and the morphology was observed with a scanning electron microscope. As a result, almost no change was observed, indicating good durability.

Example 10 Example 10 was carried out in the same manner as in Example 1, except that the polymerization temperature in the layer forming step was changed to 97 ° C. When the electrostatic image developing toner obtained in Example 10 was evaluated, the average particle size measured using a Coulter counter was 6.36 μm.
GSD is 1.21 and shape factor SF1 is 122.5
And a spherical shape was observed.

Next, in the cross-sectional image of the toner for developing an electrostatic charge image observed by a transmission electron microscope (TEM), a substance having a low softening point is dispersed in the toner particles for developing an electrostatic charge image.
The arithmetic mean diameter was 2,920 nm, and the thickness of the acid value carrying layer was 350 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics),
The toner for developing an electrostatic image was observed to have a rubbery flat area, and the apparent crosslink density (φen) calculated from the storage modulus G ′ at 140 ° C. was 6.3 × 10 ⁻⁷ mol / cm.
³ , and the acid value determined by KOH titration is 13.2 mgK
OH.

The toner for developing an electrostatic image of Example 10 was used in a similar manner to that of Example 1 by using a modified X500 made by Fuji Xerox Co., Ltd. under an environment of 28 ° C. and 85% humidity and a humidity of 10.0%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the toner without external addition was −27 μC / g, and the toner after external addition was −27 μC / g.
It was as good as 28 μC / g. Furthermore, the durability was stable at −26 μC / g even after running, showing excellent performance. In addition, the image exhibited a sufficient image density, was free of background stain (fogging) and scattering, and was able to obtain a clear image even at the endurance of 10,000 sheets.
When the chargeability was evaluated under an environment of 10 ° C. and a humidity of 30%, it was -29 μC / g, and almost no environmental difference was recognized.

When the fixability was evaluated, good fixability was obtained at 130 ° C., and no occurrence of offset was observed even at 230 ° C. Further, a part of the toner before and after the endurance was sampled, and the morphology was observed with a scanning electron microscope. As a result, almost no change was observed, indicating good durability.

Example 11 The procedure of Example 1 was repeated, except that the content of the low softening point substance in the agglomerated particles was changed to 5 g. When the electrostatic image developing toner obtained in Example 11 was evaluated, the average particle diameter measured using a Coulter counter was 6.26 μm, the GSD was 1.22, and the shape factor SF1 was 13
0.0 and was observed to be spherical.

Next, in the cross-sectional image of the toner for developing an electrostatic image in a transmission electron microscope (TEM) observation, a substance having a low softening point is dispersed in the toner particles for developing an electrostatic image.
The arithmetic mean diameter was 110 nm, and the thickness of the acid value carrying layer was 180 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics), the toner for developing an electrostatic image was observed to have a rubber-like flat area, and the apparent crosslinking density (calculated from the storage modulus G ′ at 140 ° C.) φen) is 5.1 × 10 ⁻⁷ mol / cm ³
And the acid value determined by KOH titration was 13.9 mg KO.
H.

The toner for developing an electrostatic charge image of Example 11 was used in the same manner as in Example 1 by using a modified X500 manufactured by Fuji Xerox Co., Ltd. under the environment of 28 ° C. and 85% humidity and a humidity of 10.0%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the toner with no external addition was −26 μC / g, and the toner after external addition was −26 μC / g.
It was as good as 27 μC / g. Furthermore, the durability was stable at −25 μC / g even after running, showing excellent performance. In addition, the image exhibited a sufficient image density, was free of background stain (fogging) and scattering, and was able to obtain a clear image even at the endurance of 10,000 sheets.
When the chargeability was evaluated under an environment of 10 ° C. and a humidity of 30%, it was −26 μC / g, and almost no environmental difference was recognized.

When the fixability was evaluated, good fixability was obtained at 130 ° C., and no occurrence of offset was observed even at 230 ° C. Further, a part of the toner before and after the endurance was sampled, and the morphology was observed with a scanning electron microscope. As a result, almost no change was observed, indicating good durability.

Example 12 In Example 1, except that the content of the low softening point substance in the agglomerated particles was set to 30 g,
It was the same as in Example 1. When the electrostatic image developing toner obtained in Example 12 was evaluated, the average particle size measured using a Coulter counter was 6.33 μm, the GSD was 1.23, and the shape factor SF1 was 12
8.1 and were observed to be spherical.

