JP2003241426A - Method for manufacturing toner particle, toner particle and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing toner particles by association coagulation in a water-based medium to obtain toner particles having excellent fixing property, offset resistance and long-term storage property and long-term development stability. <P>SOLUTION: In the method for manufacturing toner particles by associating and fusing a plurality of polymer fine particles dispersed in a water-based medium, fine particles of a high melting point wax coated with at least a low molecular weight polymer are associated and melted with fine particles of a low melting point wax coated with a high molecular weight polymer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing toner particles used in an electrostatic image developing toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, toner jet, etc. It relates to particles and toner.

[0002]

2. Description of the Related Art Conventionally, a generally used toner has been manufactured by a so-called pulverization method, which is a method in which a binder resin, a colorant and the like are melt-kneaded, and then pulverized and classified. In recent years, it is produced by a method of directly producing a toner by a suspension polymerization method or the like, or a method of associating and fusing polymer fine particles obtained by an emulsion polymerization method, and is called a polymerization method toner or the like.

In Japanese Patent Laid-Open No. 11-84730, it is disclosed that toner particles are synthesized in an aqueous medium by using a dispersion obtained by emulsion-polymerizing a monomer in the presence of modified polypropylene and carbon black. 2000
No. 35690 discloses that a wax having a penetration of 4 or less is used.

In Japanese Patent Application Laid-Open No. 11-194541, a high molecular weight latex and a low molecular weight latex are mixed,
It is disclosed that a toner having a two-peak molecular weight distribution is produced by associative fusion.

However, the toner produced by the method of associative fusion has a feature that the particle size distribution and the like can be efficiently sharpened as compared with the toner produced by the conventional pulverization method. However, the fixability is often inferior, and since the soft component is increased as the resin component to satisfy the fixability, the offset resistance at the time of fixing is inferior and the problem of long-term storage property (blocking property) occurs. Further, since the amount of wax contained in the toner is increased, long-term development stability is lacking.

JP-A-2001-27821 discloses a toner in which emulsion polymerization is carried out in the presence of a wax to form particles that are said to contain the wax, and the particles are associated and fused to each other, which is excellent in fixability. Although a toner is provided, a toner having an effect on fixability has a problem in long-term storage stability, and a further improvement method is desired also in this respect.

In the present invention, in view of the above-mentioned prior art,
It is an object of the present invention to provide a toner particle having excellent fixing property and anti-offset property, which has development stability for a long period of time, in a manufacturing method of associating and fusing in a water-based medium.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing toner particles by associating and aggregating them in an aqueous medium, in which the particle size distribution is efficiently sharpened, the fixing property and the offset resistance are excellent, and the product is stored for a long period of time. An object of the present invention is to provide a method for producing toner particles having excellent properties.

A further object of the present invention is to provide a method for producing toner particles by associating and aggregating toner particles in an aqueous medium, which has good fixability and long-term development stability. To provide.

Another object of the present invention is a toner particle or a toner produced by associating and agglomerating toner particles in an aqueous medium, which has excellent fixability and offset resistance, excellent long-term storage stability, and long-term storage stability. The present invention provides a toner particle or toner having development stability.

[0011]

In order to solve the above-mentioned problems, the invention according to claim 1 of the present invention is a toner obtained by associating and fusing a plurality of polymer fine particles dispersed in an aqueous medium. In the method for producing particles, at least high melting point wax fine particles coated with a low molecular weight polymer and low melting point wax fine particles coated with a high molecular weight polymer are associated and fused.

According to the invention described in claim 2, in the invention described in claim 1, the high melting point wax fine particles coated with a low molecular weight polymer or the low melting point wax coated with a high molecular weight polymer are wax fine particles. It is characterized by being obtained by polymerizing a polymerizable monomer in the presence.

The invention described in claim 3 is the invention according to claim 1 or 2.
In the invention described in (1) above, the temperature at which they are fused in an aqueous medium is equal to or lower than the melting point of the high melting point wax and is equal to or higher than the melting point of the low melting point wax.

The invention according to a fourth aspect is the first to the third aspects.
In the invention described in (3), the weight average diameter of the toner particles is 3
To 9 μm, SF2 is 120 to 170, and the variation coefficient of SF2 is 4.0 to 8.0.

The invention according to claim 5 is produced by associating and fusing at least high melting point wax fine particles coated with a low molecular weight polymer and low melting point wax fine particles coated with a high molecular weight polymer in an aqueous medium. In the toner particles, the weight average diameter of the toner particles is 3 to 9 μm, SF2
Is 120 to 170 and the coefficient of variation of SF2 is 4.0 to 8.0.

The invention according to claim 6 is produced by associating and fusing high melting point wax fine particles coated with at least a low molecular weight polymer and low melting point wax fine particles coated with a high molecular weight polymer in an aqueous medium. A toner using toner particles has a hydrophobic inorganic fine powder on the surface, a weight average diameter of 3 to 9 μm, SF2 of 120 to 170, and a variation coefficient of SF2 of 4.0 to 8.0. Characterize.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, in a method for producing toner particles by associating and fusing a plurality of polymer fine particles dispersed in an aqueous medium, at least a high molecular weight polymer coated with a low molecular weight polymer is used. The melting point wax fine particles and the low melting point wax fine particles coated with the high molecular weight polymer are associated and fused.

The low molecular weight polymer or the high molecular weight polymer means gel permeation chromatography (hereinafter referred to as G
A weight average molecular weight (hereinafter referred to as PC) is measured by the following description.

The melting point of the wax is defined by the maximum endothermic peak at the time of heating in the DSC curve measured by a differential scanning calorimeter.

With this structure, the wax is less biased in the associative fusion process in the production of toner particles,
The wax can be reliably incorporated into the toner particles, and the amount of liberated wax can be reduced.
In addition, even when the high molecular weight polymer is fused, the effect of the low melting point wax is such that it is relatively easy to soften and strong toner particles can be produced.

By combining a low-molecular-weight polymer excellent in low-temperature fixability but inferior in high-temperature offset property with a high-melting-point wax, an effect of preventing high-temperature offset is imparted while maintaining low-temperature fixability, and high-temperature offset property is excellent. By integrating the low-melting-point wax with the high-molecular-weight polymer having poor low-temperature fixability, these have a synergistic effect, and unexpectedly remarkable low-temperature fixability and high-temperature offset property can be obtained. .

