JP5510726B2 - Method for producing toner for developing electrostatic image - Google Patents

Description

  The present invention relates to a toner manufacturing method corresponding to high image quality of an image forming technique using an electrophotographic process such as a copying machine, a laser printer, or a facsimile.

  In recent years, development of electrophotographic apparatuses and toners has been promoted due to the strong demand for higher image quality from the market. As a toner compatible with high image quality, a spherical toner particle toner having a narrow particle size distribution is known. Thereby, the behavior of the toner at the time of development is aligned, and the reproducibility of the minute dots can be improved. However, a spherical toner having a small particle size and a narrow particle size distribution has a problem that the cleaning property is lowered. In particular, in blade cleaning, it is difficult to stably clean such toner.

  For this reason, it is known that the shape of the toner particles is irregular, particularly in the case of so-called chemical toners. Thereby, the fluidity of the toner particles can be reduced, and the toner particles can be easily removed by blade cleaning. However, if the toner particles are too deformed, there is a problem that the behavior of the toner during development becomes unstable and the reproducibility of the fine dots is lowered. Furthermore, since the filling rate of the toner in the toner layer on the transfer medium before fixing is lowered, there is a problem that the thermal conductivity in the toner layer at the time of fixing is reduced and the low-temperature fixability is lowered. In particular, this tendency becomes prominent when the pressure applied during fixing is small.

  For example, a step of mixing a binder resin and a colorant in a solvent immiscible with water, a step of dispersing the obtained composition in an aqueous medium in the presence of a dispersion stabilizer, and heating from the obtained suspension And / or a method for producing a toner for developing an electrostatic charge image having a step of removing particles by reducing pressure to form particles having irregularities on the surface and a step of spheroidizing or deforming toner particles by heating (see FIG. JP-A-9-15903 of Patent Document 1). However, there is a problem that charging stability is lowered because an irregularly shaped toner having no regularity can be obtained.

In addition, methods have been proposed in which toner particles are obtained by mixing and emulsifying a mixture of a binder resin and a colorant with an aqueous medium (Japanese Patent Laid-Open No. 5-66600 of Patent Document 2 and Japanese Patent Laid-Open No. 8 of Patent Document 3). -21655)), and can easily cope with the reduction in the particle size and spheroidization of the toner as in the suspension polymerization method. Furthermore, a wide range of binder resin types can be selected by suspension polymerization, and the reduction of volatile organic compounds is easy. Further, it has an advantage that it is easy to arbitrarily change the concentration of the colorant from a low concentration to a high concentration, and has an excellent feature as a method for producing a spherical toner having a small particle diameter.

Such a polymerized toner needs to remove the solvent component in the water-insoluble droplet after emulsification due to the property of producing the water-insoluble droplet in the water-soluble medium.
There is a method of distillation under reduced pressure for solvent component removal, and it is generally used widely because heat can be given below the glass transition point of the resin by lowering the boiling point of the volatile component and the necessary heat energy can be reduced. ing.

When the emulsification / dispersion process is performed continuously, reducing the pressure inside the tank will affect the back pressure of the emulsifier and complicate the emulsification control. In addition, the volume of the infused emulsified dispersion must be extracted with a vacuum pump. Since the adjustment of the pressure in the tank becomes complicated, it is common to perform distillation under reduced pressure in a batch manner after emulsification is completed.
In Japanese Patent Application Laid-Open No. 2002-55484 of Patent Document 4, the obtained toner particles are supplied to a container that can be decompressed and heated, and saturated water vapor, superheated water vapor, high humidity water having a temperature lower than the glass transition temperature Tg of the toner particles. There has been proposed a method of removing unreacted polymerizable monomer by batch-type heat treatment while introducing air or the like into a container.

However, when distilled under reduced pressure in a batch system, the initial emulsified dispersion continuously emulsified was left in the tank for a long time with a high solvent concentration, and was obtained at the time of emulsification dispersion by aggregation and coalescence. The small particle size and sharp particle size distribution cannot be maintained, and the solid content concentration of the emulsified dispersion increases in the vacuum distillation process described above, so the particles tend to aggregate and the scale on the inner wall of the tank is also generated. It becomes easy to do. In addition, the batch method has a low removal efficiency of the solvent component in the water-insoluble droplets, which becomes a bottleneck in a series of toner manufacturing processes, and reduces the overall efficiency of toner manufacturing.

A method is known in which a solvent is flowed substantially vertically downward along a heated wall surface, and the organic solvent is continuously removed. However, when this method is applied to a resin-containing solvent, the solvent film is thin and immediately. Since the resin is scorched, it was conventionally considered difficult to apply, but the present inventors set the wall surface heating temperature to a temperature lower than the glass transition point of the toner base particles and continuously remove the organic solvent. A toner manufacturing method that enables this is proposed (see Japanese Patent Application No. 2009-298824 of Patent Document 5).
However, in this method, the toner base particles may coalesce, and a process for industrially producing a spherical toner having a small particle size and a narrow particle size distribution, in particular, the toner composition is dissolved or dissolved in an organic solvent. It was found in the subsequent examination process that the process of dispersing the dispersed solution or dispersion in an aqueous medium and removing the solvent of the obtained emulsified dispersion is not sufficient.

The present invention corresponds to a further improvement of the toner manufacturing method including the step of flowing down the emulsified dispersion along the substantially vertical wall surface and removing the organic solvent, and prevents coalescence of toner base particles. It is another object of the present invention to provide a method for producing a toner having high solvent removal capability and energy saving.
It is another object of the present invention to provide a toner production method capable of producing a toner having a narrow particle size distribution, uniform shape, and excellent reproducibility and cleanability of fine dots.

The present invention is solved by the following (1) to ( 10 ).
(1) A method for producing a toner for developing an electrostatic charge image comprising a step of removing an organic solvent from an oil droplet containing a toner material in an organic solvent to produce toner base particles,
The oil droplets emulsify, in an aqueous medium, an oil phase (first liquid) in which a toner material containing at least a binder resin and / or a binder resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent. Or distributed,
In the organic solvent removal step, the oil-containing aqueous medium (second liquid) is caused to flow along a substantially vertical wall surface to form a liquid film,
A method for producing a toner for developing an electrostatic charge image, wherein the liquid film is brought into contact with reduced-pressure steam and heated from the wall surface to remove an organic solvent in oil droplets.
(2) The method for producing a toner for developing an electrostatic charge image according to (1) above, wherein the substantially vertical wall surface is an inner wall surface of a tube, and reduced-pressure steam is supplied from an upper portion of the tube.
(3) The method for producing a toner for developing an electrostatic charge image according to (2) above, wherein the tube has a V-shaped groove (V notch) structure on an upper end circumference.
(4) Said 2nd liquid WHEREIN: The viscosity measured value of the rotation speed 60rpm of the Brookfield viscometer in 25 degreeC is 50 mPa * s-1,000 mPa * s, The said (1) thru | or characterized by the above-mentioned. A method for producing a toner for developing an electrostatic charge image according to any one of items (3).
(5) The method for producing a toner for developing an electrostatic charge image according to any one of items (1) to (4), wherein the organic solvent is continuously removed from the second liquid.
( 6 ) The method for producing a toner for developing an electrostatic charge image according to any one of (1) to ( 5 ), wherein the toner base particles have a volume average particle diameter of 3 μm or more and 7 μm or less. .
( 7 ) The ratio (Dv / Dn) of the volume particle diameter (Dv) to the number average particle diameter (Dn) of the toner base particles is 1.0 or more and 1.2 or less. A method for producing a toner for developing an electrostatic charge image according to any one of items 1) to ( 6 ).
( 8 ) The electrostatic charge image development according to any one of items (1) to ( 7 ), wherein the toner base particles have an average circularity of 0.94 or more and 0.99 or less. Of manufacturing toner.
( 9 ) The electrostatic charge image according to any one of (1) to ( 8 ), wherein the toner base particles have a content of particles of 2 μm or less of 10% by number or less. A method for producing a developing toner.
( 10 ) The toner for developing an electrostatic charge image according to any one of (1) to ( 9 ) above, wherein the toner base particles have a glass transition point of 40 ° C. or higher and 70 ° C. or lower. Manufacturing method.