Next, in the cross-sectional image of the electrostatic image developing toner observed by a transmission electron microscope (TEM), a low softening point substance is dispersed in the electrostatic image developing toner particles.
The arithmetic mean diameter was 2870 nm, and the thickness of the acid value carrying layer was 190 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics),
The toner for developing an electrostatic image was observed to have a rubbery flat area, and the apparent crosslink density (φen) calculated from the storage elastic modulus G ′ at 140 ° C. was 1.4 × 10 ⁻⁸ mol / cm.
³ , and the acid value determined by KOH titration is 13.6 mgK
OH.

The toner for developing an electrostatic image of Example 12 was used in the same manner as in Example 1 by using a modified X500 manufactured by Fuji Xerox Co., Ltd. under the conditions of 28 ° C. and 85% humidity and an environment of 10.0%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the toner with no external addition was −26 μC / g, and the toner after external addition was −26 μC / g.
It was as good as 27 μC / g. Furthermore, the durability was stable at −24 μC / g even after running, showing excellent performance. In addition, the image exhibited a sufficient image density, was free of background stain (fogging) and scattering, and was able to obtain a clear image even at the endurance of 10,000 sheets.
When the chargeability was evaluated under an environment of 10 ° C. and a humidity of 30%, it was -27 μC / g, and almost no environmental difference was recognized.

When the fixability was evaluated, good fixability was obtained at 130 ° C., and no occurrence of offset was observed even at 230 ° C. Further, a part of the toner before and after the endurance was sampled, and the morphology was observed with a scanning electron microscope. As a result, almost no change was observed, indicating good durability.

Comparative Example 1 The procedure of Example 1 was repeated, except that the amount of civinylbenzene in the polar resin solution in the layer forming step was changed to 3.0 g. Comparative Example 1
Was evaluated using the Coulter counter, the average particle diameter was 6.32 μm, the GSD was 1.22, and the shape factor SF1 was 119.4. And it was observed to be spherical.

Next, in a cross-sectional image of the toner for developing an electrostatic image in a transmission electron microscope (TEM) observation, a substance having a low softening point is dispersed in the toner particles for developing an electrostatic image.
The arithmetic mean diameter was 3040 nm, and the thickness of the acid value carrying layer was 100 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics),
The electrostatic image developing toner was observed to have a rubbery flat area, and the apparent crosslink density (φen) calculated from the storage elastic modulus G ′ at 140 ° C. was 1.1 × 10 ⁻⁵ mol / cm.
³ , and the acid value determined by KOH titration is 13.1 mgK.
OH.

The toner for developing an electrostatic charge image of Comparative Example 1 was used in the same manner as in Example 1 by using a modified X500 manufactured by Fuji Xerox Co., Ltd. under an environment of 28 ° C. and 85% humidity and a humidity of 10.0%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the toner with no external addition was −36 μC / g, and the toner after external addition was −36 μC / g.
The value was as good as 33 μC / g. Furthermore, regarding the durability, a charge-up tendency of -43 [mu] C / g was observed after running. As for the image, a decrease in image density was observed. Further, background dirt (fogging) and scattering were slightly observed at the time of startup even in the durability of 10,000 sheets. When the fixing property was evaluated, no fixing property was obtained even at 180 ° C.

Comparative Example 2 The procedure of Example 2 was repeated except that the amount of divinylbenzene in the polar resin solution in the layer forming step was changed to 3.0 g. Comparative Example 2
Was evaluated using the Coulter counter, the average particle diameter was 6.35 μm, the GSD was 1.24, and the shape factor SF1 was 120.1. And it was observed to be spherical.

Next, in the cross-sectional image of the electrostatic image developing toner observed by a transmission electron microscope (TEM), a low softening point substance is dispersed in the electrostatic image developing toner particles.
The arithmetic mean diameter was 2940 nm, and the thickness of the acid value carrying layer was 40 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was performed by RDA.
II (manufactured by Rheometrics), the toner for developing an electrostatic image was observed to have a rubber-like flat area, and the apparent crosslinking density (calculated from the storage modulus G ′ at 140 ° C.) φen) is 1.3 × 10 ⁻⁵ mol / cm ³
And an acid value determined by KOH titration of 13.3 mg KO
H.

