JP4137126B2 - Toner production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a toner by which generation of scale-like extraneous matter in a container in which a treatment liquid is stirred can be prevented, and by which a toner showing excellent developing performance, transferability and fixability, when an image is formed with an obtained toner, is obtained. <P>SOLUTION: In the method for manufacturing a toner synthesized in an aqueous medium, a container 1 in which a treatment liquid 2 containing at least colored particles is stirred is used, and after discharging the treatment liquid, a cleaning liquid is sprayed from a nozzle 9, 10 or 11 on the inside of the container. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a toner manufacturing method used in an image forming method for revealing an electrostatic latent image and a toner jet recording method.

  Conventionally, a number of methods are known as electrophotographic methods. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is formed with toner. Development is performed to make a visible image, and a toner image is transferred to a transfer material such as paper as necessary. Then, the toner image is fixed on the transfer material by heat or pressure to obtain a copy or printed matter. .

  Various methods have been proposed for developing with toner or fixing a toner image.

  Conventionally, toners used for these purposes are generally obtained by melt-kneading a colorant composed of a dye or pigment in a thermoplastic resin, uniformly dispersing it, and then finely pulverizing it with a fine pulverizer. Toner having a desired particle size has been produced by classification with a classifier.

  Although this method of manufacture can produce fairly good toner, there are certain limitations, i.e., limited choice of toner materials. For example, the resin colorant dispersion must be sufficiently brittle and capable of being finely pulverized with economically possible production equipment. However, if the resin colorant dispersion is made brittle in order to satisfy these requirements, when the dispersion is actually pulverized at high speed, the particle size range of the formed particles tends to be widened, and in particular, a relatively large proportion of fine particles Is included in this.

  Further, the toner obtained from such a brittle material is likely to be further pulverized or powdered in a developing device such as a copying machine. Also, with this method, it is difficult to completely disperse solid fine particles such as a colorant in the resin. Depending on the degree of dispersion, an increase in fog at the time of image formation, a decrease in image density, color mixing, or transparency Sufficient attention must be paid to the dispersion of the colorant, as this can cause poor color. Further, exposure of the colorant to the fracture surface of the pulverized particles may cause a change in development characteristics.

  On the other hand, in order to overcome the problems of the toner by the pulverization method, the toner by the chemical synthesis not including the pulverization step including the suspension polymerization method toner according to Patent Document 1, Patent Document 2, and Patent Document 3, and the manufacturing method thereof Has been proposed. For example, in a suspension polymerization toner, a monomer composition is prepared by uniformly dissolving or dispersing a polymerizable monomer, a colorant and a polymerization initiator and, if necessary, a crosslinking agent, a charge control agent, and other additives. After that, the monomer composition is dispersed in a medium containing a dispersion stabilizer, for example, an aqueous phase using a suitable stirrer, and at the same time, a polymerization reaction is carried out, followed by filtration and drying. Toner particles having a particle size are obtained. In addition, in the emulsion aggregation method toner, the monomer is emulsion-polymerized in a liquid to which an emulsion of necessary additives is added to produce fine polymer particles, and then an organic solvent, an aggregating agent, etc. are added. And can be manufactured by the method of meeting together. A method of preparing by mixing with a dispersion liquid such as a release agent and a colorant necessary for the composition of the toner at the time of association, and a toner component such as a release agent and a colorant dispersed in the monomer And then emulsion polymerization. The steps after filtration and drying can be performed in the same manner as in the suspension polymerization method. Here, the term “association” means that a plurality of resin particles and colorant particles are fused. In general, a toner by chemical synthesis that does not include a pulverization step, such as a suspension polymerization toner and an emulsion aggregation toner, is referred to as a polymerization toner or a polymerization toner. In these methods, since the pulverization step is not included at all, the toner does not need to be brittle, a soft material can be used as the resin, and there is no exposure of the colorant to the surface of the particles. There is an advantage that a toner having frictional charging properties can be obtained. In addition, since the particle size distribution of the obtained toner is relatively sharp, even if the classification process is omitted or classified, the toner can be obtained in high yield, saving energy, shortening time, improving process yield, etc. The cost reduction effect is great. In addition, since a large amount of a low softening point substance can be encapsulated in the toner as a release agent, there is an advantage that the obtained toner has excellent offset resistance.

  In the production process of these polymerized toners, there is a process in which the object to be treated is a liquid substance or a slurry existing in a suspended state in a liquid (hereinafter, the liquid substance and the slurry are collectively referred to as “treatment liquid”), Each processing solution is generally processed in a batch manner in a container such as a tank. Moreover, it is common to carry out with stirring so that the treatment is uniformly carried out in the same batch. Furthermore, it is preferable to control the processing temperature to be constant so that there is no difference in the degree of processing between different batches. In general, the treatment temperature is 30 ° C. or more and 120 ° C. or less, and is constant on the heating side from room temperature.