As will be understood from the following detailed and specific description, the electrostatic charge image developing method of the present invention includes the step of removing the organic solvent from the oil droplets containing the toner material in the organic solvent to produce toner base particles. A method for producing a toner, wherein the oil droplet is an oil phase (first phase) in which a toner material containing at least a binder resin and / or a binder resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent. Liquid) is emulsified or dispersed in an aqueous medium, and in the organic solvent removing step, the aqueous medium (second liquid) containing the oil droplets flows down along a substantially vertical wall surface. According to the method for producing a toner having a base particle, forming a film, bringing reduced-pressure steam into contact with the liquid film, and heating from the wall surface to remove the organic solvent in the oil droplets, Continuously large amounts of toner with excellent cleaning properties It is possible to produce a toner, it is possible to save energy.
The toner having the base particles obtained by the above manufacturing method has a small particle size and a narrow particle size distribution, and is excellent in low-temperature fixability, heat-resistant storage, reproducibility of fine dots and cleanability, so that a stable high-quality image is maintained. Can be output automatically.

It is a schematic block diagram which shows an example of the pipe | tube used in the process which volatilizes the organic solvent in the manufacturing method of the toner which has the base particle which concerns on this invention. It is the schematic which shows an example of the shape of the upper end part of the pipe | tube used in the process of volatilizing the organic solvent in the manufacturing method of the toner which has the base particle which concerns on this invention. FIG. 3 is a diagram illustrating an example of a conventionally known image forming apparatus that can be applied when an image is formed using a toner obtained by a method for producing a toner having base particles according to the present invention. It is a figure which shows the example of the state of the inner wall of the pipe | tube which removed the organic solvent.

The method for producing the toner of the present invention will be described in detail below.
As described above, the method for producing a toner of the present invention is a method for producing a toner for developing an electrostatic image by removing an organic solvent from an oil droplet containing a toner material in an organic solvent to produce toner base particles. The oil droplets emulsify, in an aqueous medium, an oil phase (first liquid) in which a toner material containing at least a binder resin and / or a binder resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent. Alternatively, the aqueous medium (second liquid) containing the oil droplets is allowed to flow along a substantially vertical wall surface to form a liquid film, and the liquid film is brought into contact with reduced-pressure steam, and The organic solvent in the oil droplets is removed by heating from the wall surface.

  In the toner manufacturing method of the present invention, the flow of the liquid film of the second liquid is caused to flow down along the wall surface, so that the flow of the liquid film is stabilized, the distance between the oil droplets (toner base particles) is not reduced, and the unidirectionally Since it flows, coalescence can be prevented. Further, by using the second liquid as a thin film fluid, the heat transfer area and the evaporation area of the organic solvent can be increased, and the organic solvent can be removed efficiently and continuously. In addition, by bringing the reduced pressure water vapor into contact with the liquid film, the water vapor is condensed and latent heat is given to the second liquid. Therefore, the temperature of the wall surface is not increased, so that energy can be saved and toner base particles adhere to the wall surface. -Prevents seizure and does not disturb the flow of the liquid film. In addition, water in the aqueous medium (second liquid) is azeotroped with the organic solvent and discharged as a mixed vapor, but since more water than the amount discharged is condensed, the second liquid is Solids are not concentrated, coalescence can be prevented, toner particle size distribution is not deteriorated, organic solvent can be removed efficiently and continuously, and toner with excellent reproducibility and cleanability of micro dots is manufactured. It becomes possible to do.

In the toner production method of the present invention, as described above, the organic solvent is volatilized by heating with the wall surface and the reduced-pressure steam. When the reduced-pressure water vapor of the gas comes into contact with the second liquid and the water vapor condenses and changes into a liquid, the second liquid is given latent heat and the organic solvent of the second liquid is vaporized. The latent heat of water at 100 ° C. is as large as 539 kcal / kg, and heat exchange with phase change can exchange a large amount of heat compared to heat exchange without phase change.
Only by heating from the reduced-pressure steam, heat is removed from the wall surface and the like, and sufficient heat is not supplied to the second liquid, so that the organic solvent cannot be removed efficiently.
In order to improve the efficiency of removing the organic solvent, the heating from the wall surface needs to make the temperature of the wall surface higher than the second liquid to be supplied and ensure the temperature difference between the second liquid and the wall surface. In this case, in order to prevent aggregation of the base particles, the upper limit of the temperature of the wall surface is limited, and it is preferable to set the liquid temperature of the second liquid to be equal to or lower than the glass transition point of the base particles.
When the temperature of the second liquid flowing along the wall surface exceeds the glass transition point of the toner base particles, the second liquid particles tend to aggregate and the aggregate of the second liquid accumulates on the wall surface. The liquid film becomes non-uniform and it may be difficult to volatilize the organic solvent efficiently.
By bringing the water vapor into contact with the vacuum, the glass transition point of the wall surface can be lowered, and the organic solvent with high heat transfer efficiency can be removed without the risk of a decrease in heat transfer capacity due to scale adhesion to the wall surface. is there.

  In the toner manufacturing method of the present invention, it is preferable to volatilize the organic solvent under reduced pressure. Under atmospheric pressure, it becomes difficult to volatilize the organic solvent efficiently. In general, an organic solvent having a boiling point of less than 100 ° C. at 1 atm has a higher vapor pressure than water, and when a mixture of water and an organic solvent is distilled under reduced pressure, the organic solvent volatilizes first and eventually. Organic solvent and water azeotrope. Further, after the organic solvent is volatilized, the water evaporates and becomes equal to the boiling point when water is simply distilled. In the case of steam distillation, even if the composition ratio of the organic solvent and water changes, the liquid temperature does not become higher than the boiling point of water. That is, if the pressure in the distillation system is determined, the upper limit temperature of the liquid to be distilled is determined. Therefore, if the pressure in the organic solvent removal step is controlled, the liquid temperature of the second liquid is made lower than the glass transition point of the base particles. It is relatively easy to prevent aggregation of the base particles, and the pressure in the system for removing the organic solvent is preferably less than 20 kPa.

  The second liquid used in the toner production method of the present invention preferably has a viscosity measurement value of 50 mPa · s to 1,000 mPa · s at 25 ° C. and a Brookfield viscometer at a rotation speed of 60 rpm, preferably from 100 Pa · s to More preferably, it is 300 mPa · s. If it is less than 50 mPa · s, it becomes difficult to form a liquid film uniformly on the wall surface in the tube, and if it exceeds 1000 Pa · s, the film thickness of the liquid film becomes thick and it becomes difficult to volatilize the organic solvent efficiently.

