JP4347176B2 - Toner manufacturing method and image forming method - Google Patents

Description

  The present invention relates to a toner used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, and the like, and an electrophotographic image forming method using the toner. More specifically, the present invention relates to a toner for electrophotography and an image forming method used for a copying machine, a laser printer, a plain paper fax machine, and the like using a direct or indirect electrophotographic developing system. Further, the present invention relates to a method for forming a toner image for electrophotography used in a full-color copying machine, a full-color laser printer, a full-color plain paper fax machine and the like using a direct or indirect electrophotographic multicolor developing system.

  In the developing process, the developer used in electrophotography, electrostatic recording, electrostatic printing, etc. is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then After being transferred from the photoreceptor to a transfer medium such as transfer paper in the transfer process, it is fixed on the paper surface in the fixing process. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer not requiring a carrier (magnetic toner, Non-magnetic toners are known.

  In order to obtain high-quality and high-quality images, improvements have been made by reducing the particle size of the toner or narrowing its particle size distribution. The particle shape is indeterminate, and when it is used as a one-component developer in the machine, it is agitated with a carrier in the developing unit, or contacted by a developing roller and a toner supply roller, a layer thickness regulating blade, a friction charging blade, etc. Further, the toner is further pulverized by the stress, and fine particles are generated, or a fluidizing agent is embedded in the toner surface, resulting in a phenomenon that the image quality is deteriorated. Further, due to its shape, the fluidity as a powder is poor, and a large amount of fluidization is required, and the filling rate into the toner bottle is low, which is an obstacle to downsizing.

  Furthermore, the process of transferring images formed from multicolor toners from a photoconductor to a transfer medium or paper to create a full-color image has become complicated, and the transferability due to an irregular shape such as pulverized toner has been increased. Due to the inconvenience, problems have arisen such that the transferred image is missing and the amount of toner consumed is large to compensate for it.

  Accordingly, there is a growing demand for further improvement in transfer efficiency to obtain a high-quality image with no loss of toner by reducing toner consumption, or to reduce running costs. If the transfer efficiency is very good, there is no need for a cleaning unit to remove untransferred toner from the photoconductor or transfer medium, and the equipment can be reduced in size and cost, and waste toner is eliminated. However, in reality, it is difficult to completely transfer the toner from the photosensitive member or the intermediate transfer medium, and the toner is collected and reused using a cleaner. It was difficult. In order to compensate for the drawbacks of the spherical and irregular shape effects, various toner manufacturing methods have been devised that are slightly distorted from the spherical shape.

On the other hand, a method has been proposed in which fine particles are aggregated to form an aggregate composed of amorphous particles, and then the fine particles are fused. However, the fine particles may not be fused and remain alone. The toner containing these must be separated as an unnecessary component because it causes a transfer failure when an image is formed. However, there is a problem in discarding such unnecessary components because of environmental protection.
Patent Document 1 proposes a method of dispersing and reusing coarse particle components and ultrafine particle components, so-called non-predetermined toner particles, separated in a drying assisting step in a polymerizable monomer system. However, when these non-predetermined toner particles are mixed in the liquid, they tend to become lumps and uniform dispersion is difficult.

JP-A-10-301330

  Accordingly, the present invention has been made in view of the above-mentioned problems, and the problem is that a method for producing an electrophotographic toner in which a pigment is uniformly dispersed in a toner, and an image using an electrophotographic toner produced by this production method. It is to provide a forming method.

The features of the present invention, which is a means for solving the above problems, are listed below.
1. In the method for producing an electrophotographic toner of the present invention, a toner material containing at least a binder resin and a colorant is dissolved and / or dispersed in an organic solvent, and this is emulsified and / or dispersed in an aqueous medium, followed by particle formation. In the method for producing an electrophotographic toner obtained by performing wet classification later, the electrophotographic toner production method includes a binder resin in which ultrafine particles containing moisture generated by being removed by wet classification are added to a toner material. , A master batch melt-kneaded with a colorant is included , and the mixing ratio of the master batch is 50% by weight or less of the whole toner material, and solids of ultrafine particles containing moisture generated by being removed by wet classification min concentration characterized in that 20% to 50%.

2. The electrophotographic toner of the present invention is obtained by dissolving and / or dispersing a toner material containing at least a binder resin and a colorant in an organic solvent that can be dissolved or swelled, and emulsifying and / or dispersing the toner material in an aqueous medium. An electrophotographic toner obtained by wet classification after particle formation, wherein the electrophotographic toner is produced by binding ultrafine particles containing water generated by wet classification to a toner material. A masterbatch melt-kneaded with a resin and a colorant is included , and the mixing ratio of the masterbatch is 50% by weight or less of the whole toner material, and ultrafine particles containing moisture generated by being removed by wet classification The solid content concentration is 20% to 50% .
3. The electrophotographic image forming method of the present invention is characterized in that in the electrophotographic image forming method for visualizing an electrostatic latent image with a toner, the electrostatic latent image is visualized with the electrophotographic toner described in 1 above .

4). According to the method for producing a color toner for electrophotography of the present invention, a toner material containing at least a binder resin, a colorant for yellow, magenta, cyan, and black is dissolved / dispersed in an organic solvent and emulsified in an aqueous medium. In addition, in the method for producing a color toner for electrophotography obtained by wet classification after particle formation after dispersion, the method for producing a color toner for electrophotography is obtained by wet classification for each colorant in the toner material. A master batch in which ultrafine particles containing moisture generated by removal are melt-kneaded together with a binder resin and a colorant are included , and the mixing ratio of the master batch is 50% by weight or less of the entire toner material, and wet classification the solid content of ultrafine particles containing moisture generated by being removed at the you characterized in that 20% to 50%.
5). The full-color image forming method of the present invention is an electrophotographic full-color image forming method in which an electrostatic latent image is visualized with a color toner, and the image forming method is visualized with the electrophotographic color toner described in 4 above. Features.

