JP5618798B2 - Method for producing polymerized toner - Google Patents

Description

  The present invention relates to a method for producing a polymerized toner for developing an electrostatic image, which is used in electrophotography, electrostatic recording method and the like.

  As a method for producing toner particles used in electrophotography, there has been proposed a suspension polymerization method in which toner particles are obtained by dispersing a polymerizable monomer in the form of droplets and performing polymerization. In the suspension polymerization method, a polymerizable monomer, a colorant, a release agent, and a crosslinker, a charge control agent, and other additives are uniformly dissolved or dispersed as necessary in the dissolution step. A body composition is prepared. Furthermore, a desired particle size is obtained through a granulation step in which the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer by using an appropriate stirrer or disperser, and a polymerization step in which a polymerization reaction is performed. A suspension of polymerized toner particles having

  In the polymerization step, a polymer deposit adheres to the inner wall of the polymerization vessel, the surface of the stirrer, and the like, and a polymer deposit resulting from polymerization of the monomer is a problem. When this deposit is left untreated, the amount increases each time the number of polymerization steps is repeated. In the case of remarkable adhesion, the heat transfer performance of the polymerization vessel is lowered and the stability of the polymerization reaction is adversely affected. Further, if this polymer deposit is peeled off and dropped and mixed into the toner, which is a product, the toner performance is adversely affected.

  In recent years, a polymerized toner produced by a suspension polymerization method using a magnetic material as a colorant for a black toner has been proposed (Patent Document 1). The surface of the magnetic material used in the toner is subjected to a hydrophobic treatment in order to improve dispersibility in the toner. When an attempt is made to produce a polymerized toner using this magnetic material, the aforementioned polymer deposits may be remarkably generated.

  One possible cause of the adhesion of the polymerizable monomer is considered to be the use of a magnetic material whose surface has been subjected to a hydrophobic treatment as a colorant. Hydrophobizing agents are chemically bonded to the surface of magnetic iron oxide. However, if there is an excessive amount of hydrophobizing agent relative to the surface of magnetic iron oxide, they are physically bonded to the surface of magnetic iron oxide without chemically bonding. It becomes attached and comes to exist. The hydrophobizing agent that is not chemically bonded but only attached to the surface is peeled off from the surface of the magnetic iron oxide by the shearing force of the stirrer or the disperser in the dissolution process or the granulation process and is eluted in the aqueous medium. The eluted hydrophobizing agent has a property as an emulsifier, and emulsifies and stabilizes the polymerizable monomer released from the particles of the polymerizable monomer composition in an aqueous medium. Then, the emulsified and stabilized polymerizable monomer eventually adheres to the inner wall of the polymerization vessel and the like, and this polymerizes in situ to form a polymer deposit. The polymer deposit remains in the polymerization vessel even after the completion of the polymerization process.

  As a technique for suppressing the occurrence of polymer deposits, there is a method of demulsifying a polymerizable monomer emulsified and stabilized in an aqueous medium with alcohol. There is Patent Document 2 as a technique for containing an alcohol in an aqueous medium. However, in a method for producing a polymerized toner using a magnetic material that has been subjected to a hydrophobization treatment, in the technique described in Patent Document 2, the amount of alcohol in the aqueous medium at the initial stage of polymerization is not effective in suppressing the occurrence of polymer deposits. It was enough.

  Moreover, there exists patent document 3 as a similar technique. However, in the technique described in Patent Document 3, the alcohol concentration in the aqueous medium is high, and the alcohol is adsorbed on the dispersion stabilizer, so that the dispersion stability of the toner particles in the aqueous medium is impaired. For this reason, the toner particle size distribution is broadened, and it cannot be said that the toner performance is satisfied.

JP 2001-235897 A Special WO05 / 093521 JP 2000-355639 A

  The present invention provides a production method for suppressing the formation of polymer deposits in a polymerization vessel in a polymerization step in the production of a polymerized toner containing a magnetic material having a hydrophobic surface applied as a colorant. With the goal.

As a result of intensive studies to solve the above problems, the present inventors have found the following method.
(1) (i) a polymerizable monomer, a magnetic material hydrophobic treatment is applied to the surface, the polymerizable monomer composition and containing not added to the aqueous medium, the polymerizable monomer composition A granulation step of forming particles of
(Ii) and Ru polymerization process by polymerizing polymerizable monomer contained in the particles,
A method for producing a polymerized toner having
The beginning of the polymerization process, in aqueous medium, the production method of polymerized toner, which comprises adding alcohol to 4 and boiling points 8 5 ° C. The number 1 or more carbon atoms.
(2) the concentration of 4 or less and a boiling point 85 ° C. or more alcohols the one or more carbon atoms in the said aqueous medium, wherein the polymerizable monomer polymerization conversion of 30% at the time of, der in 6000ppm following range of 2100ppm ( 1) The method for producing a polymerized toner according to ( 1).
(3) the until polymerization conversion of the polymerizable monomer reaches 80% by the addition of alcohol the number 1 to 4 and a boiling point 85 ° C. or more carbon atoms in the aqueous medium, the aqueous medium in method for producing a polymerized toner according to the concentration of the number of 1 or more 4 or more or less and a boiling point 85 ° C. carbon alcohol, to 6000ppm to less than 2100 ppm (1) or (2) in.
(4) the polymerizable monomer the polymerization apparatus are found use in the polymerization has a polymerization vessel,
The In the polymerization vessel, wherein the liquid phase of the aqueous medium with particles of the polymerizable monomer composition, and the gas phase, is formed,
The polymerization vessel has a vent pipe for exhausting the gas phase portion, and a carrier gas inlet ,
Wherein until the polymerization conversion of the polymerizable monomer reaches 80% while introducing 40 ° C. or higher 120 ° C. or less under a carrier gas to the gas phase portion, the volatile components generated in the gas phase portion the method for producing a polymerized toner according to any one of you exhaust from the vent pipe (1) to (3).