Further, by placing a high melting point wax on the low molecular weight polymer and a low melting point wax on the high molecular weight polymer, and fusing at a temperature above the melting point of the low melting point wax and below the melting point of the high melting point wax. It is possible to reduce contamination of the low-molecular weight polymer by the high-melting-point wax and reduce the contamination of the low-melting-point wax by the high-molecular-weight polymer, which act synergistically, and when the toner particles of the present invention are used,
Contamination of the development carrier or the charging member by the wax component or the binding component can be extremely reduced, and stable development stability can be maintained for a long period of time.

The high melting point wax fine particles coated with the low molecular weight polymer in the present invention are prepared by adding a polymerizable monomer and a polymerization initiator to a dispersion liquid in which the wax fine particles are dispersed, and polymerizing the wax fine particles as a seed. It can be preferably manufactured.

The dispersion liquid in which the wax fine particles are dispersed is, for example, a cationic surfactant, an anionic surfactant or a nonionic surfactant, and a cationic surfactant, an anionic surfactant or a nonionic surfactant is used in an aqueous medium. A homogenizer or pressure-dispersing disperser that can disperse with one or more polymer electrolytes such as an ionic surfactant, a polymer acid, and a polymer base, heat it to a temperature equal to or higher than its melting point, and impart strong shearing force. Can be used to make fine particles. Examples of the aqueous medium include distilled water, water such as ion-exchanged water, alcohols and the like. The particle size of the dispersed wax is preferably 0.01 μm to 3 μm, and more preferably 0.05 to 2 μm. If the wax dispersion diameter is less than 0.01 μm, the coating with the low molecular weight polymer becomes difficult, and if it exceeds 3 μm, the dispersion of the wax in each toner particle formed becomes uneven, which may adversely affect the developability. .

Examples of the above-mentioned surfactant include anionic surfactants such as sulfate ester type, sulfonate type, phosphoric acid ester type and soap type; cationic surfactants such as amine salt type and quaternary ammonium salt type. Agents and the like. Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, alkylbenzenedimethylammonium chloride, alkyltrimethylammonium chloride, distearylammonium chloride and the like. . Polyethylene glycol type,
Examples thereof include alkylphenol ethylene oxide adduct-based and polyhydric alcohol-based nonionic surfactants.

In order to obtain high melting point wax fine particles coated with a low molecular weight polymer, the following method can be given as an example. For the wax dispersion,
A monomer having an acidic polar group or a basic polar group, and
By adding other polymerizable monomers,
One of the preferable manufacturing methods is to advance the polymerization in a dispersion liquid containing a wax. At this time, the monomers may be added separately, or a plurality of monomers may be mixed in advance and added. Further, it is possible to change the monomer composition during the addition of the monomer. Further, the monomer may be added as it is, or may be added as an emulsified liquid prepared by mixing and adjusting with water or a surfactant in advance. Here, a high melting point wax coated with a low molecular weight polymer can be obtained, and at the same time, low molecular weight polymer fine particles not coating the surface of the wax fine particles can be simultaneously produced.

The preferable dispersion diameter of the fine particles in the dispersion liquid containing the high melting point wax fine particles coated with the low molecular weight polymer is 0.05 to 3 μm, and more preferably,
It is 0.05 to 2 μm. If it is less than 0.05 μm, the control at the time of association is difficult, and if it exceeds 3 μm, the surface of the toner particles becomes too uneven and the effect of the present invention becomes difficult to be exhibited.

Another preferred property for the solids content in the dispersion of high melting wax particles coated with a low molecular weight polymer is that its glass transition point is 50-70 ° C. More preferably, it is 55 to 65 ° C. If the glass transition point is less than 50 ° C., the long-term storage stability of the toner produced using the present dispersion liquid is deteriorated to 70 ° C.
If it exceeds, the fixability tends to deteriorate.

A preferred embodiment of the low molecular weight polymer in the present invention is a peak molecular weight measured by GPC of tetrahydrofuran (hereinafter referred to as THF) soluble component (hereinafter, the peak molecular weight of the low molecular weight polymer is described as P1). ) Is preferably 3000 to 50000, and more preferably 4000 to 30000. Peak molecular weight is 3
If it is less than 000, the offset resistance and long-term storage stability tend to be poor, and the developability tends to be poor. Also, P1 is
If it exceeds 50,000, it tends to be difficult to achieve both good fixability and long-term storage stability.

Further, the Mw and G of the low molecular weight polymer fine particles are
Regarding the number average molecular weight measured by PC (hereinafter, referred to as Mn for the number average molecular weight), preferably,
Mw is 5000 to 100000, Mn is 1000 to 30
When it is adjusted to 000, it becomes possible to more firmly perform fusion bonding during association fusion in an aqueous medium, and durability stability can be obtained.

The low melting point wax fine particles coated with the high molecular weight polymer in the present invention are prepared by adding a polymerizable monomer, a polymerization initiator and the like to a dispersion liquid in which the wax fine particles are dispersed,
By polymerizing the wax fine particles as a seed, it can be produced by a method similar to that of the high melting point wax fine particles coated with the low molecular weight polymer.

In the dispersion liquid in which the low melting point wax fine particles are dispersed, the dispersed wax has a particle diameter of 0.01 μm.
To 3 μm is preferable, and more preferably 0.05 to 2 μm.
Is preferred. In the case of a high melting point wax, if the wax dispersion diameter is less than 0.01 μm, coating with a high molecular weight polymer becomes difficult, and if it exceeds 3 μm, the dispersion of the wax in the produced toner particles becomes non-uniform, resulting in poor developability. May have an adverse effect.

The preferable dispersion diameter of the fine particles in the dispersion liquid containing the low melting point wax fine particles coated with the high molecular weight polymer is 0.05 to 3 μm, more preferably
It is 0.05 to 2 μm. If it is less than 0.05 μm, it is difficult to control the association, and if it exceeds 3 μm, it becomes difficult to control the surface shape of the toner particles to the desired one.

Another preferred embodiment of the high molecular weight polymer according to the present invention has a glass transition point of 50.
It is ~ 70 ° C. More preferably 55-6
It is 5 ° C. If the glass transition point is less than 50 ° C, the long-term storability of the toner produced using this dispersion will deteriorate, and if it exceeds 70 ° C, the fixability will tend to deteriorate.

