JP2010282206A - Method for producing developer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an encapsulated developer having good offset resistance and charging characteristics. <P>SOLUTION: A method for producing a developer includes steps of: obtaining fine particles of a toner material by applying mechanical shearing to a toner material dispersion liquid; forming aggregated particles by aggregating the fine particles of the toner material; obtaining fine particles of a binder resin by applying mechanical shearing to a binder resin dispersion liquid; and mixing the aggregated particles with the fine particles of the binder resin in an aqueous medium to form encapsulated toner particles with the aggregated particles as a core component and with the fine particles of the binder resin as a shell component. In the method, prior to applying the mechanical shearing to the binder resin dispersion liquid, a sulfosuccinic acid-based surfactant is added to the binder resin dispersion liquid. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  Embodiments described herein relate generally to a method for producing a developer for developing an electrostatic charge image and a magnetic latent image in electrophotography, electrostatic printing, and the like.

  Conventionally, as a method for producing a toner using a polyester resin, a phase inversion emulsification method in which ammonia water or the like is added to a solution dissolved in an organic solvent and water is added to the solution has been proposed. Organic solvent may remain. It is also necessary to remove and recover the organic solvent. Although a method for producing fine particles by mechanical shearing in an aqueous medium without using an organic solvent has been proposed, it is necessary to supply a molten resin or the like to a stirring device, and handling is difficult.

  However, in these cases, when the core agent is encapsulated with resin fine particles, since an organic solvent is used in the resin atomization step, washing is difficult. As a result, there is a problem that it is contained in the toner in a small amount, and odor is generated during fixing.

  Therefore, the kneaded pulverized product of the polyester resin and the pigment is subjected to wet mechanical atomization to produce aggregated particles having a uniform particle size distribution by aggregation. Next, a method for producing a toner that encapsulates agglomerated particles by adding an appropriate amount of resin fine particles that have been atomized by a wet machine in advance and heating is proposed. An anionic surfactant contained in the slurry is an alkyl ether sulfate. Since salt, alkyl sulfate, linear alkylbenzene sulfonate, and nonionic surfactant use polyoxyethylene oleyl ether, in the hetero-aggregation process, if there are few coagulants, resin fine particles that are shell materials Not adsorbed and remains as non-aggregated particles. In many cases, in addition to capsule particles, coalescence of shell materials, coalescence of core materials, shell material and core material do not heteroaggregate, and agglomerate randomly. Defective particles are generated. For this reason, it is difficult to increase the amount of adsorption, and the coverage tends to be difficult to control. In addition, since it contains a polymer surfactant that is difficult to clean, there is a drawback that charging properties and anti-scattering properties are not good as toner properties in a high-temperature and high-humidity environmental test.

JP 2008-180874 A JP-A-9-311502 JP 2008-275742 A

  An object of the present invention is to provide an encapsulated developer having good offset resistance and charging characteristics.

A method for producing a developer according to an embodiment includes a step of preparing a first aqueous dispersion containing a granulated toner material and an aqueous medium,
Finely granulating the granulated toner material by applying mechanical shear to the dispersion to obtain toner material fine particles having a size smaller than the size of the granulated toner material;
A step of aggregating the toner material fine particles to form aggregated particles;
Preparing a second aqueous dispersion containing a binder resin, a sulfosuccinic surfactant and an aqueous medium;
A step of making the binder resin fine by giving mechanical shear to the second aqueous dispersion to obtain binder resin fine particles having a size smaller than the size of the binder resin;
Mixing the agglomerated particles and the binder resin fine particles in an aqueous medium to form a third aqueous dispersion; and using the agglomerated particles as a core component and the binder resin fine particles as a shell component on the surface of the core component The method further comprises the step of forming encapsulated toner particles by agglomerating the shell component.

It is a flowchart showing an example of the manufacturing method of the developer concerning an embodiment. It is the schematic showing an example of the high voltage | pressure homogenizer structure which can be used for embodiment.

The method for producing a developer according to the embodiment includes a step of preparing a granulated toner material and a toner material dispersion containing an aqueous medium, and mechanically shearing the dispersion to finely granulate the granulated toner material. And obtaining toner material fine particles having a size smaller than the size of the granulated toner material,
A process of agglomerating toner material fine particles to form aggregated particles;
A step of preparing a binder resin dispersion containing a binder resin and an aqueous medium,
A step of obtaining binder resin fine particles having a size smaller than the size of the binder resin by making the binder resin fine by giving mechanical shear to the binder resin dispersion;
A step of mixing the agglomerated particles and binder resin fine particles in an aqueous medium to form a dispersion of the agglomerated particles and the binder resin fine particles; and agglomerated particles as a core component and the binder resin fine particles as a shell component and a shell on the core component surface. In a method comprising the step of forming encapsulated toner particles by agglomerating the components,
It is characterized in that a sulfosuccinic acid type surfactant is added before mechanically shearing the binder resin dispersion.

  According to the method for producing a developer according to the embodiment, an organic solvent is used by mixing a shell component containing a binder resin in an aqueous medium containing a surfactant having a sulfosuccinic acid structure and subjecting it to mechanical shearing. Therefore, the toner material can be granulated while being finely divided.

  In the aggregation step, the toner material fine particles and the binder resin fine particles can be agglomerated while adding a certain amount of acid and lowering the pH of the toner material fine particles based on the amount of the surfactant contained in the toner resin fine particles. The agglomerated particles obtained by adding the acid are mixed with a binder resin fine particle dispersion containing a surfactant having a sulfosuccinic acid structure, and a certain amount of the resin is obtained based on the amount of the resin atomized liquid. Monovalent acid salts can be added. Toner particles can be formed by heating particles having resin fine particles adsorbed on an aggregate containing a binder resin, a colorant and a release agent to Tg or more.

  Furthermore, the amount of adsorption can be controlled by adjusting the amount of the shell material containing a surfactant having a sulfosuccinic acid structure and the amount of the flocculant. As a result, it is possible to obtain a toner that exhibits little variation in surface composition and exhibits sufficient fixability and transferability.

  A surfactant having a sulfosuccinic acid structure is added to the binder resin slurry used for the shell material by adding a surfactant having a sulfosuccinic acid structure of 10 ppm to 10% by weight, preferably 10 ppm to 0.5% by weight. By using the agent as a dispersion aid for the resin composition, uniform atomization can be achieved in the mechanical shearing step. Further, when an appropriate amount is added to the slurry containing the aggregated particles and the dispersion is used in the encapsulation process, the proper adsorption region can be controlled by adjusting the amount of the shell component and the coagulant. In addition, the particle size distribution can be sharply controlled by using a monovalent acidic salt as the flocculant. The weight ratio of the monovalent acidic salt in the slurry of the encapsulation process to the binder resin in the shell component is preferably 1: 1 to 20, and more preferably 1: 2 to 10. When the weight ratio of the monovalent acidic salt component to the resin component in the shell material is greater than 1:20, only some resin fine particles are adsorbed to the core material, and unaggregated resin fine particles remain. In addition, when the weight ratio of the monovalent acid salt to the binder resin in the shell component is less than 1: 1, defect aggregates in which the resin fine particles and the core component are randomly aggregated are likely to be produced, and the capsule particles are difficult to manufacture. Instead, coarse grains are generated. In the fusing step, a surfactant may be further added, but it can be produced without addition. The adjustment of the particle size can be controlled by arbitrarily changing the rotation speed of the stirring blade. Further, the toner obtained by washing, drying, and external addition has an effect of improving the chargeability, filming resistance, and fixability.

  Further, by using such a toner, a good image can be formed.

  Hereinafter, embodiments will be described in more detail with reference to the drawings.

  FIG. 1 is a flowchart showing an example of a developer manufacturing method according to the embodiment.

  As shown in the figure, in the developer manufacturing method according to the embodiment, first, a coarsely granulated toner material containing a binder resin and optionally a colorant and a release agent is prepared.

  The coarsely granulated toner material can be obtained, for example, by a step of melt kneading and coarsely pulverizing a toner material mixture containing a binder resin and a colorant. Alternatively, it is obtained by granulating a toner material mixture containing a binder resin and a colorant.

  The coarsely granulated toner material preferably has a volume average particle size of 0.05 mm to 10 mm.