  When the obtained polymerized toner was closely observed, it was found that there were a small amount of toner having an irregular shape and a colorless toner not showing the color of the colorant (hereinafter referred to as an irregular toner). Amorphous toners are considered to have a different generation process from normal toners. When this ratio is increased, toner characteristics such as tribocharging properties and development characteristics when image evaluation is performed are adversely affected. Colored streaks, fogging, etc. are observed. Therefore, in the production method of the polymerized toner, preventing the generation of the irregular shaped toner is an important matter for producing a toner having a stable property.

  The irregular toner in the polymerized toner is mainly caused by the scale-like deposits generated in the container such as the above-mentioned tank. Therefore, frequent removal work of the scale-like deposits is required, which reduces the operating rate of the manufacturing apparatus. As a result, there is a problem that the cost of the product toner is increased.

Various measures for preventing the formation of scale-like deposits in each container have been proposed in Patent Document 4 and the like, but since measures were taken without paying attention to the curing rate of the deposits, the measures were not perfect. The measure was excessive and the cost was increased.

Japanese Patent Publication No. 36-10231 Japanese Patent Publication No. 43-10799 Japanese Patent Publication No. 51-14895 JP-A-10-153878

  Accordingly, an object of the present invention is to provide a method for producing a toner that solves the above-described problems and that can produce a toner having a small amount of irregular shaped toner and excellent in developing performance, transfer performance, and fixing performance.

  Another object of the present invention is to provide a method for stably producing a toner having excellent performance over a long period of time by suppressing generation of scale-like deposits in a toner production apparatus.

  The above object is achieved by the present invention described below.

That is, the present invention provides a method for producing a toner which is synthesized in an aqueous medium, at least the colored particles and the polymerizable monomer and heated in a vessel to prepare a dispersed process liquid, said after the process solution discharged A method for producing a toner in which a cleaning liquid is sprayed into a container while the discharged processing liquid is polymerized in an aqueous medium , and the temperature T3 of the cleaning liquid and the temperature T2 of the heated processing liquid are:
T3 ≦ T2-10
This is a method for producing a toner having the following relationship . Preferably, the temperature T3 (° C.) of the cleaning liquid to be sprayed and the temperature T2 (° C.) of the treatment liquid are
T3 ≦ T2-20
The method for producing a toner is characterized in that the cleaning liquid is sprayed preferably within 10 minutes, more preferably within 5 minutes after discharging the processing liquid.

  According to the present invention, it is possible to prevent the formation of scale-like deposits in a container in which a processing solution is stirred, and when an image is formed using the obtained toner, a toner having excellent development performance, transfer performance, and fixing performance is obtained. A method for producing the resulting toner is provided.

  Furthermore, according to the present invention, there is provided a method for producing a polymerized toner that can effectively use raw materials to obtain a toner having excellent economical efficiency.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

  As a result of intensive investigations to solve the above-described problems of the prior art, the present inventors have prevented the generation of scale-like deposits in the container in which the treatment liquid is agitated. It has been found that the method of spraying the cooling and / or cleaning liquid has a great influence.

  The toner of the present invention contains at least a resin and a colorant, but may contain a release agent, a charge control agent, or the like, which is a fixability improving agent, if necessary. Further, an external additive composed of inorganic fine particles or organic fine particles may be added to the toner particles containing the resin and the colorant as main components.

  In the toner of the present invention, a monomer is emulsion-polymerized in a suspension polymerization method or a liquid obtained by adding an emulsion of necessary additives to produce fine polymer particles. It can manufacture by the method of adding an agent etc. and making it associate. A method of preparing by mixing with a dispersion liquid such as a release agent and a colorant necessary for the composition of the toner at the time of association, and a toner component such as a release agent and a colorant dispersed in the monomer And a method of emulsion polymerization. Here, “association” means that a plurality of resin particles and colorant particles are fused.

  The “aqueous medium” as used in the present invention refers to a medium containing at least 50% by mass of water.

  Although it does not specifically limit as a manufacturing method of suspension polymerization method, The following manufacturing methods can be mentioned.