A preferred form of high molecular weight polymer is THF
Mw by GPC of the soluble component is 50,000 to 10,000
00 is preferable, and it is preferable that the THF insoluble content is 70% by weight or less. If the Mw is 50,000 or less, the offset resistance tends to be insufficient and the developability over a long period of time tends to be poor. If the THF-insoluble content exceeds 70% by weight, a long time or high temperature is required under the condition for fusion after association, so that the low melting point wax tends to ooze out in a large amount, and bleeding is also suppressed. The strength of the toner particles becomes low, and it tends to be difficult to obtain long-term developability.

A high melting point wax has a melting point of 9
A wax having a melting point of 50 to 120 ° C. is preferably used as the wax having a low melting point. Especially for low melting waxes,
60 to 100 ° C. is more preferable, and 60 to 90 ° C. gives better results.

As the wax used in the present invention, known wax can be used, and it can be appropriately selected and used from the melting point thereof.

Specifically, aliphatic hydrocarbon waxes (low molecular weight polyethylene, low molecular weight polypropylene, paraffin wax, Fischer-Tropsch wax, etc.), aliphatic hydrocarbon wax oxides, plant waxes (candelilla wax, Carnauba wax)
Animal wax (Mitsuwa, lanolin, etc.), Mineral wax (Ozokerite, Ceresin, Petrolactam, etc.),
Waxes containing fatty acid ester as a component (behenyl behenate, montanic acid ester, stearyl stearate, etc.), saturated or unsaturated fatty acids (palmitic acid, stearic acid, eleostearic acid, valinaric acid), saturated with alkyl for investigation Or unsaturated alcohol (stearyl alcohol, eicosyl alcohol, behenyl alcohol, etc.), polyhydric alcohol (sorbitol, etc.), aliphatic or unsaturated or aromatic amide (linoleic acid amide,
Oleic acid amide, methylenebisstearic acid amide,
Ethylene bis oleic acid amide, m-xylene bis stearic acid amide, etc.), fatty acid metal salts (calcium laurate, zinc stearate, magnesium stearate, etc.), silicones having an alkyl group, aliphatic hydrocarbon wax, styrene and acrylic acid. A wax grafted with a vinyl-based monomer such as

The wax preferably used is a polyolefin obtained by radically polymerizing an olefin under high pressure;
Polyolefins obtained by purifying low molecular weight by-products obtained during the polymerization of high molecular weight polyolefins; polyolefins polymerized under a low pressure by using catalysts such as Ziegler catalysts and metallocene catalysts; polyolefins polymerized by utilizing radiation, electromagnetic waves or light; polymers Low molecular weight polyolefin obtained by thermal decomposition of polyolefin; paraffin wax, microcrystalline wax, Fischer-Tropsch wax; synthetic hydrocarbon wax synthesized by the Zindole method, Hydrocoal method, Arge method, etc .; monomer having 1 carbon atom A synthetic wax, a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group;
A mixture of a hydrocarbon wax and a wax having a functional group; a wax obtained by graft-modifying a vinyl monomer such as styrene, maleic acid ester, acrylate, methacrylate or maleic anhydride using these waxes as a matrix.

Further, these waxes are pressed by a sweating method,
Those with sharpened molecular weight distribution using solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method or fused liquid crystal method,
A low molecular weight solid fatty acid, a low molecular weight solid alcohol, a low molecular weight solid compound, and those from which other impurities have been removed are also preferably used.

As the monomer having an acidic polar group used in the present invention, a monomer having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and cinnamic acid, and a sulfonic acid group such as sulfonated styrene. And the like. Examples of the monomer having a basic polar group include a nitrogen-containing heterocyclic ring-containing monomer such as aminostyrene and a quaternary salt thereof, vinylpyridine and vinylpyrrolidone, and an amino group such as dimethylaminoethyl acrylate and diethylaminoethyl methacrylate. ) Acrylic acid esters and (meth) acrylic acid esters having an ammonium salt obtained by quaternizing these amino groups, and further acrylamide, N-propylacrylamide, N, N-dimethylacrylamide,
Examples thereof include N, N-dipropyl acrylamide, N, N-dibutyl acrylamide, and acrylic acid amide.

Other polymerizable monomers include styrenes such as styrene, methylstyrene, chlorostyrene, dichlorostyrene, p-tert-butylstyrene, pn-butylstyrene, pn-nonylstyrene, and acrylics. Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate,
Mention may be made of (meth) acrylic acid esters such as ethylhexyl methacrylate. Among these, styrene, n-butyl (meth) acrylate, 2-ethylhexyl acrylate, and the like are particularly preferable.

As the polymerization initiator, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate,
And a redox initiator obtained by combining these persulfates as a component with a reducing agent such as sodium acid sulfite, hydrogen peroxide, 4,4′-azobiscyanovaleric acid, t-butyl hydroperoxide, cumene hydroperoxide, etc. And a redox initiator system in which these water-soluble polymerizable initiators are combined as one component with a reducing agent such as a ferrous salt, benzoyl peroxide, 2,2′-
Azobis-isobutyronitrile, etc. are used. These polymerization initiators may be added to the polymerization system before, at the same time as, or after the addition of the monomer, and these addition methods may be combined as necessary.

In the present invention, it is preferable to use a chain transfer agent. Particularly, it is preferably used when preparing relatively low molecular weight polymer fine particles. As such a chain transfer agent, known ones can be used. Specific examples include t-dodecyl mercaptan, 2-mercaptoethanol, diisopropylxanthogen, carbon tetrachloride, trichlorobromomethane, and the like. The chain transfer agent may be used alone or in combination of two or more kinds, and is used in an amount of 0 to 5% by weight based on the polymerizable monomer.

The means for assembling and fusing particles by mixing the dispersions obtained as described above will be described in detail.

The formation of associated particles is to form associated particles in the mixed solution to prepare an associated particle particle dispersion liquid. The associated particles can be formed in the mixed solution by adding, for example, a pH adjuster, a coagulant, and a stabilizer to the mixed solution, mixing them, and appropriately adding temperature, mechanical power and the like.

Examples of the pH adjusting agent include alkalis such as ammonia and sodium hydroxide, and acids such as nitric acid and citric acid. As the coagulant, sodium, potassium, etc. 1
Examples thereof include divalent metal salts; divalent metal salts such as calcium and magnesium; trivalent metal salts such as iron and aluminum; alcohols such as methanol, ethanol and propanol.

Examples of the stabilizer include the polar surfactant itself or an aqueous medium containing the same. For example, when the polar surfactant contained in the aqueous dispersion is anionic, a cationic one can be selected as the stabilizer.