  If the volume average particle size is less than 0.03 mm, strong stirring is required to disperse in the aqueous medium, and bubbles generated by stirring tend to lower the dispersion of the mixed product. When the volume average particle diameter exceeds 10 mm, the particle diameter is larger than the gap provided in the shearing part of the mechanical shearing device, so that the shearing part is clogged with particles or the energy received inside and outside the mixture. There is a tendency that particles having a non-uniform composition and particle size are generated due to the difference.

  The coarsely granulated toner material more preferably has a volume average particle size of 0.1 mm to 5 mm.

  The coarsely granulated toner material is dispersed in an aqueous medium to form a first aqueous dispersion (Act 1).

  In the step of forming the first aqueous dispersion of the toner material coarsely granulated, at least one of a surfactant and a pH adjuster can be optionally added to the aqueous medium.

  By adding a surfactant, it can be easily dispersed in an aqueous medium due to the action of the surfactant adsorbed on the surface of the mixture. Grain becomes difficult. Moreover, self-dispersibility can be improved by increasing the dissociation degree of the dissociable functional group on the surface of the mixture or increasing the polarity by adding a pH adjuster.

  Subsequently, the obtained mixed liquid is subjected to mechanical shearing, and the coarsely granulated toner material is finely granulated to form fine particles (Act 2).

  According to the embodiment, by performing mechanical shearing in an aqueous medium at a temperature equal to or higher than the Tg of the binder resin, the viscosity of the coarsely granulated binder resin can be secured, and finely divided and granulated. it can. According to the embodiment, it is obtained by adjusting the processing temperature of mechanical shearing, the processing time, the number of passes of the high-pressure atomizer, the rotational speed of the stirring atomizer, the ultrasonic intensity of the ultrasonic atomizer, and the like. The size of the fine particles can be controlled.

  Next, a dispersion of a binder resin, a colorant, and a release agent-containing material and a flocculant are charged into a container.

  These fine particles are aggregated to a desired size to form aggregated particles (Act 3).

  An acid can be introduced into the dispersion to form agglomerated particles.

  In the step of forming the agglomerated particles, a plurality of fine particles can be agglomerated by using at least one process of acid addition and temperature adjustment. It is possible to control the shape of the aggregated particles obtained by adjusting these processes.

  The acid has an acidity of preferably 1.0 to 6.5 when added to the atomization liquid containing the binder resin, the colorant, and the release agent. If the pH is 7.0 or more, when added to the slurry as a flocculant, the pH cannot be lowered, so that cohesion and fusion are difficult. Tends to occur, making uniform stirring difficult, and tending to generate particles with non-uniform particle sizes.

  Next, coarsely granulated binder resin particles are prepared.

  The coarsely granulated binder resin particles are obtained, for example, by a step of coarsely pulverizing the binder resin and optional additives. Alternatively, for example, it is obtained by granulating particles containing binder resin particles.

  The coarsely granulated particles preferably have a volume average particle size of 0.05 mm to 10 mm.

  If the volume average particle size is less than 0.03 mm, strong stirring is required to disperse in the aqueous medium, and bubbles generated by stirring tend to lower the dispersion of the mixed product. The particle size is large compared to the gap provided in the shearing part of the mechanical shearing device, so the particles are clogged in the shearing part, or the composition and particle size are uneven due to the difference in energy received inside and outside the mixture There is a tendency to generate new particles.

  The coarsely granulated binder resin more preferably has a volume average particle diameter of 0.1 mm to 5 mm.

Next, the coarsely granulated binder resin is dispersed in an aqueous medium to form a coarsely granulated binder resin mixed solution (Act 4).

  In the step of forming a coarsely granulated binder resin mixed solution, a surfactant having a sulfosuccinic acid structure and a pH adjusting agent can be optionally added to the aqueous medium.

  Examples of the surfactant having a sulfosuccinic acid structure used in the embodiment include dioctyl sodium sulfosuccinate, diethylhexyl sodium sulfosuccinate, diethylhexyl sodium sulfosuccinate, dilauryl sodium sulfosuccinate, polyoxyethylene alkyl (12-14). ) Sulfosuccinic acid ester salts such as disodium sulfosuccinate and disodium sulfosuccinate polyoxyethylene lauroylethanolamide can be added.

  By adding a surfactant having a sulfosuccinic acid structure, it can be easily dispersed in an aqueous medium by the action of the surfactant adsorbed on the surface of the mixture. Further, when 0.5% or more and 10% or less are added, granulation in the subsequent capsule process becomes easier. Moreover, self-dispersibility can be improved by increasing the dissociation degree of the dissociable functional group on the surface of the mixture or increasing the polarity by adding a pH adjuster.

  Subsequently, the obtained mixed liquid is subjected to mechanical high pressure shearing, and the coarsely granulated binder resin is finely granulated to form fine particles (Act 5).

  According to the embodiment, by performing mechanical shearing in an aqueous medium at a temperature equal to or higher than the Tg of the binder resin, the viscosity of the coarsely granulated binder resin can be secured, and finely divided and granulated. it can. Further, according to the embodiment, by adjusting the processing temperature of the mechanical shear, the processing time and the number of passes of the high-pressure atomizer, the rotation speed of the stirring atomizer, the ultrasonic intensity of the ultrasonic atomizer, etc. The size of the fine particles obtained can be controlled.

  Next, the toner material fine particles obtained in (Act 3), the binder resin fine particles obtained in (Act 5), and the flocculant are mixed together with an aqueous medium and charged into a container (Act 6).

  The fine particles are adsorbed by aggregation until a desired adsorption amount is reached, and the resin fine particles are adsorbed on the colored aggregate particles (Act 7).

  In order to adsorb the resin fine particles to the colored aggregated particles, a monovalent acidic salt can be introduced into the dispersion as an aggregating agent.

  In the step of adsorbing the resin fine particles to the colored aggregated particles, the resin fine particles can be adsorbed to the colored aggregated particles using at least one of the adjustment of the addition amount of the resin fine particles, the adjustment of the addition amount of the flocculant, and the temperature adjustment. . It is possible to control the appropriate adsorption region obtained by adjusting these processes.

  The flocculant is more preferably a monovalent water-soluble acid salt among water-soluble salts. Monovalent water-soluble neutral salts can be produced, but when an appropriate amount of monovalent water-soluble acidic salt is used, the particle size distribution tends to be uniform. The monovalent water-soluble acidic salt has an acidity of preferably 1.0 to 6.5 in pH of a solution in which 50 g is made up to 1 L with ion exchange water. If the pH of a solution in which 50 g is made up to 1 L with ion-exchanged water is 7.0 or more, it can be produced when added to the slurry as a flocculant, but the fusion after aggregation is easier when the pH is lowered. is there. If it is less than 1, production is possible, but since the agglomeration behavior is relatively large, the slurry tends to thicken, making uniform stirring difficult, and controlling the particle size distribution. Is necessary, and particles having a non-uniform particle size are generated, and the process tends to be complicated.

  This dispersion can be heated to a temperature of about +5 to + 80 ° C. with respect to the glass transition point of the binder resin, for example. According to the embodiment, the size and circularity of the fused particles obtained can be controlled by adjusting the processing temperature after the aggregation, the processing time, and the rotational speed of the stirring device.

  The agglomerated particles preferably have a volume average particle size of 1 to 15 μm.

  The agglomerated particles preferably have a circularity of 0.8 to 1.0.

  After forming the agglomerated particles, the dispersion is cooled to, for example, 5 ° C. or below the glass transition point, and then washed with, for example, a filter press (Act 8) and dried (Act 9) to obtain toner particles. It is done.

  As the binder resin, a polyester resin excellent in fixability and transparency can be used, but other resins can be used in combination. For example, polystyrene, styrene / butadiene copolymer, styrene resin such as styrene / acrylic copolymer, polyethylene, polyethylene / vinyl acetate copolymer, polyethylene / norbornene copolymer, ethylene / vinyl alcohol copolymer, etc. Examples thereof include resins, acrylic resins, phenol resins, epoxy resins, allyl phthalate resins, polyamide resins, and maleic resins. Two or more of these resins may be used in combination.

  The binder resin preferably has an acid value of 1 or more.