  That is, various constituent materials such as a colorant and, if necessary, a release agent, a charge control agent, and a polymerization initiator are added to the polymerizable monomer, and then a homogenizer, a sand mill, a sand grinder, an ultrasonic disperser, etc. Various constituent materials are dissolved or dispersed in the polymerizable monomer. The polymerizable monomer in which these various constituent materials are dissolved or dispersed is dispersed in oil droplets of a desired size as a toner in an aqueous medium containing a dispersion stabilizer using a homomixer or a homogenizer. Then, it transfers to the reaction apparatus which has a stirring mechanism, and a polymerization reaction is advanced by heating. After completion of the reaction, the dispersion stabilizer is removed, filtered, washed, and dried to prepare the toner of the present invention.

  Further, as a method for producing the toner of the present invention, a method in which resin particles are prepared by fusing in an aqueous medium can also be mentioned. The method is not particularly limited, and examples thereof include methods disclosed in JP-A-5-265252, JP-A-6-329947, and JP-A-9-15904. That is, a method of associating a plurality of dispersed particles of constituent materials such as resin particles and a colorant, or a plurality of fine particles composed of a resin and a colorant, particularly after dispersing them in water using an emulsifier, the critical aggregation concentration The toner of the present invention is obtained by adding the above flocculant and salting out, and simultaneously heat-melting the formed polymer itself at a temperature equal to or higher than the glass transition temperature, and heating and drying the particles in a fluid state while containing water. Can be formed. Here, an organic solvent that is infinitely soluble in water may be added simultaneously with the flocculant.

  Specific examples of preferable monomers used in the present invention include styrene monomers such as styrene, o (m-, p-)-methylstyrene, m (p-)-ethylstyrene; Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic (Meth) acrylate monomers such as behenyl acid, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate; butadiene, isoprene, cyclohexene, (meth) An ene monomer such as acrylonitrile and acrylamide is preferably used. These monomers are used alone or generally so that the theoretical glass transition temperature (Tg) described in the publication polymer handbook 2nd edition III-P139-192 (manufactured by John Wiley & Sons) is 40-75 ° C. It is used by mixing appropriately. When the theoretical glass transition temperature is less than 40 ° C., there are problems in terms of storage stability of the toner and durability of the developer. On the other hand, when it exceeds 75 ° C., the fixing point is increased. In some cases, the color toners are not sufficiently mixed, resulting in poor color reproducibility. Further, the transparency of the OHP image is remarkably lowered, which is not preferable from the viewpoint of high image quality.

  The molecular weight of the outer shell resin is measured by GPC (gel permeation chromatography). As a specific GPC measurement method, toner is extracted with a toluene solvent for 20 hours in advance using a Soxhlet extractor, and then toluene is distilled off with a rotary evaporator. Further, the low softening point substance is dissolved but the outer shell resin is dissolved. After washing thoroughly with an organic solvent that cannot be dissolved, such as chloroform, a sample obtained by filtering a solution soluble in THF (tetrahydrofuran) with a solvent-resistant membrane filter having a pore size of 0.3 μm was manufactured by Waters. Using 150C, the column configuration can connect A-801, 802, 803, 804, 805, 806, 807 manufactured by Showa Denko, and measure the molecular weight distribution using a standard polystyrene resin calibration curve. The number average molecular weight (Mn) of the obtained resin component is 5,000 to 100,000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) is 2-100. Preferred for the invention.

  In the present invention, when a toner having a core / shell structure is produced, it is particularly preferable to further add a polar resin to the outer shell resin in order to encapsulate the low softening point substance.

  As the polar resin used in the present invention, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a saturated polyester resin, and an epoxy resin are preferably used. The polar resin is particularly preferably one that does not contain much unsaturated groups that can react with the outer shell resin or monomer. If a polar resin having many unsaturated groups is included, a cross-linking reaction occurs with the monomer forming the outer shell resin layer. This is disadvantageous and not preferable.

  In the present invention, an outermost resin layer may be further provided on the toner surface. The glass transition temperature of the outermost shell resin layer is preferably designed to be higher than the glass transition temperature of the outer shell resin layer in order to further improve the blocking resistance, and is preferably crosslinked to such an extent that the fixing property is not impaired. . Further, the outermost resin layer preferably contains a polar resin or a charge control agent in order to improve chargeability.

The method for providing the outermost shell layer is not particularly limited, and examples thereof include the following methods.
1. In the latter half of the polymerization reaction or after completion, if necessary, add a monomer in which a polar resin, charge control agent, cross-linking agent, etc. are dissolved and dispersed in the reaction system and adsorb to the polymer particles, and then add a polymerization initiator to perform polymerization. How to do.
2. If necessary, emulsion-polymerized particles or soap-free polymerized particles consisting of monomers containing a polar resin, a charge control agent, a crosslinking agent, etc. are added to the reaction system and aggregated on the surface of the polymerized particles. How to fix.
3. A method in which emulsion-polymerized particles or soap-free polymerized particles comprising monomers containing a polar resin, a charge control agent, a crosslinking agent, etc. are mechanically fixed to the toner particle surface in a dry manner as required.
It is.