Addition and mixing of the aggregating agent and the like are preferably carried out at a temperature below the glass transition point of the resin contained in the mixed solution. When the mixing is performed under this temperature condition, the association proceeds in a stable state. The mixing can be performed using, for example, a mixing device, a homogenizer, a mixer and the like known per se.

The average particle size of the associated particles formed here is not particularly limited, but is usually controlled to be approximately the same as the average particle size of the toner to be obtained. In the control, for example, the temperature and the conditions of the stirring and mixing are appropriately set /
This can be easily done by changing it. By the above-mentioned associated particle forming step, associated particles having an average particle diameter substantially the same as the average particle diameter of the toner are formed, and an associated particle dispersion liquid in which the associated particles are dispersed is prepared.

The fusion step is a step in which the associated particles are heated and fused. Before entering the fusing step, in order to prevent fusing between the toner particles, the pH adjusting agent, the polar surfactant, the non-polar surfactant and the like can be appropriately added.

The heating temperature may be from the glass transition temperature of the resin contained in the aggregated particles to the decomposition temperature of the resin. Therefore, the temperature of the heating is different depending on the type of resin of the resin particles and the resin particles,
Although it cannot be specified unconditionally, it is generally from the glass transition temperature of the resin contained in the aggregated particles or the adhered particles to 140 ° C. In the present invention, it is more preferable to carry out at a temperature not lower than the melting point of the low melting point wax and not higher than the melting point of the high melting point wax. The heating can be performed using a heating device / tool known per se.

As the fusion time, a shorter time is required if the heating temperature is high, and a longer time is required if the heating temperature is low. That is, the fusion time cannot be unconditionally specified because it depends on the heating temperature, but it is generally 30 minutes to 10 hours.

In the present invention, the fused particles obtained after the completion of the fusion step are washed and dried under appropriate conditions to obtain toner particles.

In order to satisfy the fixing property and the offset property,
As for the manufactured toner particles, the peak molecular weight by GPC of the THF-soluble component is preferably 3,000 to 50,000. If the peak molecular weight is less than 3,000, the long-term storage stability of the toner tends to be poor and the developability tends to be poor. When P1 exceeds 50,000, it becomes difficult to achieve both fixability and long-term storage stability. More preferably 400
It is 0 to 30,000. In addition, the Mw of the THF soluble component is
It is preferably 10,000 to 500,000, and the THF insoluble content is preferably 50% by weight or less based on the binder component of the toner. If the Mw of the THF-soluble component is less than 10,000, the offset resistance tends to be insufficient, and if the THF-insoluble component exceeds 50% by weight with respect to the binder component of the toner, the fixing property becomes insufficient and However, stable developability over a long period of time may not be obtained. More preferably, it is 40% by weight or less.

Further, the toner particles obtained in the present invention preferably have a weight average diameter of 3 to 9 μm. If it exceeds 9 μm, the image quality may be insufficient. If it is less than 3 μm, it is difficult to use it and the sufficient image density cannot be obtained in many cases using the current development technology. SF2 is preferably 120 to 170, and more preferably 130 to 160. SF2 is 120
If it does not meet the requirements, the cleaning property may be poor, and 170
If it exceeds, the shape may be too irregular and the reproducibility of the latent image may be deteriorated. Further, the coefficient of variation of SF2 is 4.0 to 8.
It is preferably 0, more preferably 4.5 to
It is 7.5. If the coefficient of variation of SF2 is less than 4.0, the fusion is considerably advanced and the low melting point wax tends to exude to the surface. If it exceeds 8.0, the abundance ratio of toner particles with insufficient strength is present. In addition to the large number of particles, there are too many variations on the surface, which tend to adversely affect the environmental dependence.

In the method for producing the toner particles of the present invention, the colorant may be incorporated by the following method, for example. The method of adding the dispersion of the colorant at the time of association, the method of adding the obtained dispersion to the polymerization reaction in the presence of the colorant, the method of performing the polymerization reaction in the presence of the wax particles and the colorant, Examples of the method include a method of associating with each other.

In the toner particles of the present invention, for example, the following colorants are used. Examples thereof include phthalocyanine pigments, monoazo pigments, bisazo pigments, magnetic powders and quinacridone pigments. Specific examples of these include, for example, carbon black, chrome yellow, Hansa yellow, benzidine yellow, slen yellow,
Quinoline Yellow, Permanent Orange GTR, Pyrazolone Orange, Balkan Orange, Watch Young Red, Permanent Red, Brilliant Kamine 3B,
Brilliant Ankamine 6B, DuPont Oil Red, Pyrazolone Red, Resole Red, Rhodamine B Rake,
Various pigments such as lake red C, rose bengal, aniline blue, ultramarine blue, chalco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate; acridine-based, xanthene-based, azo-based, benzoquinone-based, Azine, anthraquinone, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black,
Various dyes such as polymethine type, triphenylmethane type, diphenylmethane type, thiazine type, thiazole type and xanthene type dyes; These colorants may be used alone or in combination of two or more.

The average particle size of the colorant particles is 0.
It is preferably 5 μm or less, more preferably 0.2 μm or less. When the average particle diameter exceeds 0.5 μm, diffuse reflection of visible light cannot be prevented, and when coarse particles are present, coloring power, color reproducibility, and OHP transparency are adversely affected, and aggregated particles described below In the forming step, the resin particles and the colorant particles do not aggregate, or even if they aggregate, they may be detached at the time of fusing, which is not preferable because the quality of the obtained toner may deteriorate. On the other hand, when the average particle diameter is within the range, it is advantageous in that the above-mentioned defects are not present, uneven distribution among the toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are reduced. .

A particle dispersion liquid in which the following appropriately selected particles are dispersed may be further mixed. Internal additive particles,
Examples thereof include charge control agent particles, inorganic particles, and abrasive particles. Examples of the internal additive particles include particles such as ferrite, magnetite, reduced iron, cobalt, nickel, manganese, and other metals, alloys, and magnetic materials such as compounds containing these metals. Examples of the charge control agent particles include particles of a quaternary ammonium salt compound, a nigrosine compound, a compound including a complex of aluminum, iron, chromium, zinc, zirconium, or the like. In addition, as the charge control agent particles in the present invention, from the viewpoint of controlling the ionic strength which influences the stability at the time of association and fusion and the reuse of waste water, it is preferable to use a material which is hardly dissolved in water. Examples of the inorganic particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, calcium phosphate, cerium oxide, and all the particles usually used as an external additive on the toner surface. Examples of the abrasive particles include particles of the aforementioned silica, alumina, cerium oxide and the like.