  According to the present invention, it is possible to suppress the occurrence of polymer deposits generated in the polymerization container in the polymerization step during the production of the polymerized toner particles. This prevents heat conduction from being hindered by the polymer deposit and blockage of piping due to the polymer deposit falling off, thereby reducing the removal work of the polymer deposit and improving the productivity.

  A specific method for producing polymerized toner particles in the method of the present invention will be described below, but the present invention is not limited to the description.

(Dissolution process)
A polymerizable monomer composition is prepared by mixing and stirring at least the surface of the polymerizable monomer that has been hydrophobized.

(Granulation process)
After the dissolving step, the polymerizable monomer composition is transferred to a granulation container. Here, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using a normal stirrer or disperser to obtain a polymerizable monomer composition dispersion.

  The addition of the polymerization initiator can be carried out at any time and required time after the granulation step, but the initiator efficiency should be completed before the polymerization conversion of the polymerizable monomer reaches 90%. Desirable in terms.

(Polymerization process)
After the granulation step, the polymerizable monomer composition dispersion is transferred to a polymerization vessel to carry out polymerization. In the polymerization step, the polymerizable monomer composition dispersion is stirred while maintaining a predetermined temperature to obtain a polymer fine particle dispersion. For the polymerization vessel, the same stirring means as that used for the granulation vessel can be used. The polymerization temperature is 40 ° C or higher, preferably 50 to 90 ° C.

  In the previous dissolving step and granulating step, the hydrophobizing agent adhering to the magnetic iron oxide surface without being chemically bonded is peeled off and eluted into the aqueous medium due to the shearing force of the stirrer or disperser. The eluted hydrophobizing agent acts as an emulsifier, and the polymerizable monomer released from the polymerizable monomer composition particles into the aqueous medium or the polymerizable monomer refluxed from the vapor into the aqueous medium is aqueous. Emulsify and stabilize in medium. If the emulsion-stabilized polymerizable monomer is allowed to stand, it will adhere to the inner wall of the polymerization vessel, the surface of the stirrer, etc., and polymerization will begin on the spot soon. In this way, many polymer deposits are generated in the polymerization vessel. In order to suppress emulsification of the polymerizable monomer, the alcohol is introduced into the polymerization container when the transfer of the polymerizable monomer composition dispersion liquid to the polymerization container is completed (this time is referred to as the start of polymerization). It is effective to add. The added alcohol has a function of demulsifying the emulsified and stabilized polymerizable monomer. Since the demulsified polymerizable monomer becomes unstable in the aqueous medium, it returns to the particles of the polymerizable monomer composition or evaporates and moves from the liquid phase to the gas phase.

  The alcohol to be added is preferably one having 1 to 4 carbon atoms and high hydrophilicity and soluble in an aqueous medium. When the number of carbon atoms is 5 or more, the solubility in water is reduced, and the carbon is not uniformly dispersed in the aqueous medium, and the emulsified alcohol cannot be efficiently demulsified. Examples of the alcohol having 4 or less carbon atoms include methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and allyl alcohol. Is mentioned.

  Furthermore, since the alcohol having a boiling point of 85 ° C. or more hardly evaporates during the polymerization step and stays in the aqueous medium, the emulsified polymerizable monomer can be efficiently demulsified. Examples of the alcohol having a boiling point of 85 ° C. or higher include allyl alcohol (97 ° C.), n-propyl alcohol (97 ° C.), n-butyl alcohol (boiling point 117 ° C.), iso-butyl alcohol (boiling point 108 ° C.), sec- Examples include butyl alcohol (boiling point: 100 ° C.) and n-pentanol (137.5 ° C.).

  Therefore, examples of the alcohol satisfying both of 1 to 4 carbon atoms and a boiling point of 85 ° C. or higher include allyl alcohol, n-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol and the like.

  Further, the amount of alcohol added at the start of the polymerization is determined to be emulsified if the polymerized monomer is contained in an aqueous medium in the range of 2100 ppm or more and 6000 ppm or less when the polymerization conversion rate of the polymerizable monomer reaches 30%. This is preferable because the demulsification of the monomer proceeds sufficiently. When the alcohol concentration in the aqueous medium is less than 2100 ppm, some of the emulsified polymerizable monomer is not de-emulsified due to the small amount of alcohol, and the emulsified and stabilized polymerizable monomer adheres to the inner wall of the polymerization vessel. And a polymer deposit. On the other hand, when the alcohol concentration in the aqueous medium exceeds 6000 ppm, the particle size distribution of the toner particles becomes broad and the yield decreases. This is considered to be because when the alcohol concentration in the aqueous medium is high, the alcohol is adsorbed on the dispersion stabilizer, so that the dispersion stability of the toner particles in the aqueous medium is impaired.