  Examples of the colorant include carbon black, organic or inorganic pigments and dyes. For example, carbon black includes acetylene black, furnace black, thermal black, channel black, ketjen black, and the like. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 81, 83, 93, 95, 97, 98, 109, 117, 120, 137, 138, 139, 147, 151, 154, 167, 173, 180, 181, 183, 185, C.I. I. Bat yellow 1, 3, 20, etc. are mentioned. These may be used alone or in combination. Examples of magenta pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 150, 163, 184, 185, 202, 206, 207, 209, 238, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned. These may be used alone or in combination. Examples of cyan pigments include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 and the like. These may be used alone or in combination.

  In the coarsely granulated binder resin, at least one of a wax and a charge control agent can be further added.

  Examples of the wax include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax, and aliphatic hydrocarbon waxes such as oxidized polyethylene wax. Oxide of wax or block copolymer thereof, candelilla wax, carnauba wax, wood wax, jojoba wax, plant wax such as rice wax, beeswax, animal wax such as lanolin, whale wax, ozokerite, ceresin Mineral waxes such as petrolatum, montanic ester waxes, waxes based on fatty acid esters such as castor wax, and fatty acid esters such as deoxidized carnauba wax. The other is exemplified such as those de-oxidation all. Further, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group, unsaturated fatty acids such as brassic acid, eleostearic acid, parinaric acid, stearyl alcohol , Saturated alcohols such as eicosyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, melyl alcohol, or long chain alkyl alcohols having a long chain alkyl group, polyhydric alcohols such as sorbitol, linoleic acid amide, oleic acid Amide, fatty acid amide such as lauric acid amide, methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, saturated fatty acid bis amide such as hexamethylene bis stearic acid amide, Unsaturated fatty acid amides such as lenbis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide, m-xylene bis stearic acid amide, Aromatic bisamides such as N, N'-distearylisophthalamide, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soap), aliphatic hydrocarbons The hydroxyl groups obtained by hydrogenating waxes grafted with vinyl monomers such as styrene and acrylic acid, partially esterified products of fatty acids and polyhydric alcohols such as behenic monoglyceride, and vegetable oils and fats. Having methyl esthetic Compounds.

  As the charge control agent for controlling the triboelectric charge amount, for example, a metal-containing azo compound is used, and the metal element is preferably a complex, complex salt of iron, cobalt, chromium, or a mixture thereof. In addition, a metal-containing salicylic acid derivative compound can be used, and the metal element is preferably a complex, complex salt of zirconium, zinc, chromium, boron, or a mixture thereof.

  It is desirable to use an amine compound as a usable pH adjuster. Examples of amine compounds include dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, sec-butylamine, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine. , Isopropanolamine, dimethylethanolamine, diethylethanolamine, N-butyldiethanolamine, N, N-dimethyl-1,3-diaminopropane, N, N-diethyl-1,3-diaminopropane and the like.

  Examples of usable surfactants include anionic surfactants such as sulfate, sulfonate, phosphate, and soap, and cationic interfaces such as amine salts and quaternary ammonium salts. Nonionic surfactants such as activators, polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols can be mentioned.

  Examples of the mechanical shearing device include a high-pressure homogenizer such as NANO3000 (Bigrain Co., Ltd.), Ultra Tarrax (manufactured by IKA Japan), TK auto homomixer (manufactured by Primix), and TK pipeline homomixer (Primix). TK Philmix (manufactured by Primix), Claremix (manufactured by M Technique), Claire SS5 (manufactured by M Technique), Cavitron (manufactured by Eurotech), Fine Flow Mill (manufactured by Taiheiyo Kiko) ) Medialess stirrer such as Visco Mill (made by Imex), Apex Mill (made by Kotobuki Kogyo Co., Ltd.), Star Mill (made by Ashizawa, Finetech), DCP Super Flow (made by Japan Eirich), MP Mill (made by Inoue Manufacturing Co., Ltd.) ), Spike mill (manufactured by Inoue Seisakusho), mighty mill (I Examples thereof include media agitators such as Kami Seisakusho Co., Ltd. and SC Mill (Mitsui Mining Co., Ltd.).

  FIG. 2 is a schematic diagram illustrating an example of a high-pressure homogenizer configuration that can be used in the embodiment.

  As shown, the high-pressure homogenizer 10 includes a hopper tank 1, a liquid feed pump 2, a high-pressure pump 3, check valves 12 and 13 provided on the upstream side and the downstream side of the high-pressure pump 3, a heating unit 4, and atomization. The structure which has arrange | positioned the part 5, the pressure reduction part 6, the cooling part 7, and the pressure reduction part 8 in order, and the piping which connects each part are included.

  The hopper tank 1 is a tank into which the dispersion liquid is charged. When the apparatus is in operation, it is necessary to always fill the liquid so as not to send air into the apparatus. In the case where the treatment liquid has a large particle size and a sedimentation property, a stirrer can be further provided.

  The liquid feed pump 2 is installed to continuously send the dispersion liquid to the high-pressure pump 3. It is also effective for avoiding clogging at the check valves 12 and 13 provided on the upstream side and the downstream side of the high-pressure pump 3 respectively. As the liquid feed pump 2, for example, a diaphragm pump, a tubing pump, a gear pump, or the like can be used.

  The high-pressure pump 3 is a plunger type pump and has check valves at a processing liquid inlet and a processing liquid outlet (not shown). The number of plungers is 1 to 10 depending on the production scale. In order to reduce the pulsating flow as much as possible, two or more are desirable.

  The heating unit 4 is provided with a high-pressure pipe 9 formed in a spiral shape in order to increase the heat exchange area in a heating apparatus such as an oil bath. The heating unit 4 has no problem on the upstream side or the downstream side of the high-pressure pump 3 with respect to the flow direction of the dispersion liquid, but it needs to be at least upstream of the atomization unit 5. When the heating unit 4 is installed on the upstream side of the high-pressure pump 3, a heating device may be provided to the hopper 1, but since the residence time at a high temperature is long, hydrolysis of the binder resin is likely to occur.

  The atomizing portion 5 includes a nozzle having a minute diameter for applying a strong shear. There are various nozzle diameters and shapes, but the nozzle diameter is desirably 0.05 mm to 0.5 mm, and the shape is desirably a pass-through nozzle or a collision nozzle. In addition, this nozzle may be composed of multiple stages, and in the case of multiple stages, a plurality of different nozzle diameters may be arranged. The method of arranging a plurality may be parallel or serial. The nozzle material is diamond or the like that can withstand high pressure.

  The cooling unit 7 is provided with a pipe 11 that is formed in a spiral shape in order to increase the heat exchange area in a bath in which cold water flows continuously.

  If necessary, decompression units 6 and 8 can be provided before and after the cooling unit 7. As a configuration of the decompression unit, one or more cells having a flow path larger than the nozzle diameter of the atomization unit 5 and smaller than the diameter of the connection pipe or one or more two-way valves are arranged.

  The treatment by this high pressure type wet atomizer is performed as follows.

  First, the processing liquid is put into a hopper and atomization processing is performed.

  The treatment liquid is heated to the glass transition temperature Tg or higher of the binder resin. The reason for heating is to melt the binder resin.

  This heating temperature varies depending on the melting characteristics of the binder resin. Resins that are easily melted are satisfactory even at low temperatures, but resins that are difficult to melt require high temperatures. Further, in the case of the method of heating by passing through the heat exchanger continuously, the flow rate of the dispersion and the length of the heat exchange pipe are also affected. When the flow rate is fast or when the piping is short, a high temperature is required. Conversely, when the flow rate is slow or when the piping is long, the dispersion is sufficiently heated, so that the treatment can be performed at a low temperature. When the flow rate is 300 to 400 cc / min, the heat exchange pipe is 3/8 inch and 12 m high pressure pipe, the binder resin Tg is 60 ° C., and the toner softening point Tm is 130 ° C., the heating temperature is 100 ° C. to 200 ° C. Good. The heating temperature is preferably in the range of glass transition temperature Tg to Tg + 150 ° C. When the heating temperature is too high, the binder resin tends to be hydrolyzed. When the heating temperature is about Tg to Tg + 150 ° C., there is no problem that the fixing property is deteriorated.

The softening point of the toner is measured by the temperature rising method of a flow tester CFT-500 manufactured by Shimadzu Corporation, and the point on the curve corresponding to 2 mm of the plunger lowering amount is defined as the softening point from the flowchart.

  Next, the heated dispersion is sheared while applying a pressure of 10 MPa or more. At this time, it is the nozzle that gives the shear. The molten toner component is atomized by passing through the nozzle while applying a high pressure of 10 MPa or more. The pressure at this time is preferably 10 MPa to 300 MPa.