  As the colorant used in the present invention, a black colorant that is toned in black using carbon black, a magnetic material, and the following yellow / magenta / cyan colorant is used.

  As the yellow colorant, compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168, etc. are preferably used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.

  As the cyan colorant used in the present invention, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like can be used particularly preferably.

  These colorants can be used alone or in combination and further in the form of a solid solution.

  In the case of a color toner, the colorant used in the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin.

  When a magnetic material is used as the black colorant, it is used by adding 4 to 150 parts by mass with respect to 100 parts by mass of the resin, unlike other colorants.

  As the charge control agent used in the present invention, known ones can be used. In the case of a color toner, in particular, a charge control agent that is colorless and has a high toner charging speed and can stably maintain a constant charge amount. preferable. Specific examples of the negative compounds include salicylic acid, naphthoic acid, dicarboxylic acid metal compounds, sulfonic acid, polymer compounds having carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, calixarene, and the like. As a positive system, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, an imidazole compound, and the like are preferably used. The charge control agent is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin.

  Examples of the polymerization initiator used in the present invention include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, and 1,1′-azobis (cyclohexane). -1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo-based polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, Peroxide-based polymerization initiators such as cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide are used.

  The addition amount of the polymerization initiator varies depending on the target degree of polymerization, but generally 0.5 to 20% by mass is added to the monomer. The kind of the initiator is slightly different depending on the polymerization method, but can be used alone or mixed with reference to the 10-hour half-life temperature. Further, in order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like can be further added and used.

  In the toner production method of the present invention, it is preferable that the dispersion stabilizer used in the polymerization is an acid-soluble inorganic oxide. Furthermore, the inorganic oxide is preferably a phosphoric acid compound. Examples of the phosphate compound include tricalcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate. These dispersion stabilizers are preferably used in an amount of 0.2 to 10.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Further, as the dispersion stabilizer, a commercially available one may be used as it is. However, in order to obtain dispersed particles having a fine uniform particle size, the inorganic compound is produced under high-speed stirring in a dispersion medium. It can also be used. For example, in the case of tricalcium phosphate, a dispersion stabilizer preferable for the suspension polymerization method can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution under high-speed stirring. Moreover, you may use together 0.001-0.1 mass part surfactant for refinement | miniaturization of these dispersion stabilizers.

  Specific examples of the surfactant include commercially available nonionic, anionic, and cationic surfactants such as sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, and lauric acid. Sodium, potassium stearate, calcium oleate and the like are preferably used.

  With reference to the drawings, a method for cooling the container and / or spraying a cleaning liquid after discharging the processing liquid to prevent the formation of scale-like deposits in the container that stirs the processing liquid, which is a feature of the present invention. This will be specifically described. FIG. 1 shows an example of a schematic diagram of a toner production apparatus used in the present invention.

  In FIG. 1, the process for producing the treatment liquid 2 which is a liquid intermediate substance in the toner production process using the toner production tank 1 includes the following processes, but the present invention is not limited to the following. Absent.

The following steps are specific to suspension polymerization.
A. Dissolving step (toner production tank) that forms a polymerizable monomer composition (treatment liquid A) by dissolving / dispersing a polymerizable monomer and a colorant, a charge control agent, a polymerization initiator, a resin, a lubricant, and the like. A). In some cases, the step of dissolving / dispersing these additives is divided into multi-stage treatment with treatment liquids A1, A2,.
B. A granulation step (toner production tank B) for producing a suspension (treatment liquid B) in which a polymerizable monomer composition is present as droplets in an aqueous dispersion medium.
C. A polymerization step (toner production tank C) in which a polymerizable monomer composition is polymerized in an aqueous dispersion medium to produce a toner suspension (treatment liquid C).
D. A distillation step (toner production tank D) in which the toner suspension is distilled to produce a purified toner suspension (treatment liquid D).

The following processes are specific to emulsion polymerization.
E. An emulsion polymerization step (toner production tank E) for producing an emulsion of fine particles (treatment liquid E) by emulsion polymerization of a polymerizable monomer or a polymerizable monomer composition.
F. An agglomeration step (toner production tank F) in which an emulsion of various additives is mixed with the fine particle emulsion as necessary to agglomerate the fine particles to produce a dispersion of the agglomerated particles (treatment liquid F).
G. A maturing step (toner production tank G) for adjusting the particle size and shape of the aggregated particles by adjusting the temperature / pH to produce a toner dispersion (treatment liquid G).

