JP5506310B2 - Method for producing polymerized toner - Google Patents

Description

  The present invention relates to a method for producing a polymerized toner used in electrophotography.

  As a method for producing toner particles, there is a polymerization method in which a colorant and a charge control agent are included in polymer particles at the stage of polymerizing a polymerizable monomer to form toner particles. For example, in the suspension polymerization method, a polymerizable monomer, a colorant, a release agent and a polymerization initiator, and if necessary, a cross-linking agent, a charge control agent and other additives are uniformly dissolved or dispersed to be polymerizable. A monomer composition is used. This is dispersed in an aqueous medium containing a dispersion stabilizer using an appropriate stirrer, and the polymerizable monomer is polymerized to obtain a suspension of toner particles having a desired particle size. If necessary, the suspension is treated with an acid or alkali to remove the dispersion stabilizer from the surface of the toner particles, and then the aqueous medium is separated in a solid-liquid separation step to obtain toner particles. When it is necessary to further reduce the water content, water is removed from the toner particles by a known drying means.

  The toner particles obtained by these methods that do not depend on the mechanical grinding method are spherical and have a uniform surface. Therefore, the fluidity and transferability are good, and good development characteristics are exhibited even when continuous development is carried out many times, the stress on the toner is small, and the occurrence of filming on the photoreceptor is small. Further, the particle size distribution of the obtained toner particles is sharp, and the yield of toner particles having a desired particle size is high even when a classification step is required.

  In the production of the toner by the suspension polymerization method described above, the polymerization step is usually carried out using a polymerization vessel having a stirring means and a heating / cooling means. When the composition adheres, it polymerizes in situ and becomes a polymer deposit. The polymer deposit remains in the polymerization vessel even after the completion of the polymerization process. 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, when this polymer deposit is peeled off and dropped and mixed into the product toner, it is observed as irregular shaped particles. If the proportion of irregularly shaped particles in the toner increases, the toner characteristics such as triboelectric chargeability and the development characteristics when the image is evaluated are adversely affected, and the product properties are degraded, such as fluctuations in image density, white streaks, and fogging. This is not preferable.

  Further, when the polymer deposit grows to a sufficient size and is peeled / dropped off, it may cause clogging or sticking in a piping part or a valve connected to the polymerization container. For this reason, the frequent removal operation | work of a deposit | attachment is needed and the fall of the operation rate of a manufacturing apparatus is caused. Furthermore, when the inside of the polymerization vessel is subjected to a surface treatment such as glass lining or fluororesin coating, the treatment surface may be damaged by a work such as chipping, and a repair work may be required. These results in an increase in the cost of the product toner.

  Several methods for efficiently removing the generated polymer deposit have been proposed. For example, a method of spraying a removing agent such as an organic solvent or an alkaline aqueous solution in a polymerization vessel, or filling the polymerization vessel and using heating and stirring together is simple and common. Various removing agents are used. For example, Patent Document 1 uses a mixture of dimethylformamide, dimethyl sulfoxide, or methyl ethyl ketone and hydrogen peroxide solution, and Patent Document 2 uses triethylene glycol after washing with acetic anhydride. Patent Document 3 uses primary or secondary amines, Patent Document 4 uses potassium hydroxide or sodium hydroxide aqueous solution, and Patent Document 5 uses N-methylpyrrolidone. However, in any of these methods, the main point is how well the polymer deposit is dissolved or swollen in the liquid, and it takes a long time to remove all the deposit even if it is heated. In addition, since the used removal agent is significantly contaminated by the deposits, it is not suitable for reuse as it is, resulting in a large amount of waste liquid being discharged, or it is necessary to take a large regeneration means for the removal agent.

  Since it is difficult to remove the polymer deposit once generated as described above, a method for preventing the polymer deposit itself has also been proposed. For example, as described in Patent Document 6, a method has been proposed in which water or a dispersion medium is sprayed on the gas phase part of the polymerization vessel at a wide angle by spraying. In this method, a stirrer shaft or When other apparatus members such as baffle plates and nozzles are present, there are portions where spraying is not performed, and it is difficult to adjust the spray intensity appropriately for the spray target. For this reason, sufficient effects cannot be obtained such as insufficient cleaning or conversely encouraging splashing of the liquid to enlarge the adhesion area. Also, this method can hardly be expected to prevent the polymer deposits generated in the liquid phase part.

Japanese Patent Laid-Open No. 9-3119 JP-A-8-48997 JP-A-5-295393 Japanese Patent Publication No.49-38033 JP-A-47-2943 JP-A-10-153878

  The present invention provides a method for producing a polymerization method toner that does not generate polymer deposits on the inner wall of the polymerization vessel, the surface of the stirring means, and the surface of the baffle plate in the polymerization step of the toner production method by the suspension polymerization method. Objective.

The present inventors pay attention to the mechanism of the formation of polymer deposits during the polymerization process, and the polymerizable monomer vaporized during the polymerization process condenses in the gas phase in the polymerization vessel, which is the inner wall of the polymerization vessel and stirring. After moving to the machine surface and polymerizing there, it was clarified that the polymer deposits grew from this, and as a result of intensive studies based on this knowledge, the following method was found.
(1) polymerizable monomer and the polymerizable monomer composition having containing a colorant is added to the aqueous medium, in aqueous medium to form particles of the polymerizable monomer composition, polymerizable Single the polymerizable monomer contained in the particles of the dimeric composition by polymerizing a method for producing the toner particles to obtain toner particles,
The polymerization temperature when polymerizing the polymerizable monomer is 50 ° C. or more and 90 ° C. or less,
A polymerization apparatus in which polymerization of the polymerizable monomer is performed has a polymerization container,
In the polymerization vessel,
A liquid phase part of an aqueous medium having particles of the polymerizable monomer composition;
The gas phase ,
Formed,
In the polymerization vessel ,
Vent pipe for evacuating the gas phase portion, and,
Carrier gas introduction piping is provided,
Until the polymerization conversion of the polymerizable monomers reaches at least 80%, in the gas phase portion, the temperature is introducing a carrier gas is 120 ° C. or less 40 ° C. or higher, and, in the polymerization vessel A method for producing a polymerized toner, characterized in that gas is exhausted from a vent pipe.
(2) the carrier gas, air, a manufacturing method of the polymerized toner according to the nitrogen Oyo Ru one gas or a mixture of two or more gases der of beauty gas selected from the group consisting of water vapor (1) .
(3) and the temperature at which the carrier gas is introduced into the polymerization vessel,
And the polymerization temperature of the polymerizable monomer,
Method for producing a polymerized toner according to the temperature difference is, Ru der within 10 ° C. (1) or (2).
And (4) the flow rate F of the carrier gas introduced into the polymerization vessel (m ³ / h),
And the volume V (m ³⁾ of the gas phase portion,
Method for producing a polymerized toner according to any one of the relationships, to satisfy 0.002 ≦ (V / F) ≦ 0.100 (1) ~ (3).
(5) The method of producing polymerized toner according to any one of the polymerization the gas phase portion formed in the container you heated by an external jacket (1) to (4).
(6) and the internal temperature of the outer jacket,
And the polymerization temperature of the polymerizable monomer,
Method for producing a polymerized toner according to the temperature difference, Ru der within 10 ° C. (5) of the.

  According to the present invention, it is possible to prevent the generation of polymer deposits generated in the polymerization container in the polymerization process during suspension polymerization method toner production, so that irregular shaped particles caused by the polymer deposits are mixed into the product toner. Can be prevented