The toner for developing an electrostatic charge image of Comparative Example 2 was used in the same manner as in Example 2 by using a modified X500 made by Fuji Xerox, under an environment of 28 ° C. and 85% humidity and a humidity of 10.0%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the charging property, the value of the non-externally added toner was −34 μC / g, and the value of −
It was as good as 31 μC / g. Further, regarding the durability, a charge-up tendency of -44 [mu] C / g was observed after running. As for the image, a decrease in image density was observed. Further, background dirt (fogging) and scattering were slightly observed at the time of startup even in the durability of 10,000 sheets. When the fixing property was evaluated, no fixing property was obtained even at 180 ° C.

Comparative Example 3 The procedure of Example 1 was repeated except that no polar resin was added to the polar resin solution in the layer forming step. When the electrostatic image developing toner obtained in Comparative Example 3 was evaluated, the average particle diameter measured using a Coulter counter was 6.0.
0 μm, the GSD is 1.27 and the shape factor SF
1 was 134.3, which was observed to be potato-shaped.

Next, in the cross-sectional image of the toner for developing an electrostatic image in a transmission electron microscope (TEM) observation, a substance having a low softening point is dispersed in the toner particles for developing an electrostatic image.
The arithmetic average diameter was 160 nm, and the thickness of the acid value carrying layer was not observed. In addition, occurrence of colorant rejection was observed during the manufacturing process. The dynamic viscoelasticity of this electrostatic image developing toner was measured by a sine wave vibration method using RDA II (manufactured by Rheometrics). The apparent crosslink density (φen) calculated from the storage modulus G ′ at 140 ° C. was 1.3 × 10 ⁻⁹ m.
ol / cm ³ , and the acid value determined by KOH titration was 3.
It was 9 mg KOH.

The toner for developing an electrostatic charge image of Comparative Example 3 was used in the same manner as in Example 1 by using a modified X500 made by Fuji Xerox, under an environment of 28 ° C. and 85% humidity and a humidity of 10.0%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the toner with no external addition was −14 μC / g, and the toner after external addition was −14 μC / g.
It was 18 μC / g. Further, with respect to durability, a tendency to decrease to -14 μC / g after running was observed. As for the image, the image density was low, and background dirt (fog) and scattering were slightly observed in the durability of 10,000 sheets. As for the fixing property, good fixing property was obtained at 130 ° C.
No occurrence of offset was observed even at ℃. Further, when a part of the toner before and after the endurance was sampled and its form was observed with a scanning electron microscope, it was found that the external additive was embedded.

(Comparative Example 4) In Example 1, divinylbenzene was added to the polar resin solution in the layer forming step.
The same procedure as in Example 1 was carried out except for the addition of weight%. Comparative Example 4
Was evaluated using the Coulter counter, the average particle diameter was 6.61 μm, and the GSD was considerably deteriorated to 1.31. In addition, the shape factor SF1 was 127.1, and it was observed that the sample had a potato shape.

Next, in the cross-sectional image of the toner for developing an electrostatic image in a transmission electron microscope (TEM) observation, a substance having a low softening point is dispersed in the toner particles for developing an electrostatic image.
The arithmetic mean diameter was 150 nm, and the thickness of the acid value carrying layer was 30 nm. The measurement of the dynamic viscoelasticity of the toner for developing an electrostatic image by the sinusoidal vibration method was carried out according to RDAI
I (manufactured by Rheometrics), the toner for developing an electrostatic image was observed to have a rubbery flat area, and the apparent crosslinking density (calculated from the storage modulus G ′ at 140 ° C.) φen) is 3.4 × 10 ⁻⁵ mol / cm ³
Met.

The toner for developing an electrostatic charge image of Comparative Example 4 was used in the same manner as in Example 1 by using a modified X500 made by Fuji Xerox under the environment of 28 ° C. and 85% humidity at 85%.
A running test of 00 sheets was performed, and the chargeability before and after running, images,
And the form of the toner. Regarding the chargeability, the toner without addition was -23 μC / g, and the toner after addition was −
It was 28 μC / g. Further, with respect to durability, a tendency to decrease to -25 μC / g after running was observed. As for the image, the image density was generally low, and background stains (fog) and scattering were slightly observed in the durability of 10,000 sheets. Regarding the fixability, the toner was not fixed up to 180 ° C.
Further, a part of the toner before and after the endurance was sampled, and the form was observed with a scanning electron microscope. As a result, no embedding of the external additive was observed.