  Mixing the treatment liquid 2 with the stirring blade 3 is important for uniformly treating the treatment liquid 2. In general, the processing temperature is controlled so that there is no difference in the degree of processing between different batches. In particular, when the treatment is a polymerization treatment, it is important to control the treatment temperature because the treatment temperature affects the polymerization rate. If the polymerization rate is non-uniform between different batches, the molecular weight of the toner produced is different, resulting in a fatal defect in toner fixability. In general, the treatment temperature is 30 ° C. or more and 120 ° C. or less, and is constant on the heating side from room temperature. As a method for controlling the processing temperature, a method in which a jacket 12 is installed around the toner production tank 1 and a heating medium or a refrigerant is supplied into the jacket 12 from the temperature control valve 4 is generally used.

  However, it is difficult to stir the processing liquid 2 without disturbing the liquid level 7, and liquid splash occurs at the liquid level 7, and the scale surface is formed on the wall surface near the liquid level 7 of the toner manufacturing tank 1 and the stirring blade 3. The deposit 8 is generated. When the processing is completed and the processing liquid 2 is transferred to the next process from the discharge valve 6 of the toner manufacturing tank 1, the scale deposit 8 remains on the wall surface of the empty toner manufacturing tank 1. If the remaining scale-like deposits 8 are not removed by the next batch, they are dried and solidified or thermally cured by heat transfer from the jacket 12. When batch production is repeated in this state, the cured scale-like deposit 8 is deposited, and when it grows so as to be subjected to stirring resistance, it peels off from the wall surface due to its own weight or vibration. When this deposit 8 is mixed into a normal processed product that is a product, it causes troubles in the post-process or quality problems in the market, and various methods for removing the deposit 8 on the wall have been proposed. However, since the measure to date has been a method of removing the deposit 8 without cooling, the deposit 8 is hardened during the removal, and the removal of the deposit 8 is often incomplete.

  The inventors of the present invention have arrived at a method for preventing the deposit 8 from being hardened by cooling the deposit 8 and facilitating the removal of the deposit 8. That is, after the treatment liquid 2 is discharged, the coolant is supplied from the coolant supply valve 5 to the jacket 12, and the deposit 8 is cooled through the wall surface of the toner manufacturing tank 1. The cooling temperature (T1) is preferably 10 ° C. or more lower than the temperature (T2) of the treatment liquid 2, and more preferably 20 ° C. or less lower than the temperature of the treatment liquid 2. The timing for cooling is preferably within 10 minutes after discharging the treatment liquid, and more preferably within 5 minutes.

  Since the cooled deposit 8 does not harden, it can be effectively used without being removed when it can be reused by mixing with the next batch. When it cannot be reused after being mixed with the next batch, the deposit 8 can be easily removed by spraying a cleaning liquid such as water. The spraying of the cleaning liquid can be performed with various nozzles, such as a wall surface nozzle 9, a stirring shaft nozzle 10, an entire spraying nozzle 11, and the like. The temperature (T3) of the sprayed cleaning liquid is preferably 10 ° C. or more lower than the temperature (T2) of the processing liquid 2, and more preferably the cleaning liquid temperature is 20 ° C. or lower than the temperature of the processing liquid 2. The timing of spraying the cleaning liquid is also preferably sprayed within 10 minutes after discharging the processing liquid, and more preferably sprayed within 5 minutes. The deposit removed together with the cleaning liquid can be added to the next step for effective use.

  An external additive may be added to the toner of the present invention to impart various toner performances. Examples of external additives used include metal oxides (aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide, etc.) and nitrides (silicon nitride, etc.) Carbide (silicon carbide, etc.), metal salts (calcium sulfate, barium sulfate, calcium carbonate, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), carbon black, silica, etc. are used.

  These external additives are used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of toner particles. These external additives may be used alone or in combination. Those subjected to hydrophobic treatment are more preferable.

  A Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter, Inc.) is used as a measuring device for the toner flat diameter and particle size distribution. As the electrolyte, first grade sodium chloride is used to prepare an approximately 1% NaCl aqueous solution.

  As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added.

  The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toners are measured by using the measuring apparatus with a 100 μm aperture as the aperture. Distribution was calculated.

  Then, a weight-based weight average particle diameter (D4) obtained from the volume distribution according to the present invention (representing the representative value of each channel as the representative value for each channel) was obtained.

The water content in the present invention is determined by collecting 5 g of water-containing particles in an aluminum dish, precisely weighing it (A [g]), leaving it in a dryer set at 105 ° C. for 1 hour, [G]) and the value calculated by the following equation.
Water content = ((A−B) / A) × 100 [%]

  The basic configuration and features of the present invention have been described above. Hereinafter, the present invention will be described more specifically with reference to examples of the present invention and comparative examples. However, of course, this does not limit the present invention.