In the toner production method of the present invention, as described above, it is preferable to produce toner base particles by volatilizing and removing the organic solvent from the second liquid, and then cleaning, drying, and purifying.
The toner base particles preferably have a volume average particle diameter of 3 to 7 μm. When the volume average particle size is less than 3 μm, when used as a one-component developer, toner filming on the developing roller or toner fusion to a member such as a blade for thinning the toner occurs. There are things to do. Further, when used as a two-component developer, the toner may be fused to the surface of the carrier due to long-term stirring in the developing device, thereby reducing the charging ability of the carrier. On the other hand, when the volume average particle size exceeds 7 μm, it becomes difficult to form a high-resolution and high-quality image, and when used as a two-component developer, the balance of the toner in the developer was performed. In some cases, the variation in the particle size of the toner may increase.

The ratio of the volume particle size (Dv) to the number average particle size (Dn) of the toner base particles is preferably 1.0 to 1.2. When this ratio exceeds 1.2, the toner behavior varies during development, and the reproducibility of the fine dots is lowered, and a high-quality image may not be obtained.
In addition, the volume average particle diameter and number average particle diameter of the base particles can be measured using a Coulter counter method.

The toner base particles preferably have an average circularity of 0.94 to 0.99. When the average circularity is less than 0.94, the shape of the toner particles is too far from the spherical shape, so that the transferability is lowered and a high-quality image may not be obtained. On the other hand, if the average circularity exceeds 0.99, a cleaning failure may occur on the photoconductor or the transfer belt, and stains may occur on the image.
The content and average circularity of the particles having a base particle size of 2 μm or less can be measured using a flow particle image analyzer.

In the present invention, the toner base particles preferably have a content of particles having a particle size of 2 μm or less of 10% by number or less. When the content of particles having a particle size of 2 μm or less exceeds 10% by number, when used as a two-component developer, the toner is fused to the surface of the carrier by long-term agitation in the developing device, and the charging ability of the carrier May be reduced.

In the present invention, the glass transition point of the toner base particles is preferably 40 to 70 ° C. If the glass transition point is less than 40 ° C., blocking in the developing machine and filming on the photoreceptor may be likely to occur, and if it exceeds 70 ° C., the low-temperature fixability may be deteriorated.

  In the present invention, known dyes and pigments can be used as the colorant used as the toner material. 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, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, parallel , Faise red, parachloroortho nitroaniline red, risor 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, Risor 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 Lake, Rhodamine Lake B , Rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil Quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Glee Nrake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Litopon, etc. may be used, and two or more may be used in combination.

  As the colorant, a composite in which a pigment and a resin are combined, that is, a master batch may be used. The master batch is obtained by applying a high shear force to the mixture of pigment and resin, and mixing and kneading. At this time, an organic solvent may be used in order to enhance the interaction between the pigment and the binder resin. A three-roll mill or the like can be used as a high shearing dispersion device that applies a high shearing force when mixing and kneading.

  Moreover, you may manufacture a masterbatch using the flushing method. Specifically, an aqueous paste containing a pigment is mixed and kneaded with a resin and an organic solvent to transfer the pigment to the binder resin side, and then moisture and the organic solvent are removed. When the flushing method is used, since the wet pigment cake can be used as it is, it is not necessary to dry it.

  As the resin used for producing the masterbatch, in addition to the above-mentioned modified polyester and polyester, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene and the like, and polymers of substituted products 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-chloromethyl methacrylate copolymer Copolymerization, styrene-acrylonitrile copolymerization , Styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Styrene copolymer of polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, 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 and the like may be used, and two or more kinds may be used in combination.

In the present invention, the release agent used as a toner material is not particularly limited, but it is a plant wax such as carnauba wax, cotton wax, wood wax, rice wax, animal wax such as beeswax, lanolin, ozokerite, cercin, etc. Mineral wax, paraffin, microcrystalline, petroleum wax such as petrolatum, synthetic hydrocarbon wax such as Fischer-Tropsch wax, polyethylene wax, synthetic wax such as ester, ketone, ether, etc. Also good.
Other release agents include 12-hydroxy stearamide, stearamide, phthalic anhydride, fatty acid amides such as chlorinated hydrocarbons, polyacrylates such as poly n-stearyl methacrylate and poly n-lauryl methacrylate. Examples include a low molecular weight crystalline polymer such as a homopolymer or a copolymer (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate), a crystalline polymer having a long-chain alkyl group in the side chain, and the like. .

The organic solvent used in preparing the first liquid preferably has a boiling point of less than 100 ° C. in view of volatilization and removal. Such an organic solvent is not particularly limited, but toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, Examples thereof include methyl acetate, ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone, and two or more kinds may be used in combination. Of these, aromatic solvents (toluene, xylene, etc.) and halogenated hydrocarbons (methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride) are preferable.
At this time, if an organic solvent in which a binder resin and / or a compound having an active hydrogen group and a polymer having a functional group capable of reacting with the active hydrogen group of the compound is soluble is used, the viscosity of the first liquid decreases. In addition, the particle size distribution of the toner can be narrowed.

  The aqueous medium used for preparing the second liquid is not particularly limited, and examples thereof include water, a water-miscible solvent and a mixed solvent of water. Solvents miscible with water are not particularly limited, but alcohols (methanol, isopropanol, ethylene glycol, etc.); dimethylformamide; tetrahydrofuran; cellsolves (methylcellsolve, etc.); lower ketones (acetone, methylethylketone, etc.), etc. Can be mentioned.

  Moreover, the aqueous medium may contain a dispersant as required. Thereby, the dispersion stability of the second liquid can be improved and the particle size distribution of the toner can be narrowed. As the dispersant, a surfactant, an inorganic fine particle dispersant, a resin fine particle dispersant and the like can be used.

  The surfactant is not particularly limited, but an anionic surfactant (alkylbenzene sulfonate, α-olefin sulfonate, phosphate ester, etc.); amine salt type cationic surfactant (alkylamine salt, amino acid) Alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc.); quaternary ammonium salt type cationic surfactant (alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt) Nonionic surfactants (fatty acid amide derivatives, polyhydric alcohol derivatives, etc.); amphoteric surfactants (alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl- N, - dimethylammonium betaine, and the like). Among these, a surfactant having a fluoroalkyl group is preferable because the addition amount can be very small.

  Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms and a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6 to C11) oxy. ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid and Metal salts, perfluoroalkyl carboxylic acids (C7 to C13) and their metal salts, perfluoroalkyl (C4 to C12) sulfonic acids and their metal salts, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2- Hydroxyethyl) perfluorooctane Examples include honamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, and the like.

Commercially available anionic surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129. (Manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon) Ink Corporation), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204, (Tochem Products), Footgent F-100, F150 (Neos) ) And the like.
Although it does not specifically limit as a cationic surfactant which has a fluoroalkyl group, The aliphatic primary, secondary or tertiary amine acid which has a fluoroalkyl group, perfluoroalkyl (C6-C10) sulfonamide propyl trimethyl ammonium salt Aliphatic quaternary ammonium salts such as benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

  Commercially available cationic surfactants having a fluoroalkyl group include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Kogyo Co., Ltd.), Mega Fuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footent F-300 (Neos Co., Ltd.) and the like can be mentioned.