  Finally, cool to below Tg. By this cooling, the melted fine particles are solidified. Since the processing liquid is rapidly cooled, aggregation and coalescence due to cooling are less likely to occur.

  If necessary, a back pressure may be applied before or after the cooling unit, or a reduced pressure may be applied. Back pressure or reduced pressure means that atmospheric pressure is not released immediately after passing through the nozzle, but is returned to near atmospheric pressure in one stage (back pressure) or multiple stages (reduced pressure). The pressure after passing through the back pressure part or the decompression part is 0.1 MPa to 10 MPa, preferably 0.1 to 5 MPa. It is further preferable that the decompression unit has a plurality of cells or valves having different diameters. By reducing the pressure in multiple stages, fine particles with few coarse particles and a sharp particle size distribution can be obtained.

  For example, an alkaline cleaning liquid can be used for cleaning the high-pressure type wet atomizer. Dirt in the piping can be easily removed, and contamination with the next processing liquid can be minimized.

  As described above, fine particles of 2 μm or less can be obtained.

  These atomizers are provided with a heat exchanger capable of heating up to about 200 ° C. upstream of the atomization section. Further, a heat exchange device capable of cooling to Tg or less of the resin is provided in the downstream part of the atomization part. Thereby, particles of micron to submicron order can be obtained.

  In the embodiment, using a mechanical shearing device, a mixture containing at least a resin and a pigment, or a kneaded product is atomized while being heated. After atomization, the mixture may be once cooled to a desired temperature, You may set to the desired temperature which aggregates.

  In the embodiment, a mixture containing a binder resin and a colorant can be kneaded to prepare a coarsely granulated toner material.

  The kneader to be used is not particularly limited as long as melt kneading is possible, and examples thereof include a single screw extruder, a twin screw extruder, a pressure kneader, a Banbury mixer, and a Brabender mixer. Specifically, FCM (made by Kobe Steel), NCM (made by Kobe Steel), LCM (made by Kobe Steel), ACM (made by Kobe Steel), KTX (made by Kobe Steel), GT (manufactured by Ikegai Co., Ltd.), PCM (manufactured by Ikegai Co., Ltd.), TEX (manufactured by Nippon Steel Works Co., Ltd.), TEM (manufactured by Toshiba Machine Co., Ltd.), ZSK (manufactured by Warner Company), and Nidex (manufactured by Mitsui Mining Company) It is done.

  In the embodiment, when the fine particles are aggregated, a monovalent acidic salt among water-soluble salts can be used. Examples of monovalent acid salts include ammonium salts such as ammonium chloride, ammonium sulfate, ammonium sulfonate, ammonium monosulfate ester, and ammonium nitrate, and hydrogen salt salts such as ammonium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, and monobasic ammonium phosphate. And amine salts such as dimethylaminoethanol hydrochloride, dimethylaminoethanol sulfate, diethylaminoethanol hydrochloride, ethylamine hydrochloride, diethylamine hydrochloride, triethylamine hydrochloride, and the like.

  In the embodiment, in order to adjust fluidity and chargeability with respect to the toner particles, 0.01 to 20% by weight of inorganic fine particles may be added and mixed with the toner particle surface with respect to the total weight of the toner. As such inorganic fine particles, silica, titania, alumina, strontium titanate, tin oxide and the like can be used alone or in admixture of two or more.

  The inorganic fine particles are preferably surface-treated with a hydrophobizing agent from the viewpoint of improving environmental stability. In addition to such inorganic oxides, resin fine particles having a size of 1 μm or less may be externally added to improve cleaning properties.

  As a mixer for inorganic fine particles, for example, Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), super mixer (manufactured by Kawata Co., Ltd.), ribocorn (manufactured by Okawara Seisakusho Co., Ltd.), nauter mixer (manufactured by Hosokawa Micron Co., Ltd.), turbulizer (Hosokawa Micron Co., Ltd.) Co., Ltd.), cyclomixer (manufactured by Hosokawa Micron Corporation), spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.), and Ladige mixer (manufactured by Matsubo).

  In the embodiment, coarse particles and the like may be further screened. As the sieving equipment used for the sieve, Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.), Gyroshifter (Tokuju Kogakusha Co., Ltd.), Vibrasonic System (manufactured by Dalton Co., Ltd.), Soniclean (manufactured by Shinto Kogyo Co., Ltd.), Turbo Screener (Manufactured by Turbo Kogyo Co., Ltd.), micro shifter (manufactured by Hadano Sangyo Co., Ltd.), circular vibrating sieve, etc.

  By adopting such a configuration, a sharp particle size distribution was obtained. Furthermore, bleeding of the release agent was suppressed. As a result, the anti-contamination property can be improved, and an electrophotographic toner having desired charging characteristics and filming resistance can be obtained, so that a good image can be provided.

  Next, an example is shown below and the embodiment is described.

Example 1
Production of granulated toner material A toner material fine particle material having the following composition was mixed and then processed by a biaxial kneader set at a temperature of 120 ° C. to obtain a kneaded product. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated toner material.

Toner material composition Polyester resin, molecular weight 5000 78 parts by weight,
Polyester resin, molecular weight 40000 12 parts by weight,
Cyan pigment, Pigment Blue 2 5 parts by weight,
5 parts by weight of ester wax
40 parts by weight of coarsely granulated toner material, 0.4 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of an amine compound, and 58.6 parts by weight of ion-exchanged water are added to NANO3000, and the sample temperature is heated to 150 ° C. The atomized product was obtained after one pass. After completion of the treatment, the mixture was cooled to 30 ° C. to obtain toner material fine particles having a volume average particle diameter of 350 nm.

  The volume average particle diameter was measured using a Coulter counter (manufactured by Beckman Coulter).

  Moreover, the value of molecular weight here is the weight average molecular weight measured by Waters2695 which is GPC made from Waters.

Production of Binder Resin Fine Particles After mixing binder resin fine particle materials having the following composition, a kneaded product was obtained by treating with a biaxial kneader set at a temperature of 120 ° C. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated binder resin.

Binder resin fine particle composition polyester resin, molecular weight 6000 98 parts by weight,
Charge control agent, salicylic acid compound 2 parts by weight Manufacture of binder resin fine particles Coarse granulated binder resin 40 parts by weight Sodium di-2-ethylhexyl sulfosuccinate 0.4 part by weight Amine compound 1 part by weight Ion-exchanged water 58.6 parts by weight The part was put into NANO3000, the sample temperature was heated to 150 ° C., and the number of passes was one to obtain fine particles. After the treatment, the mixture was cooled to 30 ° C. to obtain resin fine particles having a volume average particle diameter of 100 nm.

Production of agglomerated particles While stirring at 30 ° C,
Toner material fine particles 5 parts by weight 1N hydrochloric acid 0.2 parts by weight Ion-exchanged water 94.8 parts by weight, dimethylaminoethanol is added to adjust the pH to 6 and the mixture is heated to 50 ° C. Aggregated particles of 4.9 μm were obtained.

Production of capsule particles While stirring at 50 ° C,
After mixing 78 parts by weight of aggregated particles and 14 parts by weight of resin fine particles,
8 parts by weight of a 15% ammonium chloride aqueous solution was added, and the mixture was heated to 93 ° C. to obtain capsule particles having a volume average particle size of 5.2 μm.

  The capsule particles were washed with a centrifuge until the conductivity of the washing water reached 50 μS / cm, and dried with a vacuum dryer until the water content became 0.3% by weight to obtain toner particles.

  After drying, 2 parts by weight of hydrophobic silica and 0.5 parts by weight of titanium oxide were adhered to the surface of the colored particles to obtain a toner. As a result of measuring the volume average particle diameter of the toner with a Coulter counter (manufactured by Beckman Coulter), the average particle diameter is 5.2 μm, and as a result of measuring the circularity with FPIA (manufactured by Sysmex Corporation), it is 0.98. It was.

  5 parts by weight of capsule toner was mixed with 95 parts by weight of carrier to obtain a developer.

  This developer was introduced into a copying machine for evaluation, and fixing evaluation was performed. As a result of intentionally changing the fixing device temperature and measuring the temperature range of the fixing device capable of obtaining a good image, the temperature region (referred to as a non-offset region) capable of obtaining a good image is 70 ° C. I found out.