<Reference Example 1>
1235 g of Na ₃ PO ₄ .12H ₂ O was added to 95 kg of ion-exchanged water, heated to 60 ° C., and then stirred at 3,700 rpm using a CLEARMIX stirrer (manufactured by M Technique). An aqueous solution containing 716 g of CaCl ₂ · 2H ₂ O dissolved in 5 kg of ion exchange water was gradually added thereto to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene 12000g
n-Butyl acrylate 2500g
C. I. Pigment Blue 15: 3 1100g
2200 g of paraffin wax (mp 70 ° C.)
Di-tert-butylsalicylic acid metal compound 150 g
The above formulation was heated to 60 ° C., and uniformly dissolved and dispersed to prepare a polymerizable monomer composition (= treatment liquid).

As a toner manufacturing tank for preparing the polymerizable monomer composition, the toner manufacturing tank shown in FIG.
1) Jacket temperature when processing solution is discharged: 60 ° C
2) Jacket temperature 10 minutes after discharge of processing solution: 50 ° C
3) Spraying of cleaning solution: The temperature of the jacket was controlled so as to be none.

  The polymerizable monomer composition and the polymerization initiator, 440 g of 2,2′-azobis (2,4-dimethylvaleronitrile), were charged into the aqueous medium.

The mixture of the polymerizable monomer composition and the aqueous medium was stirred at 3,700 rpm for 10 minutes using a CLEARMIX stirrer (manufactured by M Technique) in an N ₂ atmosphere at 60 ° C. The product was granulated.

  Thereafter, the polymerizable monomer composition was transferred to a polymerization apparatus, and the liquid temperature was reacted at 60 ° C. for 5 hours, and then the liquid temperature was 80 ° C. and reacted for 3 hours.

After completion of the polymerization reaction, the polymerization solution was transferred to a distillation apparatus, and the distillation was performed for 5 hours at a liquid temperature of 80 ° C. The distilled suspension was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered and dried to obtain a polymerized toner.

  When a series of operations consisting of dissolution, granulation, polymerization, distillation, filtration, and drying was carried out continuously for 40 batches without disassembling and cleaning the apparatus, the particle size of the toner obtained in the last 40 batches was a weight average diameter of 6 It had a sharp particle size distribution at .8 μm. Moreover, the endothermic peak top temperature by DSC measurement was 70 degreeC. Moreover, the amount of residual monomers and by-products (benzaldehyde) was 50 ppm in total.

To 100 parts by mass of the obtained toner, 0.7 part by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g was externally added. To 7 parts by mass of this toner, 93 parts by mass of an acrylic-coated ferrite carrier was mixed to obtain a developer.

  When this developer and externally added toner were used to print out an image using a Canon full color copier CLC-500 remodeling machine, no odor was generated and a good image was obtained. In addition, the toner production tank after the end of 40 batches was capable of further continuous operation although a slight deposit layer was observed. The results are shown in Table 1.

<Reference Example 2>
As a toner manufacturing tank for preparing the polymerizable monomer composition, the toner manufacturing tank shown in FIG.
1) Jacket temperature when processing solution is discharged: 60 ° C
2) Jacket temperature 10 minutes after treatment liquid discharge: 40 ° C
3) Spraying of the cleaning solution: A series of operations consisting of dissolution, granulation, polymerization, distillation, filtration, and drying were performed in the same manner as in Reference Example 1 except that the jacket temperature was controlled so as to be disassembled. When 40 batches were carried out continuously, the performance of the toner obtained in the last 40th batch was the same as in Reference Example 1, and no odor was generated and a good image was obtained. Further, no deposited layer was observed in the toner production tank after 40 batches, and further continuous operation was possible. The results are shown in Table 1.

<Reference Example 3>
As a toner manufacturing tank for preparing the polymerizable monomer composition, the toner manufacturing tank shown in FIG.
1) Jacket temperature when processing solution is discharged: 60 ° C
2) Jacket temperature 10 minutes after discharge of treatment liquid: 30 ° C
3) Spraying of the cleaning solution: A series of operations consisting of dissolution, granulation, polymerization, distillation, filtration, and drying were performed in the same manner as in Reference Example 1 except that the jacket temperature was controlled so as to be disassembled. When 40 batches were carried out continuously, the performance of the toner obtained in the last 40th batch was the same as in Reference Example 1, and no odor was generated and a good image was obtained. Further, no deposited layer was observed in the toner production tank after 40 batches, and further continuous operation was possible. The results are shown in Table 1.