As is apparent from the detailed and specific description above, according to the present invention, the toner material is melt-kneaded and then dispersed and dissolved in an organic solvent to form a toner in an aqueous medium or emulsified in an aqueous medium. a process for the aggregation toner preparation until the toner size, the addition of ultrafine particles produced by a wet classification step to the masterbatch improves the pigment dispersion effect, improves the degree of coloration, economical and no waste, environmental It is possible to provide a method for producing a toner for developing an electrostatic image that is easy on the environment.

  The best mode for carrying out the present invention will be described below with reference to the drawings. Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

Here, the production method and materials for the toner and developer used in the present invention will be described in detail. Examples of the binder resin kneaded with the toner constituting material, the resin kneaded into the master batch, or the binder resin to be dissolved include polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and other styrene and substituted polymers thereof; styrene -P-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloro Methyl methacrylate copolymer, styrene-acrylic Nitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, urethane, urea-modified polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, Polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. Can be mixed and used.

  As the colorant to be kneaded with the above-mentioned binder resin or used for producing a masterbatch, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow ( 10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red , Antimon Zhu, Permanentre 4R, Parared, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Rake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Rune, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc Green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green go , Acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon and mixtures thereof can be used. The amount used is generally 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin, and 5 to 500 parts by weight with respect to 100 parts by weight of the binder resin in the master batch.

  The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEGVP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex ( Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinaclide , Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

In the present invention, the amount of charge control agent used is determined uniquely by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. Although not intended, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density Cause a decline.
The charge control agent is preferably kneaded together with the binder resin to adjust the dispersion diameter, but when emulsified in an aqueous medium, it elutes or desorbs from the dispersed phase of the oil phase to the aqueous phase side. In such a case, it may be added to the aqueous phase and incorporated into the toner during the aggregation process or drying process.

In order to impart releasability to the manufactured developer, it is preferable to include a wax in the manufactured toner. The wax has a melting point of 40 to 120 ° C., and preferably 50 to 110 ° C. When the melting point of the wax is excessive, the fixability at a low temperature may be insufficient. On the other hand, when the melting point is excessively low, the offset resistance and durability may be decreased. The melting point of the wax can be obtained by differential scanning calorimetry (DSC). That is, the melting peak value when a sample of several mg is ripened at a constant temperature increase rate, for example, (10 ° C./min) is defined as the melting point.
Examples of the release agent (wax) that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketone, fatty acid metal salt wax, and fatty acid ester. And waxes, partially saponified fatty acid ester waxes, silicone varnishes, higher alcohols and carnauba waxes. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used. Particularly, a polyolefin having a softening point of 70 to 150 ° C. by the ring and ball method is preferable, and a polyolefin having a softening point of 120 to 150 ° C. is more preferable. These charge control agents and release agents are preferably melt-kneaded with a colorant and a binder resin, or master-batch, and melt-kneaded with a resin, but of course may be added when dissolved and dispersed in an organic solvent. . At that time, it is preferable to finely disperse, but for this purpose, a method of cooling and precipitating after dissolving in an organic solvent, or mechanically finely dispersing in an organic solvent by stirring with a medium such as beads. Method is adopted.
In addition, a wax emulsion obtained by heating and stirring and emulsifying in a water-based medium using a surfactant and a dispersant described later can be prepared and agglomerated together with a colored fine dispersion during the aggregation process. good.

As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylic acid ester, acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine, nylon, thermosetting Examples thereof include polymer particles made of a resin.

Such a fluidizing agent performs surface treatment to increase hydrophobicity, and can prevent deterioration of fluidity characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

(Production method)
Prior to the kneading step, the materials are mixed mechanically and uniformly. That is, a toner component including at least a binder resin, a colorant master batch, a charge control agent, and a release agent, if necessary, and an ultra fine particle including water generated in the wet classification process of the present invention are mechanically combined. The mixing step for mixing may be performed under normal conditions using a normal mixer with rotating wings, and is not particularly limited.
When the above mixing process is completed, the mixture is then charged into a kneader and melt-kneaded. In addition to the usual two rolls and three rolls, a method of using a Banbury mixer as an open type, a continuous two roll kneader manufactured by Mitsui Mining Co., Ltd., and the like are preferably used.
Dispersing pigment aggregates to 0.001 to 0.1 μm primary particles by a normal kneading method is a limit in a normal kneading method by repeated mechanical shearing. That is, the fact that the dispersion of the pigment is bad is none other than that the aggregate cannot be crushed. Since the aggregate is crushed, the necessary condition is that the surrounding resin enters the voids inside the aggregate and efficiently wets all the primary particle surfaces. Therefore, the point of pigment dispersion is whether or not the surrounding resin can enter the voids inside the aggregate.

Organic pigments that are generally used as colorants are hydrophobic, but in the manufacturing process, they are washed with water and dried, so if some force is applied, water is soaked into the pigment aggregate. It is possible. When kneaded at a set temperature of 100 ° C. or higher with an open type kneader, the water inside the aggregates instantaneously reaches the boiling point and expands in volume, which adds a force to break up the aggregates from within the aggregates. become. The force from the inside of the aggregate can disintegrate the aggregate very efficiently compared to the force applied from the outside. In addition, when kneading, by using the ultrafine particles containing water after wet classification according to the present invention as a master batch, as described above, a small binder resin is allowed to enter the agglomerates, and the effect of pigment dispersion can be obtained. I can give you.
Since the pigment is uniformly dispersed and additionally heated to a temperature above the softening point, the viscosity is lowered and the aggregate is efficiently wetted. At the same time, water close to the boiling temperature inside the aggregate and so-called flushing are resembling. By substituting with the effect, a master batch pigment in which the pigment is dispersed in a state close to primary particles can be obtained.
Further, in the process of evaporating the water, the water in the ultrafine particles containing water takes away the heat of vaporization accompanying the evaporation from the kneaded material, so that the temperature of the kneaded material is maintained at a relatively low temperature and high viscosity of 100 ° C. or less. Therefore, it has an effect that the shearing force is effectively applied to the pigment aggregate.
The ultrafine particles containing water may contain unnecessary solvent components, which are vaporized by heat during kneading and can be prevented from being mixed into the master batch.