  The wider the non-offset region is, the more preferable it can cope with the drift of the fixing device temperature. When the temperature is 40 ° C. or lower, the probability of occurrence of a defect image is increased, which is not desirable.

  Next, the developer was put into a copying machine modified for evaluation, and a sheet passing test of 100K sheets was performed at a printing rate of 10%. As a result of collecting the developer after completion of paper passing and measuring the amount of the material that contaminated the carrier surface, the amount of carrier contamination was 0.07 parts by weight.

  In order to obtain a satisfactory image over 100K sheets, the carrier contamination amount is desirably 0.10 parts by weight or less.

  Further, the developer is left in a high temperature and high humidity environment of 30 ° C. and 85% for 16 hours, and the charge amount q / m (HH / LL (high temperature and high humidity)) measured by suction blow-off and the low temperature of 10 ° C. and 20%. Charging stability was evaluated using a charge amount q / m (low temperature and low humidity) measured by suction blow-off after being left in a low humidity environment for 16 hours. The charging stability can be obtained by dividing q / m (high temperature and high humidity) by q / m (low temperature and low humidity), and the value of the developer was 0.82. If the value of the charging stability is 0.70 or more, a good image can be obtained regardless of the environmental atmosphere.

  For filming, a 200K sheet passing test was conducted at a printing rate of 10% using each developer described above in a digital multifunction peripheral (e-STUDIO2330c: manufactured by Toshiba). As a result of observing the photosensitive drum after completion of paper passing, the filming property is visually evaluated as ◯ when the filming is not performed, △ when the filming is somewhat observed, and × when the filming is performed. As a result of the evaluation, it was found that the filming resistance was good and good.

As for transparency, each developer described above was used in a digital multi-function peripheral (e-STUDIO2330c: manufactured by Toshiba), the fixing temperature was 130 ° C., and the adhesion became 2.0 mg / cm ² of 5 cm × 5 cm. The solid image is fixed on the OHP, and the transparency of this image portion is visually examined. The evaluation is as follows: ◯ when there is no turbidity of the image, △ when there is some turbidity, and × when there is turbidity. As a result, it was found that an image with good transparency can be obtained.

  The obtained results are shown in Table 1 below.

  By adopting such a configuration, it is possible to improve the charging property, fixing property, filming resistance, and transparency.

Example 2
Production of Toner Material Fine Particles After mixing toner material fine particle materials having the following composition, the mixture was processed in a biaxial kneader set at 120 ° C. to obtain a kneaded product. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated toner material.

Toner material fine particle composition polyester resin, molecular weight 5000 78 parts by weight,
Polyester resin, molecular weight 40000 12 parts by weight,
Cyan pigment, Pigment Blue 2 5 parts by weight,
5 parts by weight of ester wax

40 parts by weight of coarsely granulated toner material, 0.4 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of an amine compound, and 58.6 parts by weight of ion-exchanged water are added to NANO3000, and the sample temperature is heated to 150 ° C. The atomized product was obtained after one pass. After completion of the treatment, the mixture was cooled to 30 ° C. to obtain toner material fine particles having a volume average particle diameter of 350 nm.

  The volume average particle diameter was measured using a Coulter counter (manufactured by Beckman Coulter).

  Moreover, the value of molecular weight here is the weight average molecular weight measured by Waters2695 which is GPC made from Waters.

Production of resin fine particles After mixing resin fine particle materials having the following composition, a kneaded product was obtained by treating with a biaxial kneader set at a temperature of 120 ° C. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated binder resin.

Resin fine particle composition polyester resin, molecular weight 6000 98 parts by weight,
Charge control agent, salicylic acid compound 2 parts by weight Production of resin fine particles Roughly granulated binder resin 40 parts by weight, di-2-lauryl sodium sulfosuccinate 0.4 part by weight, amine compound 1 part by weight, ion-exchanged water 58. 6 parts by weight was charged into NANO3000, the sample temperature was heated to 150 ° C., and the number of passes was one to obtain fine particles. After the treatment, the mixture was cooled to 30 ° C. to obtain resin fine particles having a volume average particle diameter of 100 nm.

Production of agglomerated particles While stirring at 30 ° C., 5 parts by weight of toner material fine particles, 0.2 part by weight of 1N hydrochloric acid and 94.8 parts by weight of ion-exchanged water are mixed, and then dimethylaminoethanol is added to adjust the pH to 6. And it heated to 50 degreeC and the aggregate with a volume average particle diameter of 4.9 micrometers was obtained.

Manufacture of capsule particles While stirring at 50 ° C., 78 parts by weight of aggregated particles and 14 parts by weight of resin fine particles are mixed, 8 parts by weight of 15% aqueous ammonium chloride solution is added, and the mixture is heated to 93 ° C. 2 μm capsule particles were obtained.

  The capsule particles were washed with a centrifuge until the conductivity of the washing water reached 50 μS / cm, and dried with a vacuum dryer until the water content became 0.3% by weight to obtain toner particles.

  After drying, 2 parts by weight of hydrophobic silica and 0.5 parts by weight of titanium oxide were adhered to the surface of the colored particles to obtain a toner. As a result of measuring the volume average particle diameter of the toner with a Coulter counter (manufactured by Beckman Coulter), the average particle diameter is 5.2 μm, and as a result of measuring the circularity with FPIA (manufactured by Sysmex Corporation), it is 0.98. It was.

  5 parts by weight of capsule toner was mixed with 95 parts by weight of carrier to obtain a developer. This developer was introduced into a copying machine for evaluation, and fixing evaluation was performed. As a result of intentionally changing the fixing device temperature and measuring the temperature range of the fixing device capable of obtaining a good image, the temperature region (referred to as a non-offset temperature region) capable of obtaining a good image is 70 ° C. I found that there was.

  Next, the developer was put into a copier modified for evaluation, and the amount of the substance that contaminated the carrier surface was measured in the same manner as in Example 1. As a result, the amount of carrier contamination was 0.07 parts by weight.

  Further, when the charging stability was evaluated in the same manner as in Example 1, the value of this developer was 0.82.

  As a result of evaluating the filming property in the same manner as in Example 1, it was found that the filming resistance was good and good.

  And as a result of investigating transparency like Example 1, it turned out that transparency is (circle) and a favorable image can be obtained.

The obtained results are shown in Table 1 below. By adopting such a configuration, the chargeability, fixability, filming resistance, and transparency can be improved.

Example 3
Production of Toner Material Fine Particles After mixing toner material fine particle materials having the following composition, the mixture was processed in a biaxial kneader set at 120 ° C. to obtain a kneaded product. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated toner material.

Toner material fine particle composition polyester resin, molecular weight 5000 78 parts by weight,
Polyester resin, molecular weight 40000 12 parts by weight,
Cyan pigment, Pigment Blue 2 5 parts by weight,
5 parts by weight of ester wax
40 parts by weight of coarsely granulated toner material, 0.4 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of an amine compound, and 58.6 parts by weight of ion-exchanged water are added to NANO3000, and the sample temperature is heated to 150 ° C. The atomized product was obtained after one pass. After completion of the treatment, the mixture was cooled to 30 ° C. to obtain toner material fine particles having a volume average particle diameter of 350 nm.

  The volume average particle diameter was measured using a Coulter counter (manufactured by Beckman Coulter).

  Moreover, the value of molecular weight here is the weight average molecular weight measured by Waters2695 which is GPC made from Waters.

Production of Binder Resin Fine Particles After mixing binder resin fine particle materials having the following composition, a kneaded product was obtained by treating with a biaxial kneader set at a temperature of 120 ° C. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated binder resin.

Binder resin fine particle composition polyester resin, molecular weight 6000 98 parts by weight,
Charge control agent, salicylic acid compound 2 parts by weight Manufacture of fine binder resin particles 40 parts by weight of coarsely granulated binder resin, 0.4 parts by weight of sodium di-2-ethylhexyl sulfosuccinate, 1 part by weight of amine compound, ion-exchanged water 58 .6 parts by weight were charged into NANO3000, the sample temperature was heated to 150 ° C., and the number of passes was one to obtain fine particles. After the treatment, the mixture was cooled to 30 ° C. to obtain resin fine particles having a volume average particle diameter of 100 nm.