  Even if the conversion rate of the polymerizable monomer exceeds 30%, there are many unreacted polymerizable monomers in the aqueous medium until the conversion rate reaches 80%. Therefore, the alcohol concentration is 2100 ppm or more and 6000 ppm or less. Prepare alcohol by adding alcohol so that it is within the range. Until the conversion rate reaches 80%, it is more effective to suppress polymer deposits if alcohol is contained in the aqueous medium in the above concentration range. If it is less than 2100 ppm, the amount of alcohol in the aqueous medium is not sufficient to demulsify the polymerizable monomer whose emulsion has been stabilized, and if it exceeds 6000 ppm, the particle size distribution of the toner particles becomes broad.

  The gas phase part of the polymerization vessel during the polymerization process is usually provided with a vent pipe to prevent the internal pressure from rising, and is opened to the atmosphere. However, if the vapor containing the polymerizable monomer is discharged to the outside as it is, the yield is lowered. Therefore, it is generally performed that a condenser is provided in the vent pipe to condense the vapor and return it to the polymerization vessel. Yes.

  A part of the polymerizable monomer refluxed to the liquid phase part returns to the particles of the polymerizable monomer composition, and the other part is evaporated again to become a vapor. However, as described above, the emulsion treatment is stabilized in the aqueous medium by the hydrophobizing agent eluted into the aqueous medium, and eventually, it moves to the inner wall of the polymerization vessel, the surface of the stirring blade, the surface of the baffle plate, and the polymerization reaction on the spot And become a strong deposit. Therefore, in order to more effectively suppress the generation of polymer deposits, it is necessary to suppress vapor condensation and reflux in the vapor phase portion of the polymerization vessel.

  In order to prevent the decrease in yield and to suppress the condensation and reflux of steam, it is provided in the polymerization vessel until the polymerization conversion rate of the polymerizable monomer reaches at least 80%. It is preferable to introduce a carrier gas having a temperature of 40 ° C. or higher and 120 ° C. or lower into the gas phase portion from the carrier gas inlet. Until the polymerization conversion rate reaches 80%, a large amount of unreacted polymerizable monomer is present, and therefore measures to prevent vapor condensation are essential. If the temperature of the carrier gas is lower than 40 ° C., the temperature becomes lower than the polymerization temperature, so that vapor condensation cannot be prevented. Moreover, since it is too large with respect to polymerization temperature when it exceeds 120 degreeC, since it has a bad influence on control of polymerization temperature, it is not preferable.

  The carrier gas used here is one kind of gas selected from air, nitrogen and water vapor, or a mixed gas of two or more kinds. Any gas is suitable because it is inexpensive and safe and has little polymerization inhibition. If the polymerization inhibition is large, the polymerization conversion rate of the polymerizable monomer is decreased, and the amount of unreacted polymerizable monomer remaining in the toner particles is increased. If this toner particle is used as a toner, it may be felt as an odor, which is not preferable.

  The polymerizable monomer vapor taken out of the polymerization vessel along with the carrier gas is collected by the condenser in the middle of the vent pipe so as not to return to the polymerization vessel. The recovered polymerizable monomer can be used as a raw material for the next toner production in order to improve the yield.

(Distillation process)
In order to remove volatile components (volatile impurities) such as unreacted polymerizable monomers and by-products, a distillation step may be provided after the polymerization step to distill them off. The distillation step can be performed under normal pressure or reduced pressure.

  In order to remove the dispersion stabilizer attached to the surface of the polymer fine particles, the polymer fine particle dispersion can be treated with an acid or an alkali. Thereafter, the polymer fine particles are separated from the liquid phase by a known solid-liquid separation method, but in order to completely remove the acid or alkali and the dispersion stabilizer dissolved therein, water is again added to wash the polymer fine particles. . This process is repeated several times, and after sufficient washing, solid-liquid separation is performed again to obtain toner particles. The obtained toner particles are dried by a known drying means, and if necessary, a group of particles having a particle diameter outside the predetermined range is separated by classification. The separated particle group having a particle size outside the predetermined range may be reused to improve the final yield.

  The toner obtained by the present invention may be only the polymerized toner particles obtained by the above-described polymerization method, or may be a one-component developer obtained by externally adding other additives to the toner particles as necessary.

  As the polymerizable monomer suitably used in the present invention, styrene derivatives such as styrene and α-methylstyrene, and acrylic polymerizable monomers such as methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferable. Used for. Other examples include methacrylic polymerizable monomers such as methyl methacrylate and vinyl esters such as vinyl acetate and vinyl propionate. In the present invention, the above polymerizable monomers are used alone or in combination of two or more. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in combination, or in combination with other monomers from the viewpoints of development characteristics and durability of the toner.