<Reference Example 4>
As a toner manufacturing tank for preparing the polymerizable monomer composition, the toner manufacturing tank shown in FIG.
1) Jacket temperature when processing solution is discharged: 60 ° C
2) Jacket temperature after 10 minutes from discharge of treatment liquid: 10 ° C
3) Spraying of the cleaning solution: A series of operations consisting of dissolution, granulation, polymerization, distillation, filtration, and drying were performed in the same manner as in Reference Example 1 except that the jacket temperature was controlled so as to be disassembled. When 40 batches were carried out continuously, the performance of the toner obtained in the last 40th batch was the same as in Reference Example 1, and no odor was generated and a good image was obtained. Further, no deposited layer was observed in the toner production tank after 40 batches, and further continuous operation was possible. The results are shown in Table 1.

  However, the time for returning the jacket temperature to 60 ° C. for the next batch was longer than that of Reference Example 1, and as a result, the productivity was lowered.

<Reference Example 5>
As a toner manufacturing tank for preparing the polymerizable monomer composition, the toner manufacturing tank shown in FIG.
1) Jacket temperature when processing solution is discharged: 60 ° C
2) Jacket temperature 5 minutes after treatment liquid discharge: 50 ° C
3) Spraying of the cleaning solution: A series of operations consisting of dissolution, granulation, polymerization, distillation, filtration, and drying were performed in the same manner as in Reference Example 1 except that the jacket temperature was controlled so as to be disassembled. When 40 batches were carried out continuously, the performance of the toner obtained in the last 40th batch was the same as in Reference Example 1, and no odor was generated and a good image was obtained. Further, no deposited layer was observed in the toner production tank after 40 batches, and further continuous operation was possible. The results are shown in Table 1.

<Comparative Example 1>
1 except that the toner production tank shown in FIG. 1 was used as a toner production tank when preparing the polymerizable monomer composition, and the jacket temperature was fixed at 60 ° C. regardless of whether or not the treatment liquid was discharged. As in Example 1, a series of operations consisting of dissolution, granulation, polymerization, distillation, filtration and drying were carried out continuously for 40 batches without decomposing and cleaning the apparatus, and the toner particle size obtained in the last 40 batches was the weight average. It had a diameter of 8.2 μm and a broad particle size distribution on the coarse particle side. Moreover, the endothermic peak top temperature by DSC measurement was 70 degreeC. Moreover, the amount of residual monomers and by-products (benzaldehyde) was 50 ppm in total.

To 100 parts by mass of the obtained toner, 0.7 part by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g was externally added. To 7 parts by mass of this toner, 93 parts by mass of an acrylic-coated ferrite carrier was mixed to obtain a developer.

  Using this developer and externally added toner, images were printed on a Canon full color copier CLC-500 remodeled machine, but no odor was generated, but images with white streaks and unevenness from the beginning of image printing There has occurred. In addition, the deposits of the toner production tank after the 40th batch are severely generated, and further continuous operation is impossible and it is necessary to perform disassembly and cleaning. The results are shown in Table 1.

<Example 1>
1235 g of Na ₃ PO ₄ .12H ₂ O was added to 95 kg of ion-exchanged water, heated to 60 ° C., and then stirred at 3,700 rpm using a CLEARMIX stirrer (manufactured by M Technique). An aqueous solution containing 716 g of CaCl ₂ · 2H ₂ O dissolved in 5 kg of ion exchange water was gradually added thereto to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene 12000g
n-Butyl acrylate 2500g
C. I. Pigment Blue 15: 3 1100g
2200 g of paraffin wax (mp 70 ° C.)
Di-tert-butylsalicylic acid metal compound 150 g
The above formulation was heated to 60 ° C., and uniformly dissolved and dispersed to prepare a polymerizable monomer composition (= treatment liquid).

As a toner manufacturing tank for preparing the polymerizable monomer composition, the toner manufacturing tank shown in FIG.
1) Jacket temperature when processing solution is discharged: 60 ° C
2) Jacket temperature 10 minutes after discharge of processing solution: 50 ° C
3) Temperature control of the jacket and tank cleaning were performed so that hot water of 50 ° C. was sprayed 10 minutes after the treatment liquid was discharged.

  After dissolving 440 g of a polymerization initiator, 2,2′-azobis (2,4-dimethylvaleronitrile), in the polymerizable monomer composition immediately before discharge, the polymerizable monomer composition is placed in the aqueous medium. I put it in.

The mixture of the polymerizable monomer composition and the aqueous medium was stirred at 3,700 rpm for 10 minutes using a CLEARMIX stirrer (manufactured by M Technique) in an N ₂ atmosphere at 60 ° C. The product was granulated.