  The inorganic fine particle dispersant is not particularly limited, and examples thereof include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

The resin fine particle dispersant is not particularly limited, and examples thereof include PMMA fine particles, polystyrene fine particles, and styrene-acrylonitrile copolymer fine particles.
Commercially available resin fine particle dispersants include PB-200H (manufactured by Kao Corporation), SGP (manufactured by Sokensha), technopolymer SB (manufactured by Sekisui Plastics Co., Ltd.), SGP-3G (manufactured by Sokensha), micropearl ( Sekisui Fine Chemical Co., Ltd.

  Further, an inorganic fine particle dispersant, a resin fine particle dispersant, and a polymeric protective colloid may be used in combination. The polymer protective colloid is not particularly limited, but acids (acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, etc.) A (meth) acrylic monomer containing a hydroxyl group (β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, Γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol mono Methacrylic acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc.); vinyl alcohol; ethers with vinyl alcohol (vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc.); esters of vinyl alcohol and carboxylic acid (Vinyl acetate, vinyl propionate, vinyl butyrate, etc.); Acrylamide, methacrylamide, diacetone acrylamide, methylolated products thereof; Acid chlorides (acrylic acid chloride, methacrylic acid chloride, etc.); Nitrogen atom or heterocyclic ring thereof Homopolymers or copolymers such as (vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc.) can be mentioned. Other polymer protective colloids other than these include polyoxyethylene (polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, And polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester, etc.); celluloses (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.) and the like.

  Further, a toner obtained by adhering and fixing a charge control agent to the surface of the base particle may be used as the toner. At this time, there is known a method in which the base particles and the charge control agent are mixed in the container using the rotating body. However, in the present invention, in the container in which the fixing member protruding from the inner wall of the container does not exist, It is preferable to mix at a peripheral speed of 40 to 150 m / sec.

  The charge control agent is not particularly limited, but nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (fluorine-modified quaternary ammonium salt) Salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorosurfactants, salicylic acid metal salts, metal salts of salicylic acid derivatives, copper phthalocyanines, perylenes, quinacridones, azo pigments, etc. . Examples of the charge control agent other than these include polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium base.

Commercially available charge control agents include Nigrosine 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, phenol-based condensate E-89 (above, Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industry Co., Ltd.), 4 Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (from Hoechst), LRA-901, boron complex LR- 147 (made by Nippon Carlit Co., Ltd.).
The charge control agent may be added as a composite with the resin, that is, a master batch, or may be added when preparing the first liquid.

  In addition, in order to assist the fluidity, developability, and chargeability of the base particles, it is preferable to use a toner obtained by externally adding inorganic fine particles to the base particles. The inorganic fine particles are not particularly limited, but silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. At this time, it is preferable to use the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles in combination as the inorganic fine particles, and it is particularly preferable that the average particle diameter of the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles is 50 nm or less. Thereby, it is possible to prevent the inorganic fine particles from being detached from the toner when the toner is stirred and mixed in the developing machine in order to obtain a desired charge level.

  The toner manufactured using the toner manufacturing method of the present invention can be mixed with a magnetic carrier and used as a two-component developer. Further, the toner produced by using the toner production method of the present invention can be used as a one-component developer that does not use a magnetic carrier, that is, a magnetic toner or a non-magnetic toner.

FIG. 1 shows an example (schematic configuration) of a solvent removal apparatus used in the step of volatilizing the organic solvent in the toner production method of the present invention.
In FIG. 1, the solvent removal apparatus (1) has a supply part (2) and a heating part (3), and the supply part (2) has a supply port (4) for supplying a second liquid, A vacuum steam supply port 5 is provided. The heating unit (3) includes an inner tube (6), an outer tube (7), a heat source supply port (8), a heat source discharge port (9), and an inner tube discharge port (11).
The second liquid in the supply tank (15) is supplied from a supply port (4) provided on the upper surface of the inner pipe (6), and the second liquid is supplied from the upper end of the inner pipe (6) along the inner wall surface. The reduced pressure steam adjusted by the reduced pressure steam pressure adjusting valve (18) is supplied from the reduced pressure steam supply port 5 to the inside of the inner pipe (6) from the steam supply tank (17). The liquid film is heated by coming into contact with the liquid film flowing down the inner wall surface of the pipe (6). Further, when the organic solvent is volatilized, the inner pipe (6) is depressurized to 20 kPa or less by the vacuum pump (24) and the pressure control valve (23).
At this time, the supply amount of the depressurized water vapor is adjusted by the depressurized water vapor pressure adjustment valve (18), and is controlled to a desired degree of depressurization by the vacuum pump (24) and the pressure adjustment valve (22). The solvent removal temperature is controlled, and the second liquid can be removed without exceeding the glass transition point of the toner base particles.
Further, a heat medium (10) is supplied between the inner tube (6) and the outer tube (7), the inner tube (6) is heated, and the liquid temperature of the second liquid is changed to the toner base particles. Since the temperature is controlled to be equal to or lower than the glass transition point of the binder resin, the organic solvent can be efficiently volatilized from the second liquid without the toner base particles being softened and aggregated.
A tank (12) is connected to the lower part of the inner pipe (6). For this reason, the 2nd liquid from which the organic solvent was removed, and the gas and water vapor of the organic solvent volatilized from the 2nd liquid are isolate | separated into a gas and a liquid in a tank (12).
The second liquid from which the organic solvent has been removed is discharged by the discharge pump (19) via the tank discharge port (13).
On the other hand, the gas is condensed by the cooling water in the condenser (20) via the vapor outlet (14), stored in the condensate tank (21), and discharged by the condensate discharge pump (23).

Further, it is preferable that the upper end of the inner pipe (6) has a V-shaped cutout portion as shown in FIG. 2 because the second liquid can flow down stably. By providing a V-shaped groove in the upper part of the inner pipe (6) to which the second liquid is supplied, a uniform liquid film can be formed even with a highly viscous processed product. The formation of a uniform liquid film on the inner tube by the second liquid is important in preventing sticking to the inner tube wall. If the liquid film drifts, the organic solvent may not be removed efficiently, or the generated fixed matter may be mixed into the product. In addition, since the uniform liquid film can uniformly apply heat to the toner particles, the quality of the obtained toner particles does not vary.

  The one-component developer and the two-component developer containing the toner obtained by the toner production method according to the present invention can be applied when an image is formed using a conventionally known image forming apparatus.

<Image forming apparatus>
The image forming apparatus of the present invention forms an image using the toner of the present invention. The toner of the present invention can be used as either a one-component developer or a two-component developer, but is preferably used as a one-component developer. The image forming apparatus of the present invention preferably has an endless intermediate transfer unit. Furthermore, the image forming apparatus of the present invention preferably includes a photosensitive member and a cleaning unit that cleans the toner remaining on the photosensitive member and / or the intermediate transfer unit. At this time, the cleaning means may or may not have a cleaning blade. The image forming apparatus of the present invention preferably includes a fixing unit that fixes an image using a roller having a heating device or a belt having a heating device. Further, the image forming apparatus of the present invention preferably has a fixing unit that does not require oil application to the fixing member. Furthermore, it is preferable to include other means appropriately selected as necessary, for example, static elimination means, recycling means, control means, and the like.

  In the image forming apparatus of the present invention, the photosensitive member and the constituent elements such as the developing unit and the cleaning unit may be configured as a process cartridge, and the process cartridge may be configured to be detachable from the main body of the image forming apparatus. Further, at least one of a charging unit, an exposure unit, a developing unit, a transfer unit, a separating unit, and a cleaning unit is supported together with a photosensitive member to form a process cartridge, and a single unit that is detachable from the main body of the image forming apparatus. It is good also as a structure which can be attached or detached using guide means, such as a rail of a forming apparatus main body.