The average particle size of each of the above particles is usually 1
It is less than or equal to μm, preferably 0.01 to 1 μm. When the average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner is widened, and free particles are generated, so that performance and reliability are likely to be deteriorated. On the other hand, when the average particle diameter is within the above range, the above-mentioned drawbacks are eliminated, uneven distribution between toner particles is reduced, dispersion in the toner is improved, and variations in performance and reliability are reduced, which is advantageous.

The content of the wax in the high melting point wax fine particles coated with the low molecular weight polymer and the low melting point wax fine particles coated with the high molecular weight polymer is usually 0.5 to 60% by mass, and preferably 0.5 to 60% by mass. 1-40% by mass
Is. The content of the polymer and the wax in the associative fused particle dispersion liquid when the associative fused particles are formed may be 50% by mass or less, and may be 2 to 4
It is preferably about 0% by mass.

The content of the colorant particles and the like is 1 to 1 in the dispersion liquid when the associative fused particles are formed.
It is about 10% by mass, preferably about 2 to 8% by mass.

The content of each particle such as the additive particles is about 0.01 to 5% by mass in the associated fusion particle dispersion when the association fused particles are formed,
About 5 to 2 mass% is preferable. When the content is out of the range, the particle size distribution may be broadened and the characteristics may be deteriorated.

Further, in order to control the charging property of the obtained toner, it is also preferable to add the charge control particles and the resin particles after the aggregated particles are formed.

The associative fused particles obtained as described above are filtered, washed, and if necessary, classified / dried to obtain toner particles,
It is important to obtain a desired result by adding an external additive given below as an example, particularly an inorganic fine powder, more preferably a hydrophobic inorganic fine powder, if necessary, to obtain a toner.

As the external additive used in the present invention, known inorganic fine powders or resin particles are used, but silica, alumina, and alumina are used to improve the charging stability, developability, fluidity and storage stability.
It is preferably selected from the inorganic fine powders of titania or its complex oxide. When these inorganic particles require hydrophobicity, they are hydrophobized with a silane coupling agent or titanium coupling agent, silicone oil, etc., if necessary.

Further, the following external additives are also used according to the purpose. Lubricant powders such as Teflon powder, zinc stearate powder, polyvinylidene fluoride powder;
Abrasives such as cerium oxide powder, silicon carbide powder, and strontium titanate powder; fluidity-imparting agents such as titanium oxide powder and aluminum oxide powder; anti-caking agent, or carbon black powder, zinc oxide powder, tin oxide powder, etc. Also, a small amount of the electroconductivity-imparting agent, organic fine particles and inorganic fine particles having opposite polarities can be used as a developing property improver.

The toner particles of the present invention can be used as they are or as a toner for a one-component developer or a toner for a two-component developer by preferably adding an external additive.

In the present invention, the particle size of the particles in the dispersion liquid is the number average particle size measured by using a particle size measuring device (LA-700, manufactured by Horiba Ltd.).

In the present invention, SF2 is (perimeter) ↑
It is a shape parameter expressed by 2 / projected area / 4π, and expresses unevenness on the surface of particles. A scanning electron microscope was used to take a photograph of toner particles having a horizontal chord length of 3 or more magnified 500 times, and an image analysis device (L
uzex III) and “SCANNING IMAGE
An image analysis device such as "ANALYSER" (manufactured by JEOL Ltd.) is used to analyze the photographic image. At this time, SF2 of the present invention is measured by the above calculation formula using 500 toner particles. In the present invention, the average value is S
Let F2 be the standard deviation of 500 pieces of SF2, and divide it by the average value of SF2 to obtain the variation coefficient of SF2.

As the measuring device for the weight average diameter of the toner, Coulter Counter TA-II type or Coulter Multisizer II (both manufactured by Coulter, Inc.) was used. As the electrolyte solution, an about 1% NaCl aqueous solution was prepared using primary sodium chloride.
OTONR-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, a surfactant as a dispersant, preferably 0.1 to 5 ml of alkyl versene sulfonate is added to 100 to 150 ml of the electrolyte solution, and 2 to 20 mg of a measurement sample is further added.
Add. The electrolyte solution in which the sample is suspended is subjected to dispersion treatment by an ultrasonic disperser for about 1 to 3 minutes, and the volume and the number distribution of the toner are measured by measuring the volume and number of the toner by using the 100 μm aperture as the aperture with the measuring device. Was calculated. Then, the weight-based weight average particle diameter obtained from the volume distribution according to the present invention was obtained.

In the present invention, the molecular weight distribution of the polymer by GPC using THF as a solvent is measured under the following conditions.
<Measurement of molecular weight distribution by GPC> The column is stabilized in a heat chamber at 40 ° C., and THF as a solvent is flown through the column at this temperature at a flow rate of 1 ml / min.
About 100 μl of HF sample solution is injected for measurement. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count value of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample manufactured by Tosoh Corporation or Showa Denko KK having a molecular weight of about 102 to 107 is used, and it is suitable to use a standard polystyrene sample of at least about 10 points. In addition, the detector is R
An I (refractive index) detector is used. In addition, the column is
It is better to combine a plurality of commercially available polystyrene gel columns, for example, shodex GPC manufactured by Showa Denko KK
KF-801, 802, 803, 804, 805, 80
Combination of 6,807,800P and Tosoh T
SKgel G1000H (HXL), G2000H
(HXL), G3000H (HXL), G4000H
(HXL), G5000H (HXL), G6000H
(HXL), G7000H (HXL), TSKgurd
A combination of columns can be mentioned. The sample is prepared as follows. Put the sample in THF,
After leaving it for several hours, shake it well and mix it well with THF (until the coalescence of the samples disappears), and leave it still for 12 hours or more. At that time, leave it in THF for 24 hours or more. After that, a sample processing filter (pore size 0.2 to 0.5 μm, for example, Mysholydisk H
-25-2 (manufactured by Tosoh Corporation) can be used. ) Is used as a GPC sample. The sample concentration is
The resin component is adjusted to be 0.5 to 5 mg / ml.

In the present invention, T of the resin component in the toner is
The HF insoluble matter and the THF insoluble matter of the raw material binder resin are measured as follows. <Measurement of THF-insoluble matter> Binder resin and toner 0.5 to 1.0 g are weighed (W1 g), cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kaisha, Ltd.) is put into a Soxhlet extractor, and 200 ml of THF is used as a solvent. Extraction is carried out for 10 hours, and the soluble component solution extracted by the solvent is evaporated, followed by vacuum drying at 100 ° C. for several hours, and the THF soluble resin component amount is weighed (W2g). The weight other than the resin component in the toner is determined (W3g). TH
The F insoluble content is obtained from the following formula.