  Thereafter, the polymerizable monomer composition was transferred to a polymerization apparatus, and the liquid temperature was reacted at 60 ° C. for 5 hours, and then the liquid temperature was 80 ° C. and reacted for 3 hours.

After completion of the polymerization reaction, the polymerization solution was transferred to a distillation apparatus, and the distillation was performed for 5 hours at a liquid temperature of 80 ° C. The distilled suspension was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered and dried to obtain a polymerized toner.

  When a series of operations consisting of dissolution, granulation, polymerization, distillation, filtration, and drying was carried out continuously for 40 batches without disassembling and cleaning the apparatus, the particle size of the toner obtained in the last 40 batches was a weight average diameter of 6 It had a sharp particle size distribution at .8 μm. Moreover, the endothermic peak top temperature by DSC measurement was 70 degreeC. Moreover, the amount of residual monomers and by-products (benzaldehyde) was 50 ppm in total.

To 100 parts by mass of the obtained toner, 0.7 part by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g was externally added. To 7 parts by mass of this toner, 93 parts by mass of an acrylic-coated ferrite carrier was mixed to obtain a developer.

  When this developer and externally added toner were used to print out an image using a Canon full color copier CLC-500 remodeling machine, no odor was generated and a good image was obtained. In addition, the toner production tank after the end of 40 batches was capable of further continuous operation although a slight deposit layer was observed. The results are shown in Table 1.

<Example 2>
As a toner manufacturing tank for preparing the polymerizable monomer composition, the toner manufacturing tank shown in FIG.
1) Jacket temperature when processing solution is discharged: 60 ° C
2) Jacket temperature 10 minutes after discharge of processing solution: 50 ° C
3) Dissolution, granulation, polymerization, distillation, filtration, and the like in Example 1 except that the jacket temperature was controlled and the tank was washed so that warm water of 40 ° C. was sprayed 10 minutes after the treatment liquid was discharged. When a series of operations consisting of drying was carried out continuously for 40 batches without disassembling and cleaning the apparatus, the performance of the toner obtained in the last 40 batches was the same as in Example 1, and no odor was generated and a good image was obtained. It was. Further, no deposited layer was observed in the toner production tank after 40 batches, and further continuous operation was possible. The results are shown in Table 1.

<Example 3>
As a toner manufacturing tank for preparing the polymerizable monomer composition, the toner manufacturing tank shown in FIG.
1) Jacket temperature when processing solution is discharged: 60 ° C
2) Jacket temperature 10 minutes after discharge of processing solution: 50 ° C
3) Dissolution, granulation, polymerization, distillation, filtration, and the like in Example 1 except that the jacket temperature was controlled and the tank was washed so that hot water at 50 ° C. was sprayed 5 minutes after the treatment liquid was discharged. When a series of operations consisting of drying was carried out continuously for 40 batches without disassembling and cleaning the apparatus, the performance of the toner obtained in the last 40 batches was the same as in Example 1, and no odor was generated and a good image was obtained. It was. Further, no deposited layer was observed in the toner production tank after 40 batches, and further continuous operation was possible. The results are shown in Table 1.

Judgment of image evaluation A: Good C: Judgment of defect occurrence adhesion A: No deposit. Continuous production is possible.
B: There is a slight deposit. Continuous production is possible.
C: There is a deposit. Continuous production is not possible.

It is an example of the schematic diagram of the toner manufacturing apparatus used for this invention.

Explanation of symbols

1. 1. Toner production tank 2. Treatment liquid 3. Stirring blade 4. Temperature control valve 5. Refrigerant supply valve 6. Discharge valve Liquid level 8. 8. Scale-like deposits Wall surface nozzle 10. 10. Nozzle for exclusive use of stirring shaft Whole spray nozzle 12. Jacket

Claims (4)

In the method for manufacturing a toner which is synthesized in an aqueous medium, at least the colored particles polymerizable monomer and heated in a vessel, the dispersed to prepare a treatment solution, a washing solution into the container after the process solution discharged A method for producing a toner, in which the discharged processing liquid is polymerized in an aqueous medium while spraying , wherein the temperature T3 of the cleaning liquid and the temperature T2 of the heated processing liquid are:
T3 ≦ T2-10
A method for producing a toner having the following relationship . The temperature T3 (° C) of the cleaning liquid to be sprayed and the temperature T2 (° C) of the processing liquid are
T3 ≦ T2-20
The toner production method according to claim 1, wherein: Method for producing a toner according to claim 1 or 2, characterized in that spraying a cleaning liquid within the processing liquid 10 minutes after discharge. Method for producing a toner according to claim 1 or 2, characterized in that spraying a cleaning liquid within five minutes after the treatment liquid discharge.

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