  In order to polymerize the polymerizable monomer, a polymerization initiator can be used. In the present invention, an oil-soluble polymerization initiator is preferably used because it can be easily incorporated into the polymerizable monomer composition. Examples of the polymerization initiator that can be used in the present invention include organic peroxide initiators. Furthermore, the polymerization initiator is preferably a polymerization initiator having a 10-hour half-life temperature of 40 ° C. or more and less than 60 ° C. If the 10-hour half-life temperature is less than 40 ° C., it may be difficult to control the polymerization reaction, and the particle size distribution of toner particles tends to be broad, such as an increase in coarse particles. When the 10-hour half-life temperature is 60 ° C. or more, the progress of the polymerization reaction tends to be slow, and the monomer remaining for a long time tends to become fine particles. As a result, the particle size distribution of the toner particles tends to be broad.

  Examples of the polymerization initiator used in the present invention include t-butyl peroxylaurate, t-butyl peroxypivalate, succinic peroxide, diisopropyl peroxydicarbonate, and di-2-ethoxyethyl peroxydi. Organic peroxides such as carbonate, di-2-ethylhexyl peroxydicarbonate, and di-sec-butyl peroxydicarbonate are listed. Further, in the present invention, among peroxide-based initiators, those that generate alcohol as a decomposed product are preferably used because generation of polymer deposits can be suppressed. Among these, di-sec-butyl peroxydicarbonate is a product of decomposition of sec-butyl alcohol, which is produced as a decomposition product, by demulsifying a polymerizable monomer that has been emulsified and stabilized in an aqueous medium. Can be suppressed.

  The magnetic material used in the present invention also serves as a colorant. In the present invention, the magnetic substance contained in the polymerized toner particles includes iron oxides such as magnetite, hematite and ferrite, metals such as iron, cobalt and nickel, and these metals and aluminum, cobalt, copper, lead, magnesium and tin. , Zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium metal alloys, and mixtures thereof.

  These magnetic materials have an average particle diameter of 2 μm or less, preferably about 0.1 to 0.5 μm. The content of the magnetic substance in the toner particles is 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer. good.

  In order to improve the dispersibility of these magnetic substances in the toner particles, the surface of the magnetic iron oxide is hydrophobized in the present invention. For the hydrophobization treatment, coupling agents such as a silane coupling agent and a titanium coupling agent are used, and among them, a silane coupling agent is preferably used. As silane coupling agents, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, Examples include dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, and n-octadecyltrimethoxysilane.

  As the release agent used in the present invention, a wax in a solid state at room temperature is preferable in terms of toner blocking resistance, durability of a large number of sheets, low-temperature fixability, and offset resistance. In order to improve the translucency of the image fixed on the OHP, a linear ester wax is particularly preferably used.

  The toner produced according to the present invention may contain a charge control agent. The charge control agent can be externally added to the toner particles, but can also be added inside the toner particles by dispersion in the polymerizable monomer composition or the like.

  For example, when a polymerizable monomer is polymerized, various crosslinking agents can be used. Examples of the crosslinking agent include divinylbenzene, 4,4′-divinylbiphenyl, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1, Polyfunctional compounds such as 6-hexanediol diacrylate can be mentioned.

  As a dispersion stabilizer for satisfactorily dispersing a polymerizable monomer composition in an aqueous medium, generally, a water-soluble polymer that forms a protective colloid layer and develops repulsive force due to steric hindrance, and electrostatic repulsion It is broadly classified into hardly water-soluble inorganic compounds that develop force and stabilize dispersion. Since the fine particles of the hardly water-soluble inorganic compound are dissolved by an acid or an alkali, they can be easily removed by washing with an acid or an alkali after polymerization, and thus are preferably used in the present invention. Among the hardly water-soluble inorganic compounds, metal phosphates such as aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate and zinc phosphate are preferably used. Furthermore, alkaline earth metal phosphates such as calcium phosphate are preferred. For example, in the case of tricalcium phosphate, a dispersion stabilizer suitable for the suspension polymerization method can be obtained by charging and mixing a trisodium phosphate aqueous solution and a calcium chloride aqueous solution with sufficient stirring.

  In the case of a polymerization method using an aqueous medium such as suspension polymerization, the inclusion of a release agent can be promoted by adding a polar resin to the polymerizable monomer composition. When a polar resin is present in the polymerizable monomer composition suspended in the aqueous medium, the polar resin moves to the vicinity of the interface between the aqueous medium and the polymerizable monomer composition due to the difference in affinity for water. Therefore, the polar resin is unevenly distributed on the surface of the toner particles. As a result, the toner particles have a core-shell structure, and the inclusion property of the release agent is improved even when a large amount of the release agent is contained.

  In addition, if a polar resin with a high melting temperature is selected for the shell, even if the binder resin is designed to be melted at a lower temperature for the purpose of fixing at low temperatures, the occurrence of harmful effects such as blocking during storage is suppressed. can do. As such a polar resin, since the fluidity of the polar resin itself can be expected when it is unevenly distributed on the surface of the toner particles to form a shell, a saturated or unsaturated polyester resin is particularly preferable.