Production of agglomerated particles While stirring at 30 ° C., 5 parts by weight of toner material fine particles, 0.2 part by weight of 1N hydrochloric acid and 94.8 parts by weight of ion-exchanged water are mixed, and then dimethylaminoethanol is added to adjust the pH to 6. And it heated to 50 degreeC and the aggregate with a volume average particle diameter of 4.9 micrometers was obtained.

Production of capsule particles While stirring at 50 ° C., 78 parts by weight of aggregated particles and 14 parts by weight of binder resin fine particles are mixed, 8 parts by weight of 18% ammonium sulfate aqueous solution is added, and the mixture is heated to 93 ° C. A capsule particle of 0.0 μm was obtained.

  The capsule particles were washed with a centrifuge until the conductivity of the washing water reached 50 μS / cm, and dried with a vacuum dryer until the water content became 0.3% by weight to obtain toner particles.

  After drying, 2 parts by weight of hydrophobic silica and 0.5 parts by weight of titanium oxide were adhered to the surface of the colored particles to obtain a toner. As a result of measuring the volume average particle diameter of the toner with a Coulter counter (manufactured by Beckman Coulter), the average particle diameter is 5.2 μm, and as a result of measuring the circularity with FPIA (manufactured by Sysmex Corporation), it is 0.98. It was.

  5 parts by weight of the capsule toner of the embodiment was mixed with 95 parts by weight of a carrier to obtain a developer. This developer was introduced into a copying machine for evaluation, and fixing evaluation was performed. As a result of intentionally changing the fixing device temperature and measuring the temperature range of the fixing device capable of obtaining a good image, the temperature region (referred to as a non-offset temperature region) capable of obtaining a good image is 70 ° C. I found that there was.

  Next, the developer was put into a copying machine modified for evaluation, and a sheet passing test of 100K sheets was performed at a printing rate of 10%. As a result of collecting the developer after completion of paper passing and measuring the amount of the material that contaminated the carrier surface, the amount of carrier contamination was 0.06 parts by weight.

  In addition, the charging stability was evaluated in the same manner as in Example 1. The value of charging stability was 0.80.

  As a result of observing filming in the same manner as in Example 1, it was found that the transparency was good and a good image could be obtained.

The obtained results are shown in Table 1 below. By adopting such a configuration, the chargeability, fixability, filming resistance, and transparency can be improved.

Example 4
Production of Toner Material Fine Particles After mixing toner material fine particle materials having the following composition, the mixture was processed in a biaxial kneader set at 120 ° C. to obtain a kneaded product. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated toner material.

Toner material fine particle composition polyester resin, molecular weight 5000 78 parts by weight,
Polyester resin, molecular weight 40000 12 parts by weight,
Cyan pigment, Pigment Blue 2 5 parts by weight,
5 parts by weight of ester wax

40 parts by weight of coarsely granulated toner material, 0.4 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of an amine compound, and 58.6 parts by weight of ion-exchanged water are added to NANO3000, and the sample temperature is heated to 150 ° C. The atomized product was obtained after one pass. After completion of the treatment, the mixture was cooled to 30 ° C. to obtain toner material fine particles having a volume average particle diameter of 350 nm.

  The volume average particle diameter was measured using a Coulter counter (manufactured by Beckman Coulter).

  Moreover, the value of molecular weight here is the weight average molecular weight measured by Waters2695 which is GPC made from Waters.

Production of Binder Resin Fine Particles After mixing binder resin fine particle materials having the following composition, a kneaded product was obtained by treating with a biaxial kneader set at a temperature of 120 ° C. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated binder resin.

Binder resin fine particle composition polyester resin, molecular weight 6000 98 parts by weight,
Charge control agent, salicylic acid compound 2 parts by weight Manufacture of fine binder resin particles 40 parts by weight of coarsely granulated binder resin, 0.4 parts by weight of sodium di-2-ethylhexyl sulfosuccinate, 1 part by weight of amine compound, ion-exchanged water 58 .6 parts by weight were charged into NANO3000, the sample temperature was heated to 150 ° C., and the number of passes was one to obtain fine particles. After the treatment, the mixture was cooled to 30 ° C. to obtain resin fine particles having a volume average particle diameter of 100 nm.

Production of agglomerated particles While stirring at 30 ° C., 5 parts by weight of toner material fine particles, 0.2 part by weight of 1N hydrochloric acid and 94.8 parts by weight of ion-exchanged water are mixed, and then dimethylaminoethanol is added to adjust the pH to 6. And it heated to 50 degreeC and the aggregate with a volume average particle diameter of 4.9 micrometers was obtained.

Manufacture of capsule particles While stirring at 50 ° C., 78 parts by weight of aggregated particles and 14 parts by weight of binder resin fine particles are mixed, 8 parts by weight of 16% ammonium nitrate aqueous solution is added, and the mixture is heated to 93 ° C. A capsule particle of 0.0 μm was obtained.

  The capsule particles were washed with a centrifuge until the conductivity of the washing water reached 50 μS / cm, and dried with a vacuum dryer until the water content became 0.3% by weight to obtain toner particles.

  After drying, 2 parts by weight of hydrophobic silica and 0.5 parts by weight of titanium oxide were adhered to the surface of the toner particles to obtain a toner. As a result of measuring the volume average particle diameter of the toner with a Coulter counter (manufactured by Beckman Coulter), the average particle diameter is 5.2 μm, and as a result of measuring the circularity with FPIA (manufactured by Sysmex Corporation), it is 0.98. It was.

  5 parts by weight of the capsule toner of the embodiment was mixed with 95 parts by weight of a carrier to obtain a developer.

  When the non-offset temperature region was examined in the same manner as in Example 1, it was found to be 70 ° C.

  As a result of examining the carrier contamination amount in the same manner as in Example 1, the carrier contamination amount was 0.07 parts by weight.

  In order to obtain a satisfactory image over 100K sheets, the carrier contamination amount is desirably 0.10 parts by weight or less.

  Further, when the charging stability was examined in the same manner as in Example 1, the value of the developer was 0.80.

  As a result of evaluating the filming property in the same manner as in Example 1, it was found that the filming resistance was good and good.

  And as a result of implementing transparency evaluation like Example 1, it turned out that transparency is (circle) and a favorable image can be obtained.

The obtained results are shown in Table 1 below. By adopting such a configuration, the chargeability, fixability, filming resistance, and transparency can be improved.

Comparative Example 1
Production of Toner Material Fine Particles After mixing toner material fine particle materials having the following composition, the mixture was processed in a biaxial kneader set at 120 ° C. to obtain a kneaded product. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated toner material.

Toner material fine particle composition polyester resin, molecular weight 5000 78 parts by weight,
Polyester resin, molecular weight 40000 12 parts by weight,
Cyan pigment, Pigment Blue 2 5 parts by weight,
5 parts by weight of ester wax
40 parts by weight of coarsely granulated toner material, 0.4 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of an amine compound, and 58.6 parts by weight of ion-exchanged water are added to NANO3000, and the sample temperature is heated to 150 ° C. The atomized product was obtained after one pass. After completion of the treatment, the mixture was cooled to 30 ° C. to obtain toner material fine particles having a volume average particle diameter of 350 nm.

  The volume average particle diameter was measured using a Coulter counter (manufactured by Beckman Coulter).

  Moreover, the value of molecular weight here is the weight average molecular weight measured by Waters2695 which is GPC made from Waters.

Production of Binder Resin Fine Particles After mixing binder resin fine particle materials having the following composition, a kneaded product was obtained by treating with a biaxial kneader set at a temperature of 120 ° C. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated binder resin.

Binder resin fine particle composition Polyester resin, molecular weight 6000 98 parts by weight Charge control agent, salicylic acid compound 2 parts by weight Production of binder resin fine particles Roughly granulated binder resin 40 parts by weight, sodium dodecylbenzenesulfonate 0.4 parts by weight, amine 1 part by weight of the compound and 58.6 parts by weight of ion-exchanged water were added to the NANO 3000, the sample temperature was heated to 150 ° C., and the atomized product was obtained with one pass. After the treatment, the mixture was cooled to 30 ° C. to obtain resin fine particles having a volume average particle diameter of 100 nm.

Production of agglomerated particles While stirring at 30 ° C., 5 parts by weight of toner material fine particles, 0.2 part by weight of 1N hydrochloric acid and 94.8 parts by weight of ion-exchanged water are mixed, and then dimethylaminoethanol is added to adjust the pH to 6. And it heated to 50 degreeC and the aggregate with a volume average particle diameter of 4.9 micrometers was obtained.