The kneaded product or masterbatch, resin or other toner material obtained in an organic solvent is stirred by a normal impeller, heat-treated as necessary, and dissolved and dispersed by a ball mill, sand mill, homogenizer, etc. And emulsified and dispersed in an aqueous medium. At that time, an emulsifier such as a homomixer (manufactured by Special Machine Engineering Co., Ltd.), Ebara Milder (manufactured by Ebara Seisakusho), Claremix (manufactured by M Technique Co., Ltd.) or the like is used. By controlling the concentration of the emulsifier, the concentration of the kneaded product with respect to the organic solvent, the ratio of the aqueous medium and the oily phase in which the kneaded product is dispersed, the number of rotations during the emulsification dispersion, and the time, the desired droplet size and particle size are controlled. Can be distributed. It is preferable to emulsify and disperse to 1/2 to 1/100 of the target toner particle diameter. The weight ratio between the kneaded material and the organic solvent is preferably selected between 1:10 and 1: 1, and the weight ratio between the aqueous medium and the oily phase in which the kneaded material is dispersed is appropriately selected between 10: 1 and 1: 1. However, of course, it may be outside this range.
As an aqueous medium, water, organic solvents such as methanol, ethanol, etc. that can be partially mixed with water, ethanol such as ethanol, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate are also used in combination with water. Can be used.

The organic solvent for dissolving and dispersing the toner component in the kneaded product is not particularly limited as long as it is insoluble or hardly soluble in water and partially soluble, and can dissolve the resin constituting the kneaded product and the resin used during kneading. Not particularly limited, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable.
Anionic interfaces such as alkylbenzene sulfonates, α-olefin sulfonates, phosphates, etc. as dispersants for emulsifying and dispersing the oily phase in which the toner component is dispersed in a liquid containing water to a desired particle size Activators, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts , Quaternary ammonium salt type cationic surfactants such as benzethonium chloride, nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine N- alkyl -N, amphoteric surfactants such as N- dimethyl ammonium betaine and the like.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  Examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having fluoroalkyl groups, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzas. Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

Moreover, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, etc. can be used as an inorganic compound dispersant that is hardly soluble in water.
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having nitrogen atoms or heterocyclic rings thereof, polyoxyethylene, polyoxypropylene, polymers Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. At that time, it is preferable to carry out under reduced pressure because the heating temperature can be lowered. This is to prevent the wax and other toner constituents from dissolving in the organic solvent, and to prevent abnormal aggregation, association and coalescence due to heating of the emulsified dispersion. This organic solvent removal step may be performed before the aggregation step or after the aggregation step. If the organic solvent is removed before the aggregation step, fusion and coalescence of the fine particles after aggregation can be promoted.
Another treatment method for those dissolved in an organic solvent is to spray the emulsified dispersion into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, which are combined with an aqueous dispersion. It is also possible to evaporate and remove the agent. As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.
As the agglomeration method, when fine particles are dispersed in water with an electric charge, the electric double layer is compressed by casting an electrolyte or the like to agglomerate the particles or form a high molecular weight water-soluble polymer into particles. By adsorbing and aggregating each other, or introducing a substance that is oppositely charged to the surfactant or dispersant used, the charge on the surface of the fine particles is neutralized and aggregated, or the adsorbed surfactant or dispersion A method is adopted in which the solubility of the surfactant or dispersant in the aqueous medium is changed by changing the counter ion of the agent or by introducing another substance into the aqueous medium to weaken the dispersion stability and cause aggregation. The
At that time, it is agglomerated with the wax emulsion and the resin fine particles having the polar group described above to give the manufactured toner releasability at the time of fixing, to enhance the triboelectric chargeability, By disposing the high resin fine particles relatively outside the toner, blocking of the toners during high temperature storage can be prevented.

Examples of the flocculant used include sodium sulfate, ammonium sulfate, potassium sulfate, magnesium sulfate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium chloride, calcium chloride, cobalt chloride, and strontium chloride. General inorganic or organic water-soluble salts represented by cesium chloride, barium chloride, nickel chloride, magnesium chloride, rubidium chloride, sodium chloride, potassium chloride, sodium acetate, ammonium acetate, potassium acetate, sodium benzoate, etc. Can be used. The concentration of these electrolytes ranges from 0.01 to 2.0 mol / l, more preferably from 0.1 to 1.0 mol / l, and even more preferably from 0.2 to 0.8 mol / l when a monovalent electrolyte is used. preferable. Furthermore, when a polyvalent electrolyte is used, the amount added may be smaller. In the case of a surfactant, those exemplified above, and in the case of a polymer-based aggregating agent, among those that form the above-mentioned polymer protective colloid, those of ultra high molecular weight are particularly suitable. In addition, as a substance to coagulate by coexisting in an aqueous medium, it is possible to use water-soluble organic compounds such as ethanol, butanol, isopropanol, ethyl cellosolve, butyl cellosolve, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, etc. it can.
Further, by heating the dispersion liquid after aggregation, the fine particles can be fused to adjust the shape of the toner to be produced. The particles are spheroidized by the interfacial tension, and the particle shape can be arbitrarily adjusted from spherical to indeterminate depending on the heating temperature, the viscosity of the toner, the presence of an organic solvent, and the like.