  In the production method of the present invention, an external additive can be used for the purpose of imparting various properties to the toner. The external additive preferably has a particle size of 1/10 or less of the average particle size of the toner particles from the viewpoint of durability when added to the toner. Examples of the external additive include aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide and other metal oxides, nitrides such as silicon nitride, carbides such as silicon carbide, Inorganic metal salts such as calcium sulfate, barium sulfate and calcium carbonate, fatty acid metal salts such as zinc stearate and calcium stearate, carbon black, silica and the like are used.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited at all by these. Each measurement and evaluation method is shown below.

(1) Polymerization Conversion Rate of Polymerizable Monomer The polymerization conversion rate of the polymerizable monomer was determined by measuring the amount of unreacted styrene in the toner particles by gas chromatography (GC) as follows. calculate.

  In the polymerization step, a dispersion of the polymerizable monomer composition is sampled, and about 0.4 g is precisely weighed and placed in a sample bottle. About 15 g of acetone precisely weighed is added to the lid, mixed well, and mixed well. A tabletop ultrasonic cleaner having an oscillation frequency of 42 kHz and an electric output of 125 W (for example, “B2510J-MTH”, manufactured by Branson) ) For 30 minutes. Thereafter, filtration is performed using a solvent-resistant membrane filter “Maysho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm, and 2 μl of the filtrate is analyzed by gas chromatography. Then, the amount of unreacted styrene is calculated with a calibration curve prepared in advance using styrene, and the polymerization conversion rate is measured by the ratio with the total amount of styrene extracted with acetone.

The measurement apparatus and measurement conditions are as follows.
GC: HP 6890GC
Column: HP INNOWax (200 μm × 0.40 μm × 25 m)
Carrier gas: He (constant pressure mode: 20 psi)
Oven: (1) Hold at 50 ° C. for 10 minutes, (2) Temperature rise to 200 ° C. at 10 ° C./minute, (3) Hold at 200 ° C. for 5 minutes Inlet: 200 ° C., pulsed splitless mode (20 → 40 psi, until 0.5 min)
Split ratio: 5.0: 1.0
Detector: 250 ° C. (FID)

(2) Alcohol concentration in aqueous medium The amount of alcohol in the aqueous medium is measured by the same gas chromatography (GC) as in (1) above.

  In the polymerization step, a dispersion of the polymerizable monomer composition is sampled, and solid-liquid separation is performed by vacuum filtration. About 2.0 g of filtrate is precisely weighed and placed in a sample bottle. About 15 g of precisely weighed acetone is added to this and the lid is capped, mixed well, and irradiated with ultrasonic waves for 30 minutes using the same ultrasonic cleaner as in (1). Thereafter, filtration is performed using a solvent-resistant membrane filter “Maysho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm, and 2 μl of the filtrate is analyzed by gas chromatography. Then, the alcohol is quantified using a calibration curve prepared in advance using the target alcohol.

  The measurement apparatus and measurement conditions are the same as (1).

(3) Measurement of amount of polymer deposit In order to quantify the amount of polymer deposit, a test piece of the same material as the inner wall of the vessel is placed on the inner wall of the polymerization vessel. The test piece is made of glass lining, and has a size of about 10 cm in length, about 5 cm in width, and about 1 mm in thickness. Five test pieces are installed in the polymerization container, and after toner particle production (3 batches), the test piece is removed from the polymerization container, immersed in water, washed lightly, dried, and weighed. The difference from the weight of the test piece before manufacturing the toner particles is taken, and the total weight change amount of the five test pieces is taken as the amount of polymer deposit.
A: Very good level (the amount of polymer deposit is less than 0.2 g)
B: Good level (the amount of polymer deposit is 0.2 g or more and less than 0.7 g)
C: Level with no problem (the amount of polymer deposit is 0.7 g or more and less than 1.5 g)
D: Acceptable level (the amount of polymer deposit is 1.5 g or more and less than 3.5 g)
E: Bad level (polymer deposit amount is 3.5 g or more)

(4) Evaluation of sharpness of particle size distribution As a measuring device, a precision particle size measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electric resistance method equipped with a 100 μm aperture tube. Is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Disposition System Tetora 150” (manufactured by Nikkei Bios) with an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4), volume and number-based median diameter are calculated. When the graph / volume% is set by the dedicated software, the “average diameter” on the “analysis / volume statistics (arithmetic average)” screen is the weight average particle diameter (D4), and the “median diameter” is The volume-based median diameter (Dv50). The “median diameter” on the “analysis / number statistical value (arithmetic mean)” screen when the graph / number% is set in the dedicated software is the number-based median diameter (Dn50).
(8) Using each calculated median diameter, the sharpness of the particle size distribution was determined by the following formula.
Sharpness of particle size distribution = volume-based median diameter (Dv50) ÷ number-based median diameter (Dn50)

The closer the value of the above formula is to 1, the sharper the particle size distribution.
A: Very good level (Dv50 / Dn50 value is less than 1.12)
B: Good level (Dv50 / Dn50 value is 1.12 or more and less than 1.16)
C: No problem level (Dv50 / Dn50 value is 1.16 or more and less than 1.20)
D: Permissible level (Dv50 / Dn50 value is 1.20 or more and less than 1.24)
E: Bad level (Dv50 / Dn50 value is 1.24 or more)