Production of capsule particles While stirring at 50 ° C., 78 parts by weight of aggregated particles and 14 parts by weight of resin fine particles were mixed, 8 parts by weight of 15% ammonium chloride aqueous solution was added, and the mixture was heated to 93 ° C. An incomplete capsule particle of 9 μm was obtained.

  The capsule particles were washed with a centrifuge until the conductivity of the washing water reached 50 μS / cm, and dried with a vacuum dryer until the water content became 0.3% by weight to obtain toner particles.

  After drying, 2 parts by weight of hydrophobic silica and 0.5 parts by weight of titanium oxide were adhered to the surface of the colored particles to obtain a toner. As a result of measuring the volume average particle diameter of the toner with a Coulter counter (manufactured by Beckman Coulter), the average particle diameter is 5.2 μm, and as a result of measuring the circularity with FPIA (manufactured by Sysmex Corporation), 0.88 is obtained. It was.

  As a result of measuring the non-offset temperature region, it was found that the temperature region was 38 ° C. and a good image could not be obtained.

  Next, the developer was put into a copying machine modified for evaluation, and a sheet passing test of 100K sheets was performed at a printing rate of 10%. As a result of collecting the developer after completion of paper passing and measuring the amount of the material that contaminated the carrier surface, the amount of carrier contamination was 0.25 parts by weight.

  In order to obtain a satisfactory image over 100K sheets, the carrier contamination amount is desirably 0.10 parts by weight or less.

  Further, when the charging stability was evaluated in the same manner as in Example 1, the value of the developer was 0.64.

  As a result of evaluating the filming property in the same manner as in Example 1, it was found that the filming resistance was x, which was poor.

  And as a result of implementing transparency evaluation similarly to Example 1, it turned out that transparency is x and it is unsatisfactory.

The results obtained are shown in Table 1 below. By not containing the sulfosuccinic acid surfactant, it was found that sufficient performance could not be obtained with respect to chargeability, fixability, filming resistance and transparency.

Example 5
Production of Toner Material Fine Particles After mixing toner material fine particle materials having the following composition, the mixture was processed in a biaxial kneader set at 120 ° C. to obtain a kneaded product. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated toner material.

Toner material fine particle composition polyester resin, molecular weight 5000 78 parts by weight,
Polyester resin, molecular weight 40000 12 parts by weight,
Cyan pigment, Pigment Blue 2 5 parts by weight,
5 parts by weight of ester wax
40 parts by weight of coarsely granulated toner material, 0.4 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of an amine compound, and 58.6 parts by weight of ion-exchanged water are added to NANO3000, and the sample temperature is heated to 150 ° C. The atomized product was obtained after one pass. After completion of the treatment, the mixture was cooled to 30 ° C. to obtain toner material fine particles having a volume average particle diameter of 350 nm.

  The volume average particle diameter was measured using a Coulter counter (manufactured by Beckman Coulter).

  Moreover, the value of molecular weight here is the weight average molecular weight measured by Waters2695 which is GPC made from Waters.

Production of resin fine particles After mixing resin fine particle materials having the following composition, a kneaded product was obtained by treating with a biaxial kneader set at a temperature of 120 ° C. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated binder resin.

Resin fine particle composition polyester resin, molecular weight 6000 98 parts by weight,
Charge control agent, salicylic acid compound 2 parts by weight Production of resin fine particles 40 parts by weight of coarsely granulated binder resin, 0.4 part by weight of sodium di-2-ethylhexylsulfosuccinate, 1 part by weight of amine compound, ion-exchanged water 58. 6 parts by weight was charged into NANO3000, the sample temperature was heated to 150 ° C., and the number of passes was one to obtain fine particles. After the treatment, the mixture was cooled to 30 ° C. to obtain resin fine particles having a volume average particle diameter of 100 nm.

Production of agglomerated particles While stirring at 30 ° C., 5 parts by weight of toner material fine particles, 0.2 part by weight of 1N hydrochloric acid and 94.8 parts by weight of ion-exchanged water are mixed, and then dimethylaminoethanol is added to adjust the pH to 6. And it heated to 50 degreeC and the aggregate with a volume average particle diameter of 4.9 micrometers was obtained.

Production of Capsule Particles While stirring at 50 ° C., 78 parts by weight of aggregated particles and 14 parts by weight of resin fine particles are mixed, 8 parts by weight of 15% sodium chloride aqueous solution is added, and the mixture is heated to 93 ° C. An incomplete capsule particle of 9 μm was obtained.

  The capsule particles were washed with a centrifuge until the conductivity of the washing water reached 50 μS / cm, and dried with a vacuum dryer until the water content became 0.3% by weight to obtain toner particles.

  After drying, 2 parts by weight of hydrophobic silica and 0.5 parts by weight of titanium oxide were adhered to the surface of the colored particles to obtain a toner. As a result of measuring the volume average particle diameter of the toner with a Coulter counter (manufactured by Beckman Coulter), the average particle diameter is 5.0 μm, and as a result of measuring the circularity with FPIA (manufactured by Sysmex Corporation), 0.81 is obtained. It was.

  As a result of measuring the non-offset temperature region, the temperature region was 40 ° C.

  As a result of measuring the amount of the substance that contaminated the carrier surface in the same manner as in Example 1, the amount of carrier contamination was 0.12 parts by weight.

  When the charging stability was evaluated in the same manner as in Example 1, the value of the developer was 0.68.

  As a result of evaluating the filming property in the same manner as in Example 1, it was found that the filming resistance was Δ.

  And as a result of implementing transparency evaluation like Example 1, it turned out that transparency is (triangle | delta).

The obtained results are shown in Table 1 below. Since the aggregating agent is a neutral salt (NaCl), the charging performance, fixing performance, filming resistance, and transparency are slightly higher than those of Examples 1 to 4. I found it inferior.

Example 6
Production of Toner Material Fine Particles After mixing toner material fine particle materials having the following composition, the mixture was processed in a biaxial kneader set at 120 ° C. to obtain a kneaded product. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated toner material.

Toner material fine particle composition polyester resin, molecular weight 5000 78 parts by weight,
Polyester resin, molecular weight 40000 12 parts by weight,
Cyan pigment, Pigment Blue 2 5 parts by weight,
5 parts by weight of ester wax
40 parts by weight of coarsely granulated toner material, 0.4 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of an amine compound, and 58.6 parts by weight of ion-exchanged water are added to NANO3000, and the sample temperature is heated to 150 ° C. The atomized product was obtained after one pass. After completion of the treatment, the mixture was cooled to 30 ° C. to obtain toner material fine particles having a volume average particle diameter of 350 nm.

  The volume average particle diameter was measured using a Coulter counter (manufactured by Beckman Coulter).

  Moreover, the value of molecular weight here is the weight average molecular weight measured by Waters2695 which is GPC made from Waters.

Production of Binder Resin Fine Particles After mixing resin fine particle materials having the following composition, a kneaded product was obtained by treating with a biaxial kneader set at 120 ° C. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated binder resin.

Binder resin fine particle composition polyester resin, molecular weight 6000 98 parts by weight,
Charge control agent, salicylic acid compound 2 parts by weight Manufacture of fine binder resin particles 40 parts by weight of coarsely granulated binder resin, 0.4 parts by weight of sodium di-2-ethylhexyl sulfosuccinate, 1 part by weight of amine compound, ion-exchanged water 58 .6 parts by weight were charged into NANO3000, the sample temperature was heated to 150 ° C., and the number of passes was one to obtain fine particles. After the treatment, the mixture was cooled to 30 ° C. to obtain resin fine particles having a volume average particle diameter of 100 nm.

Production of agglomerated particles While stirring at 30 ° C., 5 parts by weight of toner material fine particles, 0.2 part by weight of 1N hydrochloric acid and 94.8 parts by weight of ion-exchanged water are mixed, and then dimethylaminoethanol is added to adjust the pH to 6. And it heated to 50 degreeC and the aggregate with a volume average particle diameter of 4.9 micrometers was obtained.

Manufacture of capsule particles While stirring at 50 ° C., 78 parts by weight of aggregated particles and 14 parts by weight of resin fine particles are mixed, 8 parts by weight of 1% ammonium chloride solution is added, and the mixture is heated to 93 ° C. An incomplete capsule particle of 9 μm was obtained.