The obtained dispersion of aggregated particles is sprayed in a dry atmosphere to completely remove the water-insoluble organic solvent remaining in the aggregated particles to form toner fine particles, and the aqueous dispersant is evaporated together. It is also possible to remove it. As the dry atmosphere in which the dispersion of the aggregated particles is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, etc., especially various air currents heated to a temperature higher than the boiling point of the highest boiling solvent used are generally used. It is done. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln. If the operation of re-dispersing (reslurry) is repeated by separating the liquid into solid and liquid before drying and redispersing (reslurry), the used dispersant and emulsifier can be almost removed.
In addition, when an acid such as calcium phosphate salt or an alkali-soluble one is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as washing with water after dissolving the calcium phosphate salt with an acid such as hydrochloric acid. To do. It can also be removed by operations such as enzymatic degradation.

In the wet classification operation after the agglomeration operation, the fine particle portion is removed in the liquid by a cyclone, a decanter, centrifugal separation or the like, and the obtained ultrafine particles are returned to the master batch kneading step of the present invention and reused.
In some cases, wet classification is not performed after the agglomeration operation, and dry classification is performed after drying. In this case, the classifier includes an inertia class elbow jet, a centrifugal class microplex, a DS separator, and the like. The ultra fine powder generated at this time is returned to the master batch kneading step of the present invention and reused.

In addition, the toner powder after drying can be mixed with different types of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by applying mechanical impact force to the mixed powder. By immobilizing and fusing, it is possible to prevent the dissociation of the foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system (Made by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is 1 to 10 wt. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexa Fluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as terpolymers of emission and non-fluoride monomers including, and silicone resins. Moreover, you may make conductive powder etc. contain in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(Full color image development method)
The full-color two-component or non-magnetic one-component image forming method of the present invention includes a developing roller having a magnetic sleeve, a developing roller made of an elastic body, a roller made of metal, and a uniform layer thickness of developer supplied onto the developing roller. By means of a plurality of multicolor developing devices equipped with developing blades that regulate the size of the photosensitive member, a contact-type or non-contact corona charger consisting of a conductive brush or roller and an exposure device are used to divide the static color into each color formed on the photoreceptor. In this method, the electrostatic latent image is sequentially developed with a developer corresponding to each color and transferred to a transfer medium.
The full-color two-component or non-magnetic one-component image forming method of the present invention includes a developing roller having a magnetic sleeve, a developing roller made of an elastic body, a roller made of metal, and a layer thickness of a developer supplied onto the developing roller. A contact type comprising a plurality of multicolor developing devices equipped with uniformly regulating developing blades, and an electrostatic latent image divided into each color on a plurality of photosensitive members corresponding to the respective colors, comprising a conductive brush or roller. Alternatively, it is a method of forming with a non-contact corona charger and an exposure device, developing sequentially with a developer of the corresponding color, and transferring to a transfer medium. In this case, it is preferable to perform development by a reversal development method in which the polarity of the electrostatic latent image on the photoreceptor is the same as that of the two-component or non-magnetic one-component toner. Further, it is preferable that development is performed by rotating the developing roller at a higher speed than the photosensitive member in direct contact or non-contact with the electrostatic latent image on the photosensitive member.
The toner of the present invention is not only an electrophotographic developing apparatus equipped with a conventionally known corotron transfer apparatus, but also electrostatic transfer of the toner image to the transfer material by bringing the transfer means into contact with the surface of the electrostatic image carrier through the transfer material. An electrophotographic developing apparatus may be used.

FIG. 1 is a schematic sectional view showing an example of a color electrophotographic copying apparatus. In FIG. 1, a color image reading device (1) converts an image of a document (3) into a color sensor (4) through an illumination lamp (4), mirror groups (5a), (5b), (5c) and a lens (6). 7), and the color image information of the original is read for each color separation light of, for example, blue (hereinafter referred to as B), green (hereinafter referred to as G), and red (hereinafter referred to as R) and converted into an electrical image signal. To do. Then, based on the color separation image signal intensity levels of B, G, and R, color conversion processing is performed by an image processing unit (not shown), and black (hereinafter referred to as Bk), cyan (hereinafter referred to as C), Magenta (hereinafter referred to as “M”) and yellow (hereinafter referred to as “Y”) color image data are obtained.
With this color image data, a full-color toner image is formed on the transfer sheet as follows. In the color image recording apparatus (2) of FIG. 1, the electrophotographic photosensitive member (9) rotates counterclockwise as indicated by an arrow, and around the photosensitive member cleaning unit (including a pre-cleaning static eliminator) (10 ), Discharge lamp (11), charger (12), potential sensor (13), black development unit (14), cyan development unit (15), magenta development unit (16), yellow development unit (17), development density An optical sensor (18) for pattern detection, an intermediate transfer belt (19), and the like are disposed. Further, each developing unit has a developing sleeve rotating to bring the developer ears into contact with the surface of the photoreceptor (9) to develop the electrostatic latent image, and a developing paddle rotating to draw up and stir the developer, And a toner density sensor (14c), (15c), (16c), (17c) and the like of the developer. Each developing unit is loaded with an electrophotographic developer.

The black image data is sent to the color image recording device (2), the writing optical unit (8) converts the black image data into an optical signal, and optical writing with a laser beam is performed on the charged electrophotographic photosensitive member (9). As a result, an electrostatic latent image of a black image is formed on the electrophotographic photosensitive member (9) (for example, an image portion of −80 V to −130 V, a non-image portion of −500 V to −700 V). The electrostatic latent image of the black image is developed by the black toner on the developing sleeve that starts rotating before the leading end of the electrostatic latent image reaches the developing position of the black developing unit (14), A black toner image is formed on the photographic photoreceptor (9). When the rear end portion of the electrostatic latent image has passed the development position, the development unit (14) is retracted to the development inoperative state.
The black toner image formed on the electrophotographic photosensitive member (9) is transferred to the surface of the intermediate transfer belt (19) driven at the same speed as the photosensitive member (9) by an intermediate transfer belt unit described below. . In FIG. 1, an intermediate transfer belt (19) is stretched around a drive roller (21), a transfer bias roller (20a), a ground roller (20b), and a driven roller group, and is driven and controlled by a drive motor.