(4) High temperature offset The offset temperature was determined by passing a solid image (toner amount of 1.05 to 1.15 mg / cm ² ) having an area of 5 cm × 5 cm in the center of the front end of the recording material. At this time, a hot offset phenomenon (a phenomenon in which a part of the fixed image adheres to the surface of the fixing device and is fixed on the recording material in the next round) occurs at the rear end of the recording material in the sheet passing direction. The temperature of the surface of the fixing heating part was measured. The above temperature was defined as the hot offset phenomenon occurrence temperature, and was evaluated based on the following evaluation criteria.
A: Very good level (over 190 ° C)
B: Good level (185 ° C. or higher and lower than 190 ° C.)
C: Level with no problem (180 ° C or higher and lower than 185 ° C)
D: Acceptable level (175 ° C or higher and lower than 180 ° C)
E: Bad level (below 175 ° C)

<Example 1>
After adding 451 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 709 parts by mass of ion-exchanged water and heating to 60 ° C., 67.7 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution is gradually added. Then, an aqueous medium containing Ca ₃ (PO ₄ ) ₂ was prepared in a granulation vessel.

(Dissolution process)
The following formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.).
Styrene 74 parts by mass n-butyl acrylate 26 parts by mass Saturated polyester resin (1) 3 parts by mass (monomer composition; bisphenol A propylene oxide adduct / terephthalic acid / isophthalic acid, acid value; 7 mg KOH / g, Tg (glass Transition temperature) = 69 ° C., Mn (number average molecular weight) = 4200, Mw (weight average molecular weight) = 9000)
Negative charge control agent 2 parts by mass (T-77; monoazo dye-based Fe compound (Hodogaya Chemical Co., Ltd.))
・ 90 parts by mass of magnetic material (prepared by adding 1.2 parts by mass of silane coupling agent n-C ₈ H ₁₇ Si (OC ₂ H ₅ ) ₃ to 100 parts by mass of magnetic iron oxide. Number average particle size: 0 .28Myuemu, saturation magnetization and the residual magnetization in a magnetic field 79.6 kA / m (1000 ^{oersted); 67.6Am 2 /kg(emu/g),3.9Am 2 / kg} (emu / g))
The above dispersion was heated to 60 ° C., and 18 parts by mass of HNP-9 (polyethylene wax, DSC endothermic main peak = 78 ° C.) mixed and dissolved therein were mixed and dissolved therein. Got.

(Granulation process)
The polymerizable monomer composition is charged into the aqueous medium, and granulated by dispersing at 7,000 rpm for 15 minutes in Claremix (M Technique Co., Ltd.) at 60 ° C. in an N ₂ atmosphere. A monomer composition dispersion was obtained. Further, 7 parts of di-sec-butyl peroxydicarbonate as a polymerization initiator was charged into the granulation container 5 minutes after the start of granulation.

(Polymerization process)
The polymerizable monomer composition dispersion is transferred from the granulation vessel to the polymerization vessel, and when the transfer is completed (at the start of the polymerization process), sec-butyl alcohol is added at 2600 ppm with respect to the amount of water in the aqueous medium. did. A test piece for measuring the amount of polymer deposits was previously placed on the inner wall of the polymerization vessel. The temperature of the polymerizable monomer composition dispersion was adjusted to 70 ° C. and polymerized by stirring for 5 hours with a full zone blade (manufactured by Shinko Pantech Co., Ltd.).

  When the polymerization conversion rate of the polymerizable monomer composition was 30%, the sec-butyl alcohol concentration in the aqueous medium was measured and found to be 3000 ppm. This concentration is considered to be the total concentration of sec-butyl alcohol produced as a decomposition product of the polymerization initiator and sec-butyl alcohol added at the start of the polymerization process. Further, sec-butyl alcohol was additionally added when the polymerization conversion rate was 50%, and the sec-butyl alcohol concentration in the aqueous medium was 3200 ppm when the polymerization conversion rate was 80%. Further, nitrogen gas adjusted to 70 ° C. was introduced into the gas phase part in the polymerization vessel until the polymerization conversion rate of the polymerizable monomer reached 80%. Thereby, the vapor | steam in a superposition | polymerization container was accompanied with nitrogen, and was exhausted out of the superposition | polymerization container from vent piping. The exhausted steam was condensed by a condenser in the middle of the vent pipe and recovered so as not to return to the polymerization vessel.

(Particle cleaning / solid-liquid separation / drying)
Hydrochloric acid was added to the obtained polymer fine particle dispersion and stirred to dissolve the tricalcium phosphate covering the polymer fine particles, followed by solid-liquid separation with a pressure filter to obtain polymer fine particles. This was put into water and stirred to obtain a dispersion again, followed by solid-liquid separation with the above-mentioned filter. After redispersion of polymer fine particles in water and solid-liquid separation are repeated until the tricalcium phosphate is sufficiently removed, the solid-liquid separated polymer fine particles are finally sufficiently removed by an air-flow dryer. And dried to obtain toner particles. The particle size distribution of the obtained toner particles was measured. The evaluation results of the measured values are shown in Table 1.