  FIG. 3 shows an example of the image forming apparatus of the present invention. In this image forming apparatus, a latent image carrier (1) that is driven to rotate in the clockwise direction in FIG. 2 is housed in a main body housing (not shown), and around the latent image carrier (1). In addition, a charging device (2), an exposure device (3), a developing device (4) having the electrostatic image developing toner (T) of the present invention, a cleaning unit (5), an intermediate transfer member (6), a support roller ( 7), a transfer roller (8), a charge eliminating means (not shown), and the like.

  The image forming apparatus includes a paper feed cassette (not shown) that stores a plurality of recording papers (P) as an example of a recording medium, and the recording paper (P) in the paper feed cassette is a paper feed (not shown). After the timing is adjusted by a pair of registration rollers (not shown) one by one by a roller, the sheet is fed between a transfer roller (8) as a transfer means and an intermediate transfer body (6).

  In this image forming apparatus, the latent image carrier (1) is rotated clockwise in FIG. 1 to uniformly charge the latent image carrier (1) with the charging device (2), and then the exposure device ( 3) to irradiate the laser modulated with the image data to form an electrostatic latent image on the latent image carrier (1), and to the developing device (4) on the latent image carrier (1) on which the electrostatic latent image is formed. ) To attach toner and develop. Next, a transfer bias is applied from the latent image carrier (1) on which the toner image is formed by the developing device (4) to the intermediate transfer member (6) to transfer the toner image onto the intermediate transfer member (6). By transferring the recording paper (P) between the intermediate transfer body (6) and the transfer roller (8), the toner image is transferred to the recording paper (P). Further, the recording paper (P) on which the toner image is transferred is conveyed to a fixing means (not shown).

  The fixing unit includes a fixing roller heated to a predetermined fixing temperature by a built-in heater and a pressure roller pressed against the fixing roller with a predetermined pressure, and heats the recording paper conveyed from the transfer roller (8). After pressurizing and fixing the toner image on the recording paper on the recording paper, it is discharged onto a paper discharge tray (not shown).

  On the other hand, the image forming apparatus further rotates the latent image carrier (1) on which the toner image is transferred onto the recording paper by the transfer roller (8), and the cleaning unit (5) applies the surface to the surface of the latent image carrier (1). After the remaining toner is scraped off and removed, the charge is removed by a charge removal device (not shown). The image forming apparatus uniformly charges the latent image carrier (1) neutralized by the static eliminator with the charging device (2), and then performs the next image formation in the same manner as described above.

Hereinafter, each member suitably used for the image forming apparatus of the present invention will be described in detail.
The material, shape, structure, size and the like of the latent image carrier (1) are not particularly limited and may be appropriately selected from known ones. The shape may be a drum shape or a belt shape. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon and organic photoreceptors are preferable from the viewpoint of long life.

  The electrostatic latent image can be formed on the latent image carrier (1) by, for example, charging the surface of the latent image carrier (1) and then exposing it like an image. It can be performed by latent image forming means. The electrostatic latent image forming means includes, for example, a charging device (2) for charging the surface of the latent image carrier (1) and an exposure device (3) for exposing the surface of the latent image carrier (1) imagewise. At least.

The charging can be performed, for example, by applying a voltage to the surface of the latent image carrier (1) using the charging device (2).
The charging device (2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the charging device (2) includes a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotron and scorotron.

The shape of the charging device (2) may be a magnetic brush, a fur brush or the like in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. In the case of using a magnetic brush, the magnetic brush is composed of, for example, various ferrite particles such as Zn-Cu ferrite as a charging member, and a non-magnetic conductive sleeve for supporting the same, and a magnet roll included therein. . In addition, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound around a metal or other conductive core. It is configured by pasting.
The charging device (2) is not limited to the contact type charger as described above, but an image forming apparatus in which ozone generated from the charger is reduced is obtained. Therefore, a contact type charger is used. It is preferable.

  The exposure can be performed, for example, by exposing the surface of the photoreceptor imagewise using the exposure apparatus (3). The exposure device (3) is not particularly limited as long as the surface of the latent image carrier (1) charged by the charging device (2) can be exposed like an image to be formed. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system may be used.

  The development can be performed, for example, by developing the electrostatic latent image using the toner of the present invention, and can be performed by the developing device (4). The developing device (4) is not particularly limited as long as it can be developed using the toner of the present invention, for example, and can be appropriately selected from known ones. For example, the developing device (4) contains the toner of the present invention, Preferable examples include those having at least a developing unit that can apply toner to the electrostatic latent image in a contact or non-contact manner.

  The developing device (4) carries toner on its peripheral surface, rotates in contact with the latent image carrier (1), and supplies toner to the electrostatic latent image formed on the latent image carrier (1). The developing roller (40) that performs development and a thin layer forming member (41) that contacts the peripheral surface of the developing roller (40) and thins the toner on the developing roller (40) are preferable.

  As the developing roller (40), either a metal roller or an elastic roller is preferably used. There is no restriction | limiting in particular as a metal roller, Although it can select suitably according to the objective, For example, an aluminum roller etc. are mentioned. By performing a blasting process on the metal roller, it is possible to produce the developing roller (40) having an arbitrary surface friction coefficient relatively easily. Specifically, by treating the aluminum roller with glass bead blasting, the roller surface can be roughened, and an appropriate toner adhesion amount can be obtained on the developing roller.

As the elastic roller, a roller coated with an elastic rubber layer is used, and a surface coat layer made of a material that is easily charged to a polarity opposite to that of the toner is provided on the surface. The elastic rubber layer is set to a hardness of 60 degrees or less according to JIS-A in order to prevent toner deterioration due to pressure concentration at the contact portion with the thin layer forming member (41). The surface roughness (Ra) is set to 0.3 to 2.0 μm, and a necessary amount of toner is held on the surface. Further, since the developing roller (40) is applied with a developing bias for forming an electric field with the latent image carrier (1), the elastic rubber layer has a resistance value of 10 ³ to 10 ¹⁰ Ω. Is set. The developing roller (40) rotates in the clockwise direction, and conveys the toner held on the surface to a position facing the thin layer forming member (41) and the latent image carrier (1).

  The thin layer forming member (41) is provided at a position lower than the contact position between the supply roller (42) and the developing roller (40). The thin layer forming member (41) is made of a metal leaf spring material such as stainless steel (SUS) or phosphor bronze, and the free end is brought into contact with the surface of the developing roller (40) with a pressing force of 10 to 40 N / m. Therefore, the toner that has passed under the pressure is thinned and charged by frictional charging. Further, a regulating bias having a value offset in the same direction as the charging polarity of the toner with respect to the developing bias is applied to the thin layer forming member (41) in order to assist frictional charging.

There is no restriction | limiting in particular as a rubber elastic body which comprises the surface of a developing roller (40), Although it can select suitably according to the objective, For example, a styrene-butadiene-type copolymer rubber, an acrylonitrile-butadiene-type copolymer weight Examples include coalesced rubber, acrylic rubber, epichlorohydrin rubber, urethane rubber, silicone rubber, or a blend of two or more thereof. Among these, a blend rubber of epichlorohydrin rubber and acrylonitrile-butadiene copolymer rubber is particularly preferable.
The developing roller (40) is manufactured, for example, by covering the outer periphery of the conductive shaft with a rubber elastic body. The conductive shaft is made of a metal such as stainless steel (SUS), for example.