As the intermediate transfer belt (19), for example, a carbon-dispersed fluororesin ETFE (ethylene / tetrafluoro / ethylene) can be used, and a volume resistivity of 10 9 Ωcm or less is preferable. As the transfer bias roller (20a), for example, a hydrin rubber roller covered with a PFE tube to have a volume resistivity of 10 9 Ωcm can be used. Further, as the ground roller (20b), for example, a grounded roller shaft can be used.
The toner image is transferred from the photoconductor (9) to the intermediate transfer belt (19) when the photoconductor (9) and the intermediate transfer belt (19) are in close contact with each other, with a predetermined bias voltage applied to the transfer bias roller (20a). Is applied. The contact state between the photosensitive member (9) and the intermediate transfer belt (19) is performed by pressing the intermediate transfer belt (19) against the photosensitive member (9) by the transfer bias roller (20a) and the ground roller (20b). It is.
The intermediate transfer belt (19) is grounded by the earth roller (20b), and thereby the range affected by the electric field generated by the transfer bias applied by the transfer bias roller (20a) is intermediate between that of the photoreceptor (9). The transfer belt (19) can be within a close contact range. As a result, it is possible to prevent the electric field from acting on the toner image on the photoreceptor before the intermediate transfer belt (19) is in close contact, and to prevent an increase in the interval between the toner particles due to the transfer bias electric field. Generation of voids in the image can be prevented.

  After the black toner image is transferred to the intermediate transfer belt (19), the electrophotographic photosensitive member (9) is cleaned by the photosensitive member cleaning unit (10) and is uniformly discharged by the discharging lamp (11). Charged by (12). Next, cyan image data is sent to the color image recording device (2), the writing optical unit (8) converts the cyan image data into an optical signal, and optical writing with laser light is performed on the charged electrophotographic photosensitive member (9). As a result, an electrostatic latent image of a cyan image is formed on the electrophotographic photosensitive member (9).

The electrostatic latent image of the cyan image is developed by a cyan developing unit (15) that operates in the same manner as the black developing unit (14), and a cyan toner image is formed on the electrophotographic photosensitive member (9). The cyan toner image formed on the electrophotographic photosensitive member (9) is aligned with the black toner image already transferred to the intermediate transfer belt (19), and the intermediate transfer belt (19 ) Is transferred to the surface. Thereafter, similarly, a magenta toner image and a yellow toner image are sequentially aligned and transferred onto the surface of the intermediate transfer belt (19), whereby a full-color toner image is formed on the intermediate transfer belt (19).
The full-color toner image formed on the intermediate transfer belt (19) is transferred onto the transfer sheet as follows. In FIG. 1, a transfer unit (23) for transferring a toner image from an intermediate transfer belt (19) to a transfer sheet includes a transfer bias roller, a roller cleaning blade, and a contact / separation mechanism from the belt. The bias roller is usually separated from the surface of the belt (19), but is pressed by the contact / separation mechanism at the timing when the full-color toner image formed on the intermediate transfer belt (19) is transferred to the transfer sheet. Then, a predetermined bias voltage is applied. As a result, the full-color toner image formed on the intermediate transfer belt (19) is transferred to the transfer sheet.

As shown in FIG. 1, the transfer sheet (24) has a paper feed roller (25) that matches the timing at which the leading end of the full-color toner image formed on the intermediate transfer belt reaches the transfer position to the transfer sheet. ), And is fed by a registration roller (26). The belt cleaning unit (22) includes a brush roller, a rubber blade, and a contact / separation mechanism from the belt, and the contact / separation mechanism while each color toner image is transferred onto the intermediate transfer belt (19). After the toner image is transferred from the intermediate transfer belt (19) to the transfer sheet, the cleaning unit (22) is pressed against the intermediate transfer belt (19) by the contact / separation mechanism. The surface is cleaned.
As shown in FIG. 1, the transfer sheet is transferred to the fixing device (28) by the transfer unit (27) and the fixing roller (28a) and the pressure roller (controlled to a predetermined temperature) as shown in FIG. The full-color toner image is fixed by 28b). In the fixing step, it is preferable to use a fixing method using a fixing roller in which pressure is applied and heat is supplied simultaneously for fixing. The temperature of the fixing roller is preferably set to 160 ° C. to 190 ° C. Further, a method of applying a release agent such as silicone oil to the fixing roller is also effective for preventing toner fusion to the fixing roller. When the set temperature of the fixing roller is lower than 160 ° C., the toner is not smoothly softened and a gap remains. If the temperature is set higher than 190 ° C., the heat supply from the fixing roller may not follow in continuous copying. A preferable setting temperature of the fixing roller is 170 ° C. to 185 ° C. depending on the process speed. With this temperature setting, there is little variation in the fixing roller temperature in continuous copying, so that a fixed toner image with stable quality can be obtained.

  In the above description, a case where a full-color toner image is obtained using four-color mode color image data of black, cyan, magenta, and yellow has been described. A latent image is formed, and the developing unit for that color is operated to form a toner image on the transfer sheet in the same manner as described above. When a single color toner image is formed on a transfer sheet, only the developing unit for that color is in an operating state and the intermediate transfer belt (19) is driven while being in contact with the surface of the electrophotographic photosensitive member (9). Furthermore, the cleaning unit (22) can also perform the image forming operation while being in contact with the intermediate transfer belt (19).

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited only to these examples. In the following examples, parts and% are based on weight unless otherwise specified.
Example 1
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 1] was obtained. The average particle diameter of [fine particle dispersion 1] measured with LA-920 was 105 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin component was 59 ° C., and the weight average molecular weight was 150,000.