  Furthermore, a hydrophobic silica fine powder was externally added to the obtained toner particles to obtain a toner (one-component developer). Using this toner, high temperature offset evaluation was performed. The evaluation results are also shown in Table 1.

(Measurement of polymer deposits)
After the toner particles were manufactured, the same toner particles were manufactured twice using the same polymerization container. A total of three times, after passing through the polymerization step, the test piece installed in the polymerization vessel was removed and weighed. The state of polymer adhesion in the polymerization vessel was evaluated from the amount of change in the weight of the test piece. The evaluation results are shown in Table 1.

<Example 2>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 2600 ppm of n-propyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Thereafter, the alcohol concentration in the aqueous medium (concentration of n-propyl alcohol and sec-butyl alcohol) was measured when the polymerization conversion rate of the polymerizable monomer was 30% and found to be 3000 ppm. Furthermore, sec-butyl alcohol was additionally added when the polymerization conversion was 50%, and the alcohol concentration in the aqueous medium was 3200 ppm when the polymerization conversion was 80%. Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 3>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 2600 ppm of n-butyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Thereafter, the alcohol concentration in the aqueous medium (concentration of n-butyl alcohol and sec-butyl alcohol) was measured when the polymerization conversion rate of the polymerizable monomer was 30%, and was 3000 ppm. Furthermore, sec-butyl alcohol was additionally added when the polymerization conversion was 50%, and the alcohol concentration in the aqueous medium was 3200 ppm when the polymerization conversion was 80%. Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 4>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, nitrogen gas adjusted to 120 ° C. was introduced into the gas phase portion in the polymerization vessel until the polymerization conversion rate of the polymerizable monomer reached 80%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 5>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, nitrogen gas adjusted to 40 ° C. was introduced into the gas phase in the polymerization vessel until the polymerization conversion rate of the polymerizable monomer reached 80%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 6>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, nitrogen gas adjusted to 130 ° C. was introduced into the gas phase in the polymerization vessel until the polymerization conversion rate of the polymerizable monomer reached 80%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 7>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, nitrogen gas adjusted to 35 ° C. was introduced into the gas phase in the polymerization vessel until the polymerization conversion rate of the polymerizable monomer reached 80%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 8>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, nitrogen gas adjusted to 70 ° C. was introduced into the gas phase in the polymerization vessel until the polymerization conversion rate of the polymerizable monomer reached 70%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 9>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 5650 ppm of sec-butyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Then, when the polymerization conversion rate of the polymerizable monomer was 30%, the sec-butyl alcohol concentration in the aqueous medium was measured and found to be 6000 ppm. Similarly, when the polymerization conversion was 80%, the sec-butyl alcohol concentration in the aqueous medium was measured, and it was 5600 ppm. Alcohol was not added except at the start of polymerization.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 10>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 5600 ppm of sec-butyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Then, when the polymerization conversion rate of the polymerizable monomer was 30%, the sec-butyl alcohol concentration in the aqueous medium was measured and found to be 6000 ppm. Further, sec-butyl alcohol was additionally added when the polymerization conversion rate was 50%, and the sec-butyl alcohol concentration in the aqueous medium was adjusted to 6000 ppm when the polymerization conversion rate was 80%. Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 11>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 5600 ppm of sec-butyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Then, when the polymerization conversion rate of the polymerizable monomer was 30%, the sec-butyl alcohol concentration in the aqueous medium was measured and found to be 6000 ppm. Further, sec-butyl alcohol was additionally added at a polymerization conversion rate of 50%, and the sec-butyl alcohol concentration in the aqueous medium was adjusted to 6100 ppm when the polymerization conversion rate was 80%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 12>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 1700 ppm of sec-butyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Thereafter, when the polymerization conversion rate of the polymerizable monomer was 30%, the sec-butyl alcohol concentration in the aqueous medium was measured and found to be 2100 ppm. Furthermore, sec-butyl alcohol was additionally added at a polymerization conversion rate of 50%, and the sec-butyl alcohol concentration in the aqueous medium was adjusted to 3200 ppm when the polymerization conversion rate was 80%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 13>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 1700 ppm of sec-butyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Thereafter, when the polymerization conversion rate of the polymerizable monomer was 30%, the sec-butyl alcohol concentration in the aqueous medium was measured and found to be 2100 ppm. Furthermore, sec-butyl alcohol was additionally added when the polymerization conversion rate was 50%, and the sec-butyl alcohol concentration in the aqueous medium was adjusted to 2100 ppm when the polymerization conversion rate was 80%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 14>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 1700 ppm of sec-butyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Thereafter, when the polymerization conversion rate of the polymerizable monomer was 30%, the sec-butyl alcohol concentration in the aqueous medium was measured and found to be 2100 ppm. Furthermore, sec-butyl alcohol was additionally added at a polymerization conversion rate of 50%, and the sec-butyl alcohol concentration in the aqueous medium was adjusted to 2000 ppm when the polymerization conversion rate was 80%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 15>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 1600 ppm of sec-butyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Then, when the polymerization conversion rate of the polymerizable monomer was 30%, the sec-butyl alcohol concentration in the aqueous medium was measured and found to be 2000 ppm. Furthermore, sec-butyl alcohol was additionally added at a polymerization conversion rate of 50%, and the sec-butyl alcohol concentration in the aqueous medium was adjusted to 3200 ppm when the polymerization conversion rate was 80%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Example 16>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 5800 ppm of sec-butyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Thereafter, when the polymerization conversion rate of the polymerizable monomer was 30%, the sec-butyl alcohol concentration in the aqueous medium was measured and found to be 6100 ppm. When the polymerization conversion was 80%, the alcohol concentration in the aqueous medium was measured in the same manner, and it was 5700 ppm. Alcohol was not added except at the start of polymerization.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Comparative Example 1>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, no alcohol was added at the start of polymerization. When the polymerization conversion rate of the polymerizable monomer was 30%, the sec-butyl alcohol concentration in the aqueous medium was measured and found to be 400 ppm. Furthermore, when the polymerization conversion rate was 80%, the alcohol concentration in the aqueous medium was measured, and it was 300 ppm.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Comparative example 2>
Toner particles were produced in the same manner as in Example 1 except that the granulation step and the polymerization step were performed as follows.