  The transfer can be performed, for example, by charging the latent image carrier (1), and can be performed by a transfer roller. The transfer roller includes a primary transfer unit that transfers a toner image onto an intermediate transfer member (6) to form a transfer image, and a secondary transfer unit (transfer) that transfers the transfer image onto a recording paper (P). An embodiment having a roller (8) is preferred. At this time, two or more colors, preferably full color toners are used as toners, and a primary transfer means for forming a composite transfer image by transferring the toner image onto the intermediate transfer member (6), and recording the composite transfer image An embodiment having secondary transfer means for transferring onto the paper (P) is more preferable.

The intermediate transfer member (6) is not particularly limited, and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.
The transfer means (primary transfer means, secondary transfer means) preferably has at least a transfer device that peels and charges the toner image formed on the latent image carrier (1) to the recording paper (P) side. . There may be one transfer means, or two or more transfer means. Examples of the transfer means include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

  The recording paper (P) is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base for OHP can also be used.

For example, the fixing can be performed on the toner image transferred to the recording paper (P) by using a fixing unit, and is performed each time the toner image of each color is transferred to the recording paper (P). Alternatively, it may be performed at the same time in a state where toner images of respective colors are laminated.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. However, a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. In addition, as for the heating temperature by a heating-pressing means, 80-200 degreeC is preferable.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. In addition, a part means a mass part.

  First, a resin fine particle dispersion, polyester, prepolymer, masterbatch (composite composed of a mixture of a modified layered inorganic mineral and a resin), a toner material dispersion, and an aqueous medium necessary for toner production were produced as follows.

(Production of resin fine particle dispersion)
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 Parts, 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, whereby a white emulsion was obtained. Next, the system was heated until the system temperature reached 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% by mass aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours to be a vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). ) Aqueous dispersion (resin fine particle dispersion 1). The obtained resin fine particle dispersion 1 had a volume average particle diameter of 105 nm as measured using LA-920 (manufactured by HORIBA). A resin isolated by drying a part of the resin fine particle dispersion 1 had a glass transition point of 59 ° C. and a weight average molecular weight of 150,000.

(Manufacture of polyester)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts of ethylene oxide 2-mole adduct of bisphenol A, 529 parts of propion oxide 3-mole adduct of bisphenol A, 208 parts of terephthalic acid, 46 parts of isophthalic acid, and 2 parts of dibutyltin oxide was added and reacted at 230 ° C. for 5 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to synthesize polyester 1. The obtained polyester 1 had a weight-average molecular weight of 5200 in THF, a glass transition point of 45 ° C., and an acid value of 20 mgKOH / g.

(Prepolymer production)
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 795 parts of an ethylene oxide 2-mole adduct of bisphenol A, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added, and nitrogen at normal pressure was added. The reaction was carried out at 210 ° C. for 8 hours under an air stream. Next, the mixture was reacted for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, and then cooled to 80 ° C. Further, 1300 parts of ethyl acetate and 170 parts of isophorone diisocyanate were added and reacted for 2 hours to synthesize Prepolymer 1. The obtained prepolymer 1 had a weight average molecular weight of 5000.

(Manufacture of master batch)
1200 parts of water, 174 parts of modified bentonite BENTONE57 (manufactured by ELEMENTIS) and 1570 parts of polyester 1 ion-exchanged with quaternary ammonium ions were mixed using a Henschel mixer (manufactured by Mitsui Mining). The obtained mixture was kneaded at 150 ° C. for 30 minutes using a two-roll, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch 1. The modified bentonite in the master batch had a volume average particle size of 0.4 μm and a content of particles having a particle size of 1 μm or more was 2% by volume.

(Preparation of toner material dispersion liquid [first liquid])
23.4 parts of prepolymer 1, 123.6 parts of polyester 1, 20 parts of masterbatch 1 and 80 parts of ethyl acetate were added and stirred. On the other hand, 15 parts of carnauba wax, 20 parts of carbon black and 120 parts of ethyl acetate were dispersed for 30 minutes using a bead mill. The obtained two liquids were mixed, stirred for 5 minutes at 12000 rpm using a TK homomixer, and then dispersed for 10 minutes using a bead mill. To the resulting dispersion, 2.9 parts of isophorone diamine was added, and the mixture was stirred at 12000 rpm for 5 minutes using a TK homomixer to prepare toner material dispersion 1.

(Manufacture of aqueous media)
Aqueous medium 1 was prepared by adding 529.5 parts of ion-exchanged water, 70 parts of resin fine particle dispersion 1 and 0.5 part of sodium dodecylbenzenesulfonate and stirring at 12000 rpm using a TK homomixer.

(Preparation of the second solution)
Supply 72 kg / hour of aqueous medium and 48 kg / hour of toner material dispersion to a pipeline homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), perform continuous operation at a rotation speed of 2960 rpm, and continue the second liquid at 120 kg / hour. Obtained. The obtained emulsified liquid [second liquid] had a viscosity of 200 mPa · sec at a rotation speed of 60 rpm and a temperature of 25 ° C. measured using a Brookfield viscometer. The content of ethyl acetate in the emulsion was 20% by mass.

(Removal of organic solvent)
Using the tube (solvent removal apparatus 1) having the configuration shown in FIG. 1, the organic solvent in the emulsion [second liquid] was volatilized under the following conditions.
The inner pipe (6) of this solvent removal apparatus has a length of 3 m, an inner diameter of 28.4 mm, a peripheral length (L) of the heat transfer surface of 89.2 mm, and a heat transfer area (S) of 0.27 m ² .
The decompression steam pressure adjusting valve (15) is opened so that the temperature of the inner wall surface of the inner pipe (6) is 40 ° C. and the steam supply amount is 3 kg / hour, and the pressure in the inner pipe (6) is set to 75 mmHg (10 kPa). In the solvent removal apparatus (1) (see FIG. 1), the second liquid (emulsified liquid) at a liquid temperature of 20 ° C. and a supply rate of 120 kg / hour is used to prepare the second liquid prepared in the second liquid preparation step. It supplied continuously and flowed down the inner wall surface of the inner pipe (6). At the same time, hot water (heat medium 10) of 40 ° C. is allowed to flow at 10 kg / min between the inner tube and the outer tube, and the temperature of the emulsified liquid that has been converted into a liquid film flow is passed through the wall surface of the tube to the glass transition point of the base particles. The ethyl acetate was volatilized by heating while maintaining the following.
At this time, the concentration of the organic solvent in the emulsified liquid [second liquid] that passed through the inner tube (6) was 2.5% by weight.

Next, a part of the obtained slurry was put into a jacketed tank, and the jacket was aged at a hot water temperature of 45 ° C., and then filtered, washed, dried, and air-classified to obtain spherical base particles. .
100 parts of the obtained base particles and 0.25 part of the charge control agent Bontron E-84 (manufactured by Orient Chemical Co., Ltd.) are charged into a Q-type mixer (manufactured by Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blade is set to 50 m / sec. Then, 5 cycles of mixing for 2 minutes and resting for 1 minute were performed. Next, 0.5 part of hydrophobic silica H2000 (manufactured by Clariant Japan) is added, the peripheral speed of the turbine blade is set to 15 m / second, mixing for 30 seconds and resting for 1 minute for 5 cycles, and toner Was made.