(Adjustment of aqueous phase)
990 parts of water, 99 parts of [fine particle dispersion 1], 35 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 70 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated [Aqueous Phase 1].

(Synthesis of polyester resin)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 8 hours at normal pressure, and further react for 5 hours at 10-15 mmHg reduced pressure, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. The mixture was reacted for 1.7 hours to obtain [Polyester Resin 1]. [Polyester resin 1] had a number average molecular weight of 2400, a weight average molecular weight of 6700, a peak molecular weight of 5000, a Tg of 43 ° C. and an acid value of 25.

(Synthesis of intermediate polyester)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 9 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight percentage of 1.53%.

(Synthesis of ketimine)
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

(Master Badge)
Polyester resin 50.0 parts Carbon black 40.0 parts Pigment Blue 15: 3 5.0 parts Water 50.0 parts The above is mixed with a Henschel mixer, kneaded for 1 hour, rolled and cooled, pulverized with a pulverizer, and further with a 3-roll mill. Two passes were obtained to obtain a black masterbatch. This is defined as (MB-B1).

Polyester resin 50.0 parts Pigment Yellow 17 50.0 parts Water 50.0 parts The above is mixed with a Henschel mixer, kneaded for 1 hour, rolled and cooled, pulverized with a pulverizer, and further passed 2 times with a 3 roll mill, yellow masterbatch Got. This is defined as (MB-Y1).

Polyester resin 50.0 parts Pigment Red 57 50.0 parts Water 50.0 parts The above is mixed with a Henschel mixer, kneaded for 1 hour, rolled and cooled, pulverized with a pulverizer, and further passed 2 times with a 3 roll mill, red masterbatch Got. This is defined as (MB-M1).

Polyester resin 50.0 parts Pigment Blue 15: 3 50.0 parts Water 50.0 parts The above was mixed with a Henschel mixer, kneaded for 1 hour, rolled and cooled, pulverized with a pulverizer, and further passed 2 times with a 3 roll mill. A master batch was obtained. This is defined as (MB-C1).

(Oil phase liquid)
Polyester resin 55.0 parts Ethyl acetate 78.6 parts Carnauba WAX 10.0 parts Masterbatch (MB-B1) 6.0 parts Ketimine compound 2.7 parts The above materials are placed in a tank and a TK homopolymer at 60 ° C. The mixture was stirred at 12,000 rpm for 15 minutes and dispersed at 20 ° C. for 60 minutes in a bead mill. This is designated as oil phase liquid (YS-B1). When the above oil phase liquid was prepared, the master batch was changed to MB-Y1 (YS-Y1), the oil phase liquid MB-M1 was changed to (YS-M1), and MB-C1 was changed to MB-C1. (YS-C1).

(Water phase liquid)
Ion-exchanged water 330.0 parts Ethyl acetate 30.0 parts Aqueous dispersion of vinyl resin (styrene salt copolymer of styrene-methacrylic acid-methacrylic acid etherene oxide adduct) 28.0 parts Dodecyl diphenyl ether disulfone Sodium 50% aqueous solution
12.0 parts The above materials were placed in a tank and dissolved uniformly. This is the aqueous phase liquid.

And after stirring and mixing an oil phase liquid (YS-B1) and 14.3 parts of prepolymers, a water phase liquid is added and the rotation speed of TK type homomixer is stirred at 12,000 rpm. If the particle size is large while observing with an optical microscope, the stirring speed is increased to 14,000 rpm for a further 5 minutes.
The shape control and the solvent removal step were performed by the following method. The emulsified dispersion obtained in the previous step is transferred to a tank equipped with a stirring blade and a thermometer, heated to 45 ° C., and stirred for 2 hours at a peripheral speed of the outer periphery of the stirring blade of 10.5 m / s. Got. Thereafter, the solvent was removed at 45 ° C. and atmospheric pressure (101.3 kPa). The solvent removal time required 20 hours. Thereafter, ultrafine particles were collected by wet classification using a decanter. This ultrafine particle containing water is defined as (CH-B1). Ultrafine particles containing water obtained by the same method using the oil phase liquid (YS-Y1) (CH-Y1), ultrafine particles containing water obtained by the same method using the oil phase liquid (YS-M1) Fine particles (CH-M1) and ultrafine particles containing water obtained by the same method using an oil phase liquid (YS-C1) were defined as (CH-C1). Thereafter, the water content of these ultrafine particles was adjusted and adjusted to an arbitrary solid content concentration.

(Master Badge)
Polyester resin 50.0 parts
Carbon black 45.0 parts Pigment Blue 15: 3 5.0 parts CH-B1 (solid content concentration 50%) 10.0 parts Water 40.0 parts The above is mixed with a Henschel mixer, kneaded for 1 hour, rolled and cooled, and pulverizer And pulverized with a three-roll mill to obtain a black masterbatch. This is defined as (MB-B2).

(Oil phase liquid)
Polyester resin 55.0 parts Ethyl acetate 78.6 parts Carnauba WAX 10.0 parts Masterbatch (MB-B2) 6.0 parts Ketimine compound 2.7 parts The above materials are placed in a tank and a TK homopolymer at 60 ° C. The mixture was stirred at 12,000 rpm for 15 minutes and dispersed at 20 ° C. for 60 minutes in a bead mill. This is designated as oil phase liquid (YS-B2). When the oil phase liquid was prepared, the master batch was changed to MB-Y1 (YS-Y2), the oil phase liquid MB-M1 was changed to (YS-M2), and MB-C1 was changed to MB-C1. (YS-C2).