  In the granulation step, 20 parts of di-sec-butyl peroxydicarbonate as a polymerization initiator was charged into the granulation container 5 minutes after the start of granulation.

  In the polymerization step, no alcohol was added at the start of polymerization. Then, when the polymerization conversion rate of the polymerizable monomer was 30%, the sec-butyl alcohol concentration in the aqueous medium was measured and found to be 1400 ppm. Further, when the polymerization conversion was 80%, the alcohol concentration in the aqueous medium was similarly measured, and it was 1100 ppm.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Comparative Example 3>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 2600 ppm of tert-butyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Then, when the polymerization conversion rate of the polymerizable monomer was 30%, the alcohol concentration in the aqueous medium (the total concentration of tert-butyl alcohol and sec-butyl alcohol) was measured and found to be 3000 ppm. Furthermore, tert-butyl alcohol was additionally added at a polymerization conversion rate of 50%, and the alcohol concentration in the aqueous medium was adjusted to 3200 ppm when the polymerization conversion rate was 80%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

<Comparative example 4>
Toner particles were produced in the same manner as in Example 1 except that the polymerization step was performed as follows.

  In the polymerization step, 2600 ppm of n-pentyl alcohol was added to the amount of water in the aqueous medium at the start of polymerization. Thereafter, the alcohol concentration in the aqueous medium (concentration of n-pentyl alcohol and sec-butyl alcohol) measured at a polymerization conversion rate of 30% of the polymerizable monomer was 3000 ppm. Furthermore, n-pentyl alcohol was additionally added at a polymerization conversion rate of 50%, and the alcohol concentration in the aqueous medium was adjusted to 3200 ppm when the polymerization conversion rate was 80%.

  Table 1 shows the evaluation results of the obtained toner particles and the evaluation results of the polymer adhesion state in the polymerization container.

Claims (4)

(I) a polymerizable monomer, a magnetic material hydrophobic treatment is applied to the surface, a polymerizable monomer composition containing in addition to the aqueous medium, the particles of the polymerizable monomer composition A granulating step to form;
(Ii) and Ru polymerization process by polymerizing polymerizable monomer contained in the particles,
A method for producing a polymerized toner having
The beginning of the polymerization process, in aqueous medium, the production method of polymerized toner, which comprises adding alcohol to 4 and boiling points 8 5 ° C. The number 1 or more carbon atoms. The concentration of 4 or less and a boiling point 85 ° C. or more alcohols the one or more carbon atoms in the said aqueous medium, wherein the polymerizable monomer polymerization conversion of 30% at the time of, billed Ru der within 6000ppm following range of 2100ppm Item 2. A method for producing a polymerized toner according to Item 1. Wherein until the polymerization conversion of the polymerizable monomer reaches 80% by adding the number 1 to 4 and a boiling point 85 ° C. or higher alcohol carbon in the aqueous medium, wherein during the aqueous medium The method for producing a polymerized toner according to claim 1 or 2, wherein the concentration of the alcohol having 1 to 4 carbon atoms and a boiling point of 85 ° C or higher is set to 2100 ppm or more and 6000 ppm or less. The polymerization apparatus et al is used when causing the polymerizable monomer is polymerized has a polymerization vessel,
The In the polymerization vessel, wherein the liquid phase of the aqueous medium with particles of the polymerizable monomer composition, and the gas phase, is formed,
The polymerization vessel has a vent pipe for evacuating the gas phase portion, and the inlet of the carrier gas, and
Wherein until the polymerization conversion of the polymerizable monomer reaches 80% while introducing 40 ° C. or higher 120 ° C. or less under a carrier gas to the gas phase portion, the volatile components generated in the gas phase portion the method for producing a polymerized toner according to Izu Re or one of 請 Motomeko 1-3 you exhaust from the vent pipe.