  The capsule particles were washed with a centrifuge until the conductivity of the washing water reached 50 μS / cm, and dried with a vacuum dryer until the water content became 0.3% by weight to obtain toner particles.

  After drying, 2 parts by weight of hydrophobic silica and 0.5 parts by weight of titanium oxide were adhered to the surface of the colored particles to obtain a toner. The volume average particle diameter of the toner was measured with a Coulter counter (manufactured by Beckman Coulter). As a result, the average particle diameter was 4.9 μm, and the circularity was measured with FPIA (manufactured by Sysmex Corporation). It was.

  5 parts by weight of the capsule toner of the embodiment was mixed with 95 parts by weight of a carrier to obtain a developer. This developer was introduced into a copying machine for evaluation, and fixing evaluation was performed. As a result of intentionally changing the fixing device temperature and measuring the non-offset temperature region, the temperature region was 43 ° C.

  As a result of measuring the amount of the substance that contaminated the carrier surface in the same manner as in Example 1, the amount of carrier contamination was 0.11 part by weight.

  As for the charging stability, the value of the developer was 0.65. If the value is 0.70 or more, a good image can be obtained regardless of the environmental atmosphere.

  As a result of evaluating the filming property in the same manner as in Example 1, it was found that the filming resistance was Δ.

  As a result of evaluating the transparency in the same manner as in Example 1, it was found that the transparency was Δ.

The obtained results are shown in Table 1 below. When the ratio of the monovalent acidic salt component to the resin component in the shell material is larger than 1:20, the charging property, fixing property, filming resistance, and transparency are improved. It was found that the performance was slightly inferior to Examples 1 to 4.

Example 7
Production of Toner Material Fine Particles After mixing toner material fine particle materials having the following composition, the mixture was processed in a biaxial kneader set at 120 ° C. to obtain a kneaded product. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated toner material.

Toner material fine particle composition polyester resin, molecular weight 5000 78 parts by weight,
Polyester resin, molecular weight 40000 12 parts by weight,
Cyan pigment, Pigment Blue 2 5 parts by weight,
5 parts by weight of ester wax

40 parts by weight of coarsely granulated toner material, 0.4 parts by weight of sodium di-2-ethylhexyl sulfosuccinate, 1 part by weight of an amine compound and 58.6 parts by weight of ion-exchanged water are charged into NANO3000, and the sample temperature is set to 150 ° C. And atomized product was obtained in one pass. After completion of the treatment, the mixture was cooled to 30 ° C. to obtain toner material fine particles having a volume average particle diameter of 350 nm.

  The volume average particle diameter was measured using a Coulter counter (manufactured by Beckman Coulter).

  Moreover, the value of molecular weight here is the weight average molecular weight measured by Waters2695 which is GPC made from Waters.

Production of Binder Resin Fine Particles After mixing resin fine particle materials having the following composition, a kneaded product was obtained by treating with a biaxial kneader set at 120 ° C. The kneaded product was pulverized with a hammer mill to obtain a coarsely granulated binder resin.

Bainter resin fine particle composition polyester resin, molecular weight 6000 98 parts by weight,
Charge control agent, salicylic acid compound 2 parts by weight Production of resin fine particles Roughly granulated binder resin 40 parts by weight, sodium dodecylbenzenesulfonate 0.4 part by weight, amine compound 1 part by weight, ion-exchanged water 58.6 parts by weight Was put into NANO3000, the sample temperature was heated to 150 ° C., and the number of passes was one to obtain fine particles. After the treatment, the mixture was cooled to 30 ° C. to obtain resin fine particles having a volume average particle diameter of 100 nm.

Production of agglomerated particles While stirring at 30 ° C., 5 parts by weight of toner material fine particles, 0.2 part by weight of 1N hydrochloric acid and 94.8 parts by weight of ion-exchanged water are mixed, and then dimethylaminoethanol is added to adjust the pH to 6. And it heated to 50 degreeC and the aggregate with a volume average particle diameter of 4.9 micrometers was obtained.

Production of capsule particles While stirring at 50 ° C., 78 parts by weight of aggregated particles and 14 parts by weight of resin fine particles were mixed, 8 parts by weight of ammonium chloride was added, and the mixture was heated to 93 ° C., and the volume average particle size was 6.7 μm. Incomplete capsule particles were obtained.

  The capsule particles were washed with a centrifuge until the conductivity of the washing water reached 50 μS / cm, and dried with a vacuum dryer until the water content became 0.3% by weight to obtain toner particles.

  After drying, 2 parts by weight of hydrophobic silica and 0.5 parts by weight of titanium oxide were adhered to the surface of the colored particles to obtain a toner. As a result of measuring the volume average particle diameter of the toner with a Coulter counter (manufactured by Beckman Coulter), the average particle diameter was 6.7 μm, and as a result of measuring the circularity with FPIA (manufactured by Sysmex Corporation), it was 0.71. It was.

  5 parts by weight of the capsule toner of the embodiment was mixed with 95 parts by weight of a carrier to obtain a developer. This developer was introduced into a copying machine for evaluation, and fixing evaluation was performed. As a result of intentionally changing the fixing device temperature and measuring the non-offset temperature region, the temperature region was 44 ° C.

  Next, the developer was put into a copying machine modified for evaluation, and a sheet passing test of 100K sheets was performed at a printing rate of 10%. As a result of collecting the developer after completion of paper passing and measuring the amount of the substance that contaminated the carrier surface, the amount of carrier contamination was 0.14 parts by weight.

  In addition, the charging stability was evaluated in the same manner as in Example 1. The charge stability was 0.70 for the developer.

  As a result of evaluating the filming property in the same manner as in Example 1, it was found that the filming resistance was Δ.

  And as a result of implementing transparency evaluation like Example 1, it turned out that transparency is (triangle | delta).

The obtained results are shown in Table 1 below. There are many flocculants, the ratio of the monovalent acidic salt component to the resin component in the shell material is less than 1: 1, and the sulfosuccinic acid surfactant in the shell relative to the flocculant + Due to the lack of sodium dodecylbenzenesulfonate contained in the core slurry, sufficient performance is obtained in comparison with Examples 1 to 4 in terms of chargeability, fixability, filming resistance, and transparency. I knew it was n’t there.

  3 ... High pressure pump, 5 ... Atomization part, 10 ... High pressure homogenizer, 12, 13 ... Check valve

Claims (7)

Preparing a first aqueous dispersion containing the granulated toner material and an aqueous medium;
Finely granulating the granulated toner material by applying mechanical shear to the dispersion to obtain toner material fine particles having a size smaller than the size of the granulated toner material;
A step of aggregating the toner material fine particles to form aggregated particles;
Preparing a second aqueous dispersion containing a binder resin, a sulfosuccinic surfactant and an aqueous medium;
A step of making the binder resin fine by giving mechanical shearing to the second aqueous dispersion to obtain binder resin fine particles having a size smaller than the size of the binder resin;
Mixing the agglomerated particles and the binder resin fine particles in an aqueous medium to form a third aqueous dispersion; and using the agglomerated particles as a core component and the binder resin fine particles as a shell component on the surface of the core component A method for producing a developer, comprising the step of agglomerating a shell component to form encapsulated toner particles.   The sulfosuccinic acid-based surfactant includes dioctyl sodium sulfosuccinate, diethylhexyl sodium sulfosuccinate, diethylhexyl sodium sulfosuccinate, dilauryl sodium sulfosuccinate, polyoxyethylene alkyl (12-14) disodium sulfosuccinate, and sulfosuccinic acid. The process according to claim 1, which is at least one sulfosuccinic acid ester salt selected from the group consisting of polyoxyethylene lauroylethanolamide disodium.   The method according to claim 1, wherein the binder resin is a polyester resin.   The method according to claim 1 or 2, wherein the granulated toner material further contains a colorant and / or a release agent.   The method according to any one of claims 1 to 4, wherein the granulated toner material is obtained by a step of melt-kneading and coarsely pulverizing a mixture containing the binder resin and the colorant.   The method according to any one of claims 1 to 5, wherein the mechanical shearing is performed using a high-pressure homogenizer.   The method according to claim 1, wherein the aggregation of the toner material fine particles further includes pH adjustment and heating.

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