(Water phase liquid)
Ion-exchanged water 330.0 parts Ethyl acetate 30.0 parts Aqueous dispersion of vinyl resin (styrene salt copolymer of styrene-methacrylic acid-methacrylic acid etherene oxide adduct) 28.0 parts Dodecyl diphenyl ether disulfone Sodium 50% aqueous solution
12.0 parts The above materials were placed in a tank and dissolved uniformly. This is the aqueous phase liquid.

And after stirring and mixing an oil phase liquid (YS-B2) and 14.3 parts of prepolymers, a water phase liquid is added and the rotation speed of TK type homomixer is stirred at 12,000 rpm. If the particle size is large while observing with an optical microscope, the stirring speed is increased to 14,000 rpm for a further 5 minutes.
The shape control and the solvent removal step were performed by the following method. The emulsified dispersion obtained in the previous step is transferred to a tank equipped with a stirring blade and a thermometer, heated to 45 ° C., and stirred for 2 hours at a peripheral speed of the outer periphery of the stirring blade of 10.5 m / s. Got. Thereafter, the solvent was removed at 45 ° C. and atmospheric pressure (101.3 kPa). The solvent removal time required 20 hours. Thereafter, base particles were obtained through steps of wet classification, filtration, washing, and drying.

Base particles 100.0 parts Hydrophobic silica 0.5 parts Hydrophobized titanium oxide 0.5 parts The above was mixed with a Henschel mixer at a peripheral speed of 15 m / sec for 30 seconds, and then suspended for 1 minute and mixed for 5 cycles. Thereafter, coarse particles were removed with a screen having an opening of 37 μm to obtain a black toner (TB-1).

(Example 2)
(Master Badge)
Polyester resin 50.0 parts Pigment Yellow 17 50.0 parts CH-Y1 (solid content concentration 30%) 45.0 parts Water 10.0 parts The above is mixed with a Henschel mixer, kneaded for 1 hour, rolled, cooled and pulverized with a pulverizer Further, two passes were performed with a three-roll mill to obtain a yellow master batch (MB-Y2).

(Oil phase liquid)
Polyester resin 55.0 parts Ethyl acetate 78.6 parts Carnauba WAX 10.0 parts Masterbatch (MB-Y2) 6.0 parts Ketimine compound 2.7 parts The above materials are placed in a tank and a TK homopolymer at 60 ° C. The mixer was stirred at 12,000 rpm for 15 minutes and dispersed with a bead mill at 20 ° C. for 60 minutes. This is designated as oil phase liquid (YS-Y2). After 14.3 parts of the prepolymer was stirred and mixed with this oil phase liquid, the aqueous phase liquid was added, and the number of revolutions of the TK homomixer was stirred at 12,000 rpm. Thereafter, in the same manner as in Example 1, A yellow toner (TY-1) was obtained.

(Example 3)
(Master Badge)
Polyester resin 50.0 parts
Pigment Red 57 50.0 parts CH-M1 (solid content concentration 50%) 50.0 parts Water 50.0 parts The above was mixed with a Henschel mixer, kneaded for 1 hour, rolled and cooled, pulverized with a pulverizer, and further with a three-roll mill. Two passes were performed to obtain a red master batch (MB-M2).

(Oil phase liquid)
Polyester resin 55.0 parts Ethyl acetate 78.6 parts Carnauba WAX 10.0 parts Masterbatch (MB-M2) 6.0 parts Ketimine compound 2.7 parts The above materials are placed in a tank and a TK homopolymer at 60 ° C. The mixer was stirred at 12,000 rpm for 15 minutes and dispersed with a bead mill at 20 ° C. for 60 minutes. This is designated as oil phase liquid (YS-M2). After 14.3 parts of the prepolymer was stirred and mixed with this oil phase liquid, the aqueous phase liquid was added, and the number of revolutions of the TK homomixer was stirred at 12,000 rpm. Thereafter, in the same manner as in Example 1, Magenta toner (TM-1) was obtained.

(Example 4)
(Master Badge)
Polyester resin 50.0 parts Pigment Blue 15: 3 50.0 parts CH-C1 (solid content concentration 30%) 50.0 parts Water 10.0 parts The above was mixed with a Henschel mixer, kneaded for 1 hour, rolled and cooled, and pulverizer And pulverized with a three-roll mill to obtain a blue master batch (MB-C2).
(Oil phase liquid)
Polyester resin 55.0 parts Ethyl acetate 78.6 parts Carnauba WAX 10.0 parts Masterbatch (MB-C2) 6.0 parts Ketimine compound 2.7 parts The above materials are placed in a tank and TK type homogenous at 60 ° C. The mixer was stirred at 12,000 rpm for 15 minutes and dispersed with a bead mill at 20 ° C. for 60 minutes. This is designated as oil phase liquid (YS-C2). After 14.3 parts of the prepolymer was stirred and mixed with this oil phase liquid, the aqueous phase liquid was added, and the number of revolutions of the TK homomixer was stirred at 12,000 rpm. Thereafter, in the same manner as in Example 1, Cyan toner (TC-1) was obtained.

(Comparative Example 1)
(Master Badge)
Polyester resin 50.0 parts Pigment Blue 15: 3 50.0 parts CH-C1 (solids concentration 60%) 50.0 parts Water 80.0 parts The above is mixed with a Henschel mixer, kneaded for 1 hour, rolled and cooled, and pulverizer in ground and 2 pass further on a three-roll mill to obtain a master batch of blue (MB-C3).
(Oil phase liquid)
Polyester resin 55.0 parts Ethyl acetate 78.6 parts Carnauba WAX 10.0 parts Masterbatch (MB-C3) 6.0 parts Ketimine compound 2.7 parts The above materials are placed in a tank and a TK homopolymer at 60 ° C. The mixer was stirred at 12,000 rpm for 15 minutes and dispersed with a bead mill at 20 ° C. for 60 minutes. This is an oil phase liquid . After 14.3 parts of the prepolymer was stirred and mixed with this oil phase liquid, the aqueous phase liquid was added, and the number of revolutions of the TK homomixer was stirred at 12,000 rpm. Thereafter, in the same manner as in Example 1, Cyan toner (TC-2) was obtained.