[0075]

[Outer 1]

In the present invention, the melting point of the wax is DSC.
The melting point of the wax is defined as the temperature at the peak top of the maximum endothermic peak of the wax measured in 1.
In the present invention, the DSC measurement of the wax or toner by the differential scanning calorimeter is preferably performed by a highly accurate internal heat input compensation type differential scanning calorimeter. For example, DSC-7 manufactured by Perkin Elmer can be used. The measuring method is performed according to ASTM D3418-82. The DSC curve used in the present invention is a DSC curve measured when the temperature is 10 ° C./min and the temperature is lowered in the range of 0 to 200 ° C. after the temperature is raised once and the previous history is taken. To use.

For measuring the glass transition point Tg, for example, a high precision internal heat input compensation type differential scanning calorimeter such as DSC-7 manufactured by Perkin Elmer Co. is used. The measuring method is performed according to ASTM D3418-82.

The method for measuring the triboelectric charge amount of the toner will be described below. An outline of the measuring device is shown in FIG. 23 ° C, relative humidity 60
% 0.0005 Kg of developer 30 in a metal measuring container 32 having a 500-mesh screen 33 at the bottom
And put on the lid 34 made of metal. Measuring container 3 at this time
2 Weigh the whole and set it as W1g. Next, using a suction device (at least an insulator is in contact with the measurement container 32), suction is performed from the suction port 37 and the air volume control valve 36 is adjusted to adjust the vacuum gauge 3
The pressure of 5 is 250 mmAq. In this state, suction is performed for 3 minutes to remove the developer by suction. Electrometer 39 at this time
Is set to V (volt). Here, 38 is a capacitor, and the capacity is C (mF). In addition, the weight of the entire measuring machine after suction is weighed and is W2 (Kg). The triboelectric charge amount (mC / Kg) of this developer is usually calculated by the following formula.

[0079] Triboelectric charge amount (mC / Kg) = CV / (W1-W2) Hereinafter, the present invention will be described with reference to examples.

(Dispersion Liquid Production Example) (Dispersion Liquid Production Example 1) Styrene 340 parts by mass n-Butyl acrylate 110 parts by mass Acrylic acid 25 parts by mass t-dodecyl mercaptan 10 parts by mass or more are mixed and dissolved. And prepared as a monomer mixture. Low-molecular-weight polypropylene wax dispersion having a melting point of 130 ° C. 100 parts by mass (solid content concentration 30% by mass, dispersed particle size 0.14 μm) Anionic surfactant 1.6 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) ) Nonionic surfactant 0.41 part by mass (manufactured by Sanyo Kasei Co., Ltd .: Nonipol 400) 1530 parts by mass of ion-exchanged water are dispersed in a flask, and heating is started while performing nitrogen substitution. When the liquid temperature reached 70 ° C, 6.56
A solution of 350 parts by mass of potassium persulfate dissolved in 350 parts by mass of ion-exchanged water was added. While maintaining the liquid temperature at 70 ° C., the above monomer mixture was charged and stirred, the liquid temperature was raised to 80 ° C., emulsion polymerization was continued for 5 hours, and then the liquid temperature was adjusted to 40 ° C. and then filtered with a filter to obtain dispersion A. Got Thus, the average particle size of the particles in the obtained dispersion is 0.16.
μm, the glass transition point of the solid content was 58 ° C., the weight average molecular weight (Mw) was 12,000, and P1 was 11,000. The low molecular weight polypropylene wax was contained in the polymer in an amount of 6% by mass, and it was confirmed by observing a thin piece of the solid content with a transmission electron microscope that the wax particles were encapsulated. The polymer had a THF insoluble content of substantially zero.

(Dispersion Liquid Production Example 2) Styrene 340 parts by mass n-butyl acrylate 110 parts by mass Acrylic acid 25 parts by mass The above proportions were mixed and dissolved to prepare a monomer mixture. Hydrocarbon wax dispersion having a melting point of 75 ° C. 100 parts by mass (solid content concentration 30% by mass, dispersed particle size 0.15 μm) Anionic surfactant 1.6 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen) SC) 0.41 part by mass of nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Nonipol 400) 1530 parts by mass of ion-exchanged water are dispersed in a flask, and heating is started while performing nitrogen substitution. When the liquid temperature reached 65 ° C, 5.85
A solution prepared by dissolving 300 parts by mass of potassium persulfate with 300 parts by mass of ion-exchanged water was added. While maintaining the liquid temperature at 65 ° C., the above monomer mixture was added and stirred, the liquid temperature was raised to 75 ° C., emulsion polymerization was continued for 5 hours, the liquid temperature was adjusted to 40 ° C., and the mixture was filtered with a filter to obtain dispersion B. Got Thus, the average particle size of the particles in the obtained dispersion is 0.16.
μm, the glass transition point of the solid content was 60 ° C., and the weight average molecular weight (Mw) was 600,000. The hydrocarbon wax was contained in the polymer in an amount of 6% by mass, and as a result of observing a thin piece of the solid content with a transmission electron microscope, it was confirmed that the wax particles were encapsulated. The THF insoluble content of the polymer was 7% by mass.

Dispersion Liquid Preparation Example 3 Styrene 340 parts by mass, n-butyl acrylate 110 parts by mass, acrylic acid 25 parts by mass, t-dodecyl mercaptan 10 parts by mass or more were mixed and dissolved to prepare a monomer mixture. did. Anionic surfactant 1.6 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) Nonionic surfactant 0.41 parts by mass (Sanyo Kasei Co., Ltd .: Nonipol 400) Ion-exchanged water 1530 parts by mass Parts are dispersed in a flask and heating is started while performing nitrogen substitution. When the liquid temperature reached 70 ° C, 6.56
A solution of 350 parts by mass of potassium persulfate dissolved in 350 parts by mass of ion-exchanged water was added. While maintaining the liquid temperature at 70 ° C., the above monomer mixture was charged and stirred, the liquid temperature was raised to 80 ° C., emulsion polymerization was continued for 5 hours, the liquid temperature was adjusted to 40 ° C., and the mixture was filtered with a filter to obtain dispersion C. Got In this way, the particle size of the resulting dispersion is 0.15.
μm, the glass transition point of the solid content was 58 ° C., the weight average molecular weight (Mw) was 13,000, and P1 was 12,000. The polymer had a THF insoluble content of substantially zero.