  Desolvation conditions of the organic solvent in the emulsion [second liquid] in Example 1, the time required for the volatilization step, the ethyl acetate content in the emulsion, the solid content in the emulsion [the slurry before being volatilized The solid content], the time required for the volatilization process, the temperature of the slurry after the volatilization process, the amount of residual ethyl acetate in the slurry, the solid content of the slurry after the volatilization process, and whether or not the inner pipe discharge part is attached is summarized in Table 1 below. Shown in

Example 1 is different from Example 1 except that an inner pipe (6) provided with a V-shaped groove with a height of 4.26 mm and an angle of 45 ° C. that divides the upper circumference of the inner pipe (6) shown in FIG. A toner was prepared in the same manner as in Example 1.
The concentration of the organic solvent in the emulsified liquid [second liquid] that passed through the inner tube (6) was 2.5% by weight.
2A shows a V-shaped groove structure at the upper part of the inner tube, and FIG. 2B is an enlarged view of the V-shaped groove structure.

In the preparation of the toner material dispersion, 23.4 parts of prepolymer 1, 123.6 parts of polyester 1, 20 parts of masterbatch 1 and 80 parts of ethyl acetate were added and stirred. On the other hand, 15 parts of carnauba wax, 20 parts of carbon black and 60 parts of ethyl acetate were dispersed for 30 minutes using a bead mill. A second liquid was produced in the same manner as in Example 1 except that the toner material dispersion was 70 kg / hour and the aqueous medium was 50 kg / hour. At this time, the viscosity of the emulsion at 25 ° C. was 1000 mPa · s at a rotation speed of a Brookfield viscometer of 60 rpm. The organic solvent concentration of the emulsion was 22.2% by weight.
A toner was obtained in the same manner as in Example 1 except that this second liquid was used.
The concentration of the organic solvent in the emulsified liquid [second liquid] that passed through the inner tube (6) was 1.5% by weight.

In the preparation of the toner material dispersion, 11.7 parts of prepolymer 1, 61.8 parts of polyester 1, 20 parts of masterbatch 1 and 180 parts of ethyl acetate were added and stirred. On the other hand, 15 parts of carnauba wax, 20 parts of carbon black and 120 parts of ethyl acetate were dispersed for 30 minutes using a bead mill. A second liquid was produced in the same manner as in Example 1 except that the toner material dispersion was 36 kg / hour and the aqueous medium was 84 kg / hour. At this time, the viscosity of the emulsion at 25 ° C. was 50 mPa · s at a rotation speed of a Brookfield viscometer of 60 rpm. The organic solvent concentration of the emulsion was 20.9% by weight.
A toner was obtained in the same manner as in Example 1 except that this second liquid was used.
The concentration of the organic solvent in the emulsified liquid [second liquid] that passed through the inner tube (6) was 1.3% by weight.

[Comparative Example 1]
The step of removing the organic solvent was performed by a conventional batch process using a jacketed tank capable of indirect heating. A supply port through which reduced-pressure steam flows was installed below the tank, and the reduced-pressure steam was supplied at 3 kg / hour. 120 kg of the emulsion prepared in the same manner as in Example 1, jacket heated hot water at 40 ° C., 10 kg / min, degree of vacuum in the tank 75 mmHg (10 kPa), and the organic solvent concentration is 2.5 wt. The toner was prepared by volatilizing until the concentration reached%.

[Comparative Example 2]
A toner was prepared in the same manner as in Example 1 except that no vacuum steam was supplied.
The concentration of the organic solvent in the emulsified liquid [second liquid] that passed through the inner tube (6) was 11% by weight.

Table 1 shows the operating conditions of the above examples and comparative examples.
Regarding the emulsion after the volatilization step, the volume average particle diameter (Dv), the ratio of the volume average particle diameter (Dv) to the number average particle diameter (Dn) (Dv / Dn), and the particle diameter of the base particle is 2 μm or less. Table 2 shows the evaluation results of the particle content, the average circularity of the base particles, the residual solvent concentration, and the adhesion of the inner tube or tank wall.
Table 3 shows the evaluation results of image granularity, sharpness, cleaning properties, and the number of coarse particles of the produced toner.
The base particles and toners of Examples and Comparative Examples prepared above were evaluated by the following evaluation methods.

<Pressure water vapor supply amount>
A copper pipe was wound around the outer periphery of the tank under reduced pressure filled with pure water, and steam was supplied from the reduced pressure steam pressure adjusting valve (15) to evaporate the pure water. Since the supplied reduced-pressure steam supplies heat to the pure water and condenses, the amount of steam trapped in the copper pipe was measured.

<Adhesion of inner pipe>
The case where the inner tube was not fixed after removing the organic solvent was evaluated as “◯”, the case where there was little fixing as “Δ”, and the case where there was much fixing as “X”.
FIG. 4 shows photographs of the inner tube where no sticking is observed, the inner tube with little sticking, and the inner tube with much sticking.

<Remaining amount of ethyl acetate in slurry>
4 g of toluene was weighed into a volumetric flask and diluted to 500 mL with DMF to prepare an internal standard solution. Next, 1.5 g of the slurry was diluted with DMF to about 50 mL, and 10 mL of the internal standard solution was collected with a whole pipette and charged, and then stirred at 400 rpm for 4 minutes using a stirrer. Furthermore, the obtained slurry diluent was set in an autosampler of a gas chromatograph GC-2010 (manufactured by Shimadzu Corporation) and measured. After the measurement was completed, the remaining amount of ethyl acetate in the slurry was calculated from the ratio of toluene and ethyl acetate as the internal standard substance by the internal standard method. The injection amount of the slurry diluent was 2.0 μL. The measurement conditions are shown below.
Sample vaporization chamber Injection mode: Split Vaporization chamber temperature: 180 ° C
Carrier gas: He
Pressure: 40.2kPa
Total flow rate: 56.0 mL / min Column flow rate: 1.04 mL / min Linear velocity: 20.0 cm / sec Purge flow rate: 3.0 mL / min Split ratio: 50.0
Column name: ZB-50
Liquid phase film thickness: 0.25 μm
Length: 30.0m
Inner diameter: 0.32 mm ID
Maximum column temperature: 340 ° C
Column oven Column temperature: 60 ° C
Temperature program: 60 ° C hold 6 minutes → Temperature rising rate 60 ° C / minute → 230 ° C hold 5 minutes Detector Detector temperature: 250 ° C
Make-up gas: N2 / Air
Makeup flow rate: 30.0 mL / min N2 flow rate: 47.0 mL / min Air flow rate: 400 mL / min

<Number average particle diameter (Dn) and volume average particle diameter (Dv)>
A Coulter Counter TA-II type (manufactured by Coulter) was connected to an interface (manufactured by Nikka Giken) and a PC9801 personal computer (manufactured by NEC) to output the number distribution and volume distribution, and the number average particle diameter and volume average The particle size was measured. Specifically, first, 0.1 to 5 ml of a surfactant (alkylbenzene sulfonate) Neogen SC-A (Daiichi Kogyo Seiyaku Co., Ltd.) is added to 100 to 150 ml of the electrolyte ISOTON-II (Coulter). added. Next, 2 to 20 mg of sample (matrix particles) was added and dispersed using an ultrasonic disperser for about 1 to 3 minutes. The number average particle diameter and volume average particle diameter of the obtained sample dispersion were measured using a 100 μm aperture. In addition, as a channel, it is 2.00-2.52 micrometers; 2.52-3.17 micrometers; 3.17-4.00 micrometers; 4.00-5.04 micrometers; 5.04-6.35 micrometers; 6.35- 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32. 00 μm; 13 channels of 32.00 to 40.30 μm were used, and particles having a particle size of 2.00 to 40.30 μm were measured.