[0209]

[Table 1]

[0210]

According to the present invention, the above-mentioned various problems in the related art can be solved. Further, according to the present invention, various properties such as chargeability, developability, transferability, fixability, and cleaning property, in particular, charge uniformity, charge stability, image fixability, image durability, shape control, oilless fixation. It is possible to provide a toner for developing an electrostatic image and an electrostatic image developer using the toner for developing an electrostatic image, which has excellent properties and satisfies high image quality and high reliability. Further, according to the present invention, it is possible to manufacture a toner for developing an electrostatic image capable of easily and simply manufacturing a toner for developing an electrostatic image having excellent characteristics described above without causing release of a coloring agent or a release agent. A method can be provided. Further, according to the present invention, it is possible to provide an image forming method capable of easily and simply forming a full-color image with high chroma on paper and OHP. Further, according to the present invention, there is provided an image forming method which is highly suitable for a so-called toner recycling system in which toner collected from a cleaner is reused, and which can obtain high image quality with excellent light transmittance and coloring properties. be able to.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03G 9/10 351 (72) Inventor Yasuo Kadokura 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Hideo Maehata 1600 Takematsu, Minami Ashigara City, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd.

Claims (17)

[Claims] An agglomerated particle obtained by aggregating the resin particles in a dispersion in which at least resin particles are dispersed; and a method in which the fine particles are adhered to the agglomerated particles in a fine particle dispersion in which at least the fine particles are dispersed. Is obtained by heating and fusing any of the adhered particles having an acid value-bearing layer containing a polar group and having a crosslinked structure on the surface, and having an acid value determined by KOH titration of 5 to 40 mgKOH / g. And the apparent crosslink density (φen) obtained from the measurement of dynamic viscoelasticity by the sinusoidal vibration method is 1 × 10 ⁻⁶ mol / cm ³ ≦ (φe
n) A toner for developing electrostatic images, wherein ≦ 9 × 10 ⁻⁹ mol / cm ³ . Here, φ represents a front factor, e represents a crosslinking reaction rate, and n represents an apparent crosslinking density (mol / cm ³ ). 2. A low-softening point substance in a dispersed state of 5 to 30
The toner for developing an electrostatic image according to claim 1, wherein the toner is contained in a weight percentage. 3. A transmission electron microscope (TE) of a material having a low softening point.
The median diameter measured according to M) is 100 to 3000 n
3. The electrostatic image developing toner according to claim 2, wherein m is m. 4. A transmission electron microscope (TE) of an acid value supporting layer.
The toner for developing an electrostatic image according to any one of claims 1 to 3, wherein the thickness measured by M) is 50 to 1000 nm. 5. The shape factor SF1 is 100 ≦ SF1 ≦ 1.
5. The toner for developing an electrostatic image according to claim 1, wherein the number is 30. 6. 6. The electrostatic image developing toner according to claim 1, having a volume average particle size of 2 to 9 μm. 7. The electrostatic image developing toner according to claim 1, wherein the charge amount is 10 to 40 μC / g. 8. An aggregating step of aggregating the resin particles in a dispersion in which at least the resin particles are dispersed to form agglomerated particles, a fusing step of heating and aggregating the agglomerated particles, and the fusing step. A layer forming step of forming an acid value-bearing layer on the surface of the particles obtained, and producing the electrostatic image developing toner according to any one of claims 1 to 7 for electrostatic image development. Manufacturing method of toner. 9. After the aggregation step and before the fusion step,
In the agglomerated particle dispersion in which the agglomerated particles are dispersed, a fine particle dispersion in which the fine particles are dispersed is added and mixed, and the fine particles are adhered to the agglomerated particles. The method for producing a toner for developing an electrostatic image according to claim 8, wherein the adhered particles are heated and fused. 10. The method according to claim 8, wherein the layer forming step is performed by a swelling polymerization method. 11. The method according to claim 8, wherein the resin particles have an average particle size of 1 μm or less. 12. The method for producing an electrostatic image developing toner according to claim 9, wherein at least one of the aggregated particles and the attached particles contains a colorant. 13. The method for producing an electrostatic image developing toner according to claim 8, wherein the layer forming step is performed using 0.1 to 2% by weight of a polyfunctional monomer. 14. 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 claims 1 to 7. Agent. 15. The electrostatic image developer according to claim 14, wherein the carrier has a resin coating layer. 16. 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 layer on a developer carrier to form a toner image, and An image forming method comprising: a transfer step of transferring an image onto a transfer member; and a cleaning step of removing a toner for developing an electrostatic image remaining on an electrostatic latent image carrier, wherein the developer layer comprises 8. An image forming method, comprising the electrostatic image developing toner according to any one of 7. 17. The image forming method according to claim 16, wherein the electrostatic image developing toner removed in the cleaning step is transferred to a developer layer.