Dispersion Liquid Preparation Example 4 Styrene 340 parts by mass, n-butyl acrylate 110 parts by mass, acrylic acid 25 parts by mass and more were mixed and dissolved to prepare a monomer mixture. Anionic surfactant 1.6 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) Nonionic surfactant 0.41 parts by mass (Sanyo Kasei Co., Ltd .: Nonipol 400) Ion-exchanged water 1530 parts by mass Parts are dispersed in a flask and heating is started while performing nitrogen substitution. When the liquid temperature reached 65 ° C, 5.85
A solution prepared by dissolving 300 parts by mass of potassium persulfate with 300 parts by mass of ion-exchanged water was added. While maintaining the liquid temperature at 65 ° C., the above monomer mixture was charged and stirred, the liquid temperature was raised to 75 ° C., emulsion polymerization was continued for 5 hours, the liquid temperature was adjusted to 40 ° C., and the mixture was filtered with a filter to obtain dispersion D. Got Thus, the average particle size of the particles in the obtained dispersion is 0.16.
μm, the glass transition point of the solid content was 60 ° C., and the weight average molecular weight (Mw) was 650000. The THF insoluble content of the polymer was 5% by mass.

Dispersion Preparation Example 5 Styrene 340 parts by mass, n-butyl acrylate 110 parts by mass, acrylic acid 25 parts by mass, t-dodecyl mercaptan 10 parts by mass or more were mixed and dissolved to prepare a monomer mixture. did. Hydrocarbon wax dispersion having a melting point of 75 ° C. 100 parts by mass (solid content concentration 30% by mass, dispersed particle size 0.15 μm) Anionic surfactant 1.6 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) ) Nonionic surfactant 0.41 part by mass (manufactured by Sanyo Kasei Co., Ltd .: Nonipol 400) 1530 parts by mass of ion-exchanged water are dispersed in a flask, and heating is started while performing nitrogen substitution. When the liquid temperature reached 70 ° C, 6.56
A solution of 350 parts by mass of potassium persulfate dissolved in 350 parts by mass of ion-exchanged water was added. While maintaining the liquid temperature at 70 ° C., the above monomer mixture was charged and stirred, the liquid temperature was raised to 80 ° C. and emulsion polymerization was continued for 5 hours, and then the liquid temperature was adjusted to 40 ° C. and then filtered with a filter to obtain dispersion E. Got Thus, the average particle size of the particles in the obtained dispersion is 0.16.
μm, the glass transition point of the solid content was 57 ° C., the weight average molecular weight (Mw) was 11,000, and P1 was 12000. The hydrocarbon wax was contained in the polymer in an amount of 6% by mass, and as a result of observing a thin piece of the solid content with a transmission electron microscope, it was confirmed that the wax particles were encapsulated. The polymer had a THF insoluble content of substantially zero.

(Dispersion Liquid Preparation Example 6) C.I. I. Pigment Blue 15: 3 20 parts by mass ・ Anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) ・ Ion-exchanged water 78 parts by mass or more are mixed and dispersed using a sand grinder mill. , A colorant dispersion was obtained. The average particle size of the colorant particles is
Coarse particles having a size of 0.2 μm and exceeding 1 μm were not observed.

Example 1 Dispersion A 300 parts by mass Dispersion B 150 parts by mass Colorant Dispersion Solution 1 25 parts by mass 1 liter of a separable, equipped with a stirrer, a cooling tube and a thermometer. The mixture was placed in a flask and stirred. The pH of this mixed solution was adjusted to 5.2 using 1N-potassium hydroxide.

To this mixed solution, 150 parts by mass of a 10% aqueous sodium chloride solution was added dropwise as a coagulant, and the contents of the flask were heated to 57 ° C. with stirring in an oil bath for heating.
After holding at 50 ° C. for 1 hour, it was confirmed by observation with an optical microscope that associated particles having a diameter of about 7 μm were formed.

In the subsequent fusion-bonding step, an anionic surfactant (Neogen S manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added here.
C) After adding 3 parts by mass, the stainless steel flask was closed, and the magnetic seal was used to continue stirring at 105 ° C.
Heated to and held for 3 hours. Then, after cooling, the reaction product was filtered, sufficiently washed with ion-exchanged water, and then dried to obtain cyan toner particles 1. The weight average diameter was 7.0 μm, SF2 was 145, and the coefficient of variation of SF2 was 6.4.

P1 of the present toner particles and toner is 110
00, THF insoluble matter is 3% by mass, and Mw is 210000.

BE was added to 100 parts by weight of the toner particles.
Hydrophobic silica 0.7 having a T specific surface area of 200 m2 / g
By mass, 0.7 parts by mass of hydrophobic titanium oxide having a primary particle diameter of 50 nm was added and dry mixed to obtain a toner. Weight average diameter of 7.0, SF2 of 144, and coefficient of variation of SF2 of 6.3.
Met. A two-component developer was prepared by mixing with a ferrite carrier having a particle diameter of 50 μm coated with a silicone resin containing an aminosilane coupling agent at a mass ratio of 5: 100.

P1 of the present toner particles and toner is 110
00, THF insoluble matter is 3% by mass, and Mw is 210000.

The results of the fixing test, storage stability and development stability test are shown in Table 1.

[0093]

[Table 1]

In the fixing test, a heating roller having a surface coated with FEP was used, the nip width was 5 mm, a toner image was formed in a strip shape on the recording paper, and the toner image was passed through a temperature-controlled fixing device. However, when the temperature is changed to 100 to 200 ° C., it has a minimum temperature when the toner is sufficiently adhered to the recording paper and the offset toner is not recognized on the heating roller, and a maximum temperature at which the offset toner is not observed. evaluate.

The prepared two-component developer is put in a two-component developing machine, the initial triboelectrification amount is measured, and after idling for 2 hours, the stability of development is evaluated by the change in triboelectrification amount. If the amount of change is ± 15%, it is good.

The storage stability was good because about 50% of the toner was put in a 50 ml poly cup and left in an atmosphere of 50 ° C. for 3 days, and there was no agglomerate after standing.

(Example 2) In the fusion process, the temperature was set to 1
Cyan toner particles 2 were obtained in the same manner as in Example 1 except that the temperature was set to 00 ° C. Weight average diameter 7.1 μm, SF2 is 16
5 and the coefficient of variation of SF2 were 7.6.