<Content of particles having average circularity and particle size of 2 μm or less>
Using a flow particle image analyzer FPIA-2100 and analysis software FPIA-2100 Data Processing Program for FPIA version 00-10 (manufactured by Sysmex Corporation), the average circularity and the content of particles having a particle diameter of 2 μm or less were measured. . Specifically, first, in a glass 100 ml beaker, 10% by mass surfactant (alkyl benzene sulfonate) Neogen SC-A (Daiichi Kogyo Seiyaku Co., Ltd.) 0.1 to 0.5 ml and a sample (matrix particles) After adding 0.1 to 0.5 g and stirring with a microspatel, 80 ml of ion-exchanged water was added. When the resulting dispersion is dispersed for 3 minutes using an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.), the average circularity and particle size are 2 μm or less when the concentration is 5000-15000 / μl. The content of certain particles was measured.

<Image graininess, sharpness>
Using a digital full-color copying machine imagioColor 2800 (manufactured by Ricoh), a photographic image was output in a single color, and the image graininess and sharpness were visually evaluated. Note that the image granularity and sharpness are the same as those of offset printing, ◎, slightly worse than offset printing, ◯, considerably worse than offset printing, △, about the conventional electrophotographic image ( Judgment was made with x being very bad).

<Cleanability>
The transfer residual toner on the photosensitive member that passed through the cleaning process was transferred to white paper using Scotch tape (manufactured by Sumitomo 3M). Next, the reflection density of the white paper to which the transfer residual toner was transferred and the white paper not transferred were measured using a Macbeth reflection densitometer RD514. A case where the difference in reflection density was less than 0.01 was judged as ◯ (good), and a case where the difference was 0.1 or more was judged as x (defect).

<Number of coarse particles>
On a jig with a hole having a diameter of 5 mm, a mesh having an opening of 25 μm was placed, 0.2 g of toner particles were placed thereon, and the toner particles were sucked from the opposite side. What remained on the mesh was collected with a transparent tape, and the number of particles was measured with a microscope. The evaluation was made with ◎ being less than 100 coarse particles, を being 100 or more and less than 150, Δ being 150 or more and less than 200, and × being 200 or more.

From Example 1 and Comparative Example 1, this method of forming an emulsion liquid into a liquid film in the volatilization step and continuously processing the toner does not cause sticking to the wall surface of the apparatus, and a toner having excellent quality can be produced efficiently in a short time. Was confirmed.
From Example 2, further uniformization of the liquid film can be achieved by providing a V-shaped groove in the upper part of the inner tube. By making the liquid film uniform, not only can the sticking of the inner tube be reduced, but also the aggregation of toner particles can be further reduced.
From Example 3, when the viscosity of the emulsion is increased, more organic solvent is removed in the volatilization step. If the viscosity of the emulsified liquid is high, the film thickness becomes thicker when the liquid film is used, so that it is considered that the time for staying in the apparatus becomes longer.
From Example 4, when the viscosity of the emulsion is reduced, more organic solvent is removed in the volatilization step. When the viscosity of the emulsion decreases, the film thickness decreases and the residence time decreases, but the heat transfer area increases, so it seems that the organic solvent could be removed effectively.
In Comparative Example 1, it can be seen that since the reduced-pressure steam supplied from the lower side of the tank and the emulsified liquid cannot efficiently contact each other, it takes a long time for the volatilization process, which is a bottleneck in the toner manufacturing process. In addition, toner particles are agglomerated because the toner particles are exposed to a high concentration of solvent for a long time. Furthermore, it is considered that the toner particles aggregated and adhered to the tank wall surface because the solvent and water azeotroped through the volatilization step and the toner particle concentration of the emulsion increased.
From Comparative Example 2, when the volatilization step was performed without supplying the reduced-pressure steam, the amount of heat sufficient to volatilize the solvent could not be supplied, and the solvent concentration of the emulsion after treatment was 11% by weight. Therefore, it seems that toner particles are aggregated and fixed to the inner tube.

About FIG. 1 1 Solvent removal device 2 Supply unit 3 Heating unit 4 Supply port 5 Depressurized water vapor supply port 6 Inner tube 7 Outer tube 8 Heat source supply port 9 Heat source discharge port 10 Heat medium 11 Inner tube discharge port 12 Tank 12a Channel opening / closing valve 12b Circulating channel 12c Channel opening / closing valve 13 Tank outlet 14 Steam outlet 15 Supply tank 15a Liquid film 16 of second liquid Supply pump 17 Steam supply tank 17a Steam inlet 18 Depressurized steam pressure control valve 19 Discharge pump 20 Condenser 21 Condensate receiving tank 22 Pressure adjusting valve 23 Condensate discharge pump 24 Vacuum pump

About FIG. 3 1 Latent image carrier 2 Charging device 3 Exposure device 4 Developing device 40 Developing roller 41 Thin layer forming member 42 Supply roller 5 Cleaning unit 6 Intermediate transfer member 7 Support roller 8 Transfer roller

JP 9-15903 A JP-A-5-66600 JP-A-8-21655 JP 2002-55484 A Japanese Patent Application No. 2009-298824

Claims (10)

A method for producing a toner for developing an electrostatic charge image comprising a step of removing an organic solvent from an oil droplet containing a toner material in an organic solvent to produce toner base particles,
The oil droplets emulsify, in an aqueous medium, an oil phase (first liquid) in which a toner material containing at least a binder resin and / or a binder resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent. Or distributed,
In the organic solvent removal step, the oil-containing aqueous medium (second liquid) is caused to flow along a substantially vertical wall surface to form a liquid film,
An electrostatic charge image , wherein the liquid film is brought into contact with reduced-pressure steam and heated from the wall surface to remove the organic solvent in the oil droplets at a temperature lower than the glass transition temperature of the toner base particles. A method for producing a developing toner.   2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the substantially vertical wall surface is an inner wall surface of a tube, and vacuum steam is supplied from an upper portion of the tube.   3. The method for producing a toner for developing an electrostatic charge image according to claim 2, wherein the tube has a V-shaped groove (V notch) structure on an upper end circumference. 4. The second liquid according to claim 1, wherein a viscosity measurement value of a Brookfield viscometer at 25 ° C. and a rotation speed of 60 rpm is 50 mPa · s to 1,000 mPa · s. 5. A method for producing a toner for developing electrostatic images.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein the organic solvent is continuously removed from the second liquid. The volume average particle size of the toner base particles, method for producing a toner according to any one of claims 1 to 5, characterized in that at 3μm or more 7μm or less. The ratio of the volume particle diameter to the number average particle diameter of the toner base particles (Dn) (Dv) is (Dv / Dn) is, of claims 1 to 6, characterized in that 1.0 to 1.2 A method for producing a toner for developing an electrostatic image according to any one of the above. The toner average circularity of the base particles, 0.94 to 0.99 according to claim 1 to 7 The method of producing an electrostatic charge image developing toner according to any one of and wherein the less. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 8 , wherein the toner base particles have a content of particles of 2 µm or less of 10% by number or less. The toner base particles, method for producing a toner according to any one of claims 1 to 9, wherein the glass transition point of 70 ° C. or less 40 ° C. or higher.

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