(Comparative Example 2)
(Master Badge)
Polyester resin 50.0 parts Pigment Red 57 50.0 parts CH-M1 (solid content concentration 5%) 50.0 parts Water 10.0 parts The above is mixed with a Henschel mixer, kneaded for 1 hour, rolled and cooled, and pulverized with a pulverizer Further, two passes were performed with a three-roll mill to obtain a red master batch (MB-M3).
(Oil phase liquid)
Polyester resin 55.0 parts Ethyl acetate 78.6 parts Carnauba WAX 10.0 parts Masterbatch (MB-M3) 6.0 parts Ketimine compound 2.7 parts The above materials are placed in a tank and a TK homopolymer at 60 ° C. The mixer was stirred at 12,000 rpm for 15 minutes and dispersed with a bead mill at 20 ° C. for 60 minutes. This is an oil phase liquid . After 14.3 parts of the prepolymer was stirred and mixed with this oil phase liquid, the aqueous phase liquid was added, and the number of revolutions of the TK homomixer was stirred at 12,000 rpm. Thereafter, in the same manner as in Example 1, Magenta toner (TM-2) was obtained.

(Toner unit evaluation)
1) Evaluation of degree of coloring On a white paper, each color was fixed in a single color under the conditions of an image density of 1.0 mg / cm @ 2 and a fixing temperature of 160 DEG C., and the degree of coloring was measured with a Macbeth densitometer (RD-514). The greater the value, the greater the degree of coloring.
2) Charge amount evaluation The toner and the carrier are weighed so as to have a toner concentration of 5%, and left to stand for 1 hour in a predetermined temperature environment, and then stirred and mixed in the predetermined environment for 10 minutes. This is put into a measuring gauge set with a 500 mesh net, blown off for 30 seconds, and the amount of charge Q (μC) and mass M (g) of the scattered powder are measured, and the amount of charge Q / M (μC / g ).

(Actual machine evaluation)
The obtained two-component developer was set on Rigoh's Imagio color 2800, and after running 10K sheets in the single color mode, the state of toner scattering around the developing portion was evaluated.
Table 1 shows the result of the test using the combination of the above toner and the evaluation machine.

1 is a schematic cross-sectional view showing an example of a color electrophotographic copying apparatus of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Color image reading apparatus 2 Color image recording apparatus 3 Document 4 Illumination lamp 5a Mirror group 5b Mirror group 5c Mirror group 6 Lens 7 Color sensor 8 Optical unit 8a Laser light source 8b Polygon mirror 8c Case 8d Lens 9 Electrophotographic photoreceptor 10 Photosensitive Body cleaning unit 11 Static elimination lamp 12 Charger 13 Electric potential sensor 14 Black developing unit 14c Toner density sensor 15 Cyan developing unit 15c Toner density sensor 16 Magenta developing unit 16c Toner density sensor 17 Yellow developing unit 17c Toner density sensor 18 Optical sensor 19 Intermediate transfer Belt 20a Transfer bias roller 20b Ground roller 21 Drive roller 22 Belt cleaning unit 23 Transfer unit 24 Transfer sheet 25 Paper feed roller 26 Resist Roller 27 Transport unit 28 Fixing device 28a Fixing roller 28b Pressure roller 29 Paper discharge tray 30 Paper feed bank 31 Paper feed tray 32 Paper feed tray 33 Paper feed tray 34 Paper feed unit

Claims (5)

An electrophotographic toner obtained by dissolving and / or dispersing a toner material containing at least a binder resin and a colorant in an organic solvent, emulsifying and / or dispersing the toner material in an aqueous medium, and performing wet classification after particle formation. In the manufacturing method of
The electrophotographic toner manufacturing method includes a master batch in which ultrafine particles containing water generated by being removed by wet classification are melt-kneaded with a binder resin and a colorant in the toner material ,
The mixing ratio of the master batch is 50% by weight or less of the whole toner material,
A method for producing an electrophotographic toner, wherein the solid content concentration of ultrafine particles containing water generated by being removed by wet classification is 20% to 50% . It is obtained by dissolving and / or dispersing a toner material containing at least a binder resin and a colorant in an organic solvent that can be dissolved or swelled, and emulsifying and / or dispersing the toner material in an aqueous medium, followed by wet classification after particle formation. A toner for electrophotography,
The electrophotographic toner manufacturing method includes a master batch in which ultrafine particles containing water generated by being removed by wet classification are melt-kneaded with a binder resin and a colorant in the toner material ,
The mixing ratio of the master batch is 50% by weight or less of the whole toner material,
An electrophotographic toner, wherein the solid content concentration of ultrafine particles containing water generated by removal by wet classification is 20% to 50% . In an electrophotographic image forming method for visualizing an electrostatic latent image with toner,
The image forming method is visualized with the electrophotographic toner according to claim 1. A toner material containing at least a binder resin, yellow, magenta, cyan, and black colorants is dissolved / dispersed in an organic solvent, and this is emulsified and / or dispersed in an aqueous medium, followed by wet classification after particle formation. In the method of producing a color toner for electrophotography obtained by
The method for producing a color toner for electrophotography includes a master batch in which ultrafine particles containing water generated by being removed by wet classification for each colorant are melt-kneaded together with a binder resin and a colorant. It is,
The mixing ratio of the master batch is 50% by weight or less of the whole toner material,
A method for producing a color toner for electrophotography, wherein the solid content concentration of ultrafine particles containing water generated by removal by wet classification is 20% to 50% . In an electrophotographic full color image forming method for visualizing an electrostatic latent image with color toner,
The full-color image forming method, wherein the image forming method is visualized with the color toner for electrophotography according to claim 4.

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