Table 1 shows the results of a fixing test, a storage stability and a development stability test which were carried out by mixing external additives and preparing a developer in the same manner as in Example 1. The weight average diameter of the toner after external addition mixing is 7.1 μm, SF2 is 164, and the variation coefficient of SF2 is 7.
It was 4.

P1 of the present toner particles and toner is 110
00, THF insoluble matter is 3% by mass, and Mw is 210000.

(Example 3) In the fusion process, the temperature was set to 1
Cyan toner particles 3 were obtained in the same manner as in Example 1 except that the temperature was changed to 10.degree.

The weight average diameter is 7.1 μm, SF2 is 125,
The coefficient of variation of SF2 was 4.5.

Table 1 shows the results of a fixing test, a storage stability and a development stability test, which were carried out by mixing external additives and preparing a developer in the same manner as in Example 1. The weight average diameter of the toner after external addition mixing is 7.1 μm, SF2 is 125, and the coefficient of variation of SF2 is 4.
It was 5.

P1 of the present toner particles and toner is 110
00, THF insoluble matter is 3% by mass, and Mw is 210000.

Comparative Example 1 Dispersion E instead of Dispersion A
Cyan toner particles 4 were obtained in the same manner as in Example 1 except that was used.

The weight average diameter is 7.0 μm, SF2 is 140,
The coefficient of variation of SF2 was 6.1.

Table 1 shows the results of a fixing test, a storage stability and a development stability test which were carried out by mixing external additives and preparing a developer in the same manner as in Example 1. The weight average diameter of the toner after external addition mixing is 7.0 μm, SF2 is 138, and the variation coefficient of SF2 is 6.
It was 3.

Comparative Example 2 Dispersion C 300 parts by mass Dispersion D 150 parts by mass Colorant dispersion 1 25 parts by mass Low molecular weight polypropylene wax dispersion having a melting point of 130 ° C. 6 parts by mass (solid content concentration 30% by mass, dispersion Particle size 0.14 μm) Hydrocarbon wax dispersion with a melting point of 75 ° C. 12 parts by mass (solid content concentration 30% by mass, dispersed particle size 0.15 μm) 1 liter equipped with a stirrer, cooling tube, thermometer It was put in a separable flask of and stirred. The pH of this mixed solution was adjusted to 5.2 using 1N-potassium hydroxide.

To this mixed solution, 150 parts by mass of a 10% aqueous sodium chloride solution was added dropwise as a coagulant, and the contents of the flask were heated to 57 ° C. in an oil bath for heating while stirring.
After holding at 50 ° C. for 1 hour, it was confirmed by observation with an optical microscope that associated particles having an average particle diameter of about 7 μm were formed.

In the subsequent fusion-bonding step, an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen S
C) After adding 3 parts by mass, the stainless steel flask was closed, and the magnetic seal was used to continue stirring at 105 ° C.
Heated to and held for 3 hours. Then, after cooling, the reaction product was filtered, sufficiently washed with ion-exchanged water, and then dried to obtain cyan toner particles 1.

The weight average diameter is 6.9 μm, SF2 is 155,
The coefficient of variation of SF2 was 6.8.

Table 1 shows the results of a fixing test, a storage stability and a development stability test which were carried out by mixing external additives and preparing a developer in the same manner as in Example 1. The weight average diameter of the toner after external addition mixing is 6.7 μm, SF2 is 152, and the variation coefficient of SF2 is 7.
It was 0.

Comparative Example The toner particles obtained in Example 1 were melt-kneaded in a roll mill at 140 ° C. and pulverized and classified to obtain cyan toner particles having a weight average diameter of 7.5 μm.

Table 1 shows the results of a fixing test, a storage stability and a development stability test which were carried out by mixing external additives and preparing a developer in the same manner as in Example 1.

[0114]

EFFECTS OF THE INVENTION In a method for producing toner particles by associating and fusing a plurality of polymer fine particles dispersed in an aqueous medium, (1) high melting point wax fine particles coated with a low molecular weight polymer are dispersed. Toner particles produced by associating and fusing a mixed dispersion liquid containing the first dispersion liquid (2) and the second dispersion liquid (2) in which low-melting-point wax fine particles coated with a high molecular weight polymer are dispersed As a result, it is possible to achieve low-temperature fixability and high-temperature offset resistance, excellent storage stability, and good development stability, as compared with conventional ones.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a toner triboelectric charge amount measuring device used in Examples.

[Explanation of symbols]

30 developer 32 measuring vessels 33 screens 34 Lid 35 vacuum gauge 36 Air flow control valve 37 Suction port 38 condenser 39 electrometer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/08 384

Claims (6)

[Claims] 1. A method for producing toner particles, which comprises associating and fusing a plurality of polymer fine particles dispersed in an aqueous medium, the high melting point wax fine particles coated with at least a low molecular weight polymer, and a high molecular weight polymer. A method for producing toner particles, which comprises associatively fusing low-melting-point wax fine particles coated by coalescence. 2. The high melting point wax fine particles coated with the low molecular weight polymer or the low melting point wax coated with the high molecular weight polymer is obtained by polymerizing a polymerizable monomer in the presence of the wax fine particles. The method for producing toner particles according to claim 1. 3. The temperature for fusion in an aqueous medium is not higher than the melting point of the high melting point wax and is not lower than the melting point of the low melting point wax.
3. The method for producing toner particles according to any one of items 1 to 2. 4. The toner particles have a weight average diameter of 3 to 9 μm.
4. The method for producing toner particles according to claim 1, wherein m and SF2 are 120 to 170, and the variation coefficient of SF2 is 4.0 to 8.0. 5. A toner particle produced by associating and fusing at least a high melting point wax fine particle coated with a low molecular weight polymer and a low melting point wax fine particle coated with a high molecular weight polymer in an aqueous medium. Weight average diameter is 3 to 9 μm, SF2 is 120 to 170 and S
A toner particle having a coefficient of variation of F2 of 4.0 to 8.0. 6. A toner using toner particles produced by associating and fusing at least high melting point wax fine particles coated with a low molecular weight polymer and low melting point wax fine particles coated with a high molecular weight polymer in an aqueous medium. , Having a hydrophobic inorganic fine powder on the surface of the toner particles, and having a weight average diameter of
A toner having a particle size of 3 to 9 μm, an SF2 of 120 to 170 and a variation coefficient of SF2 of 4.0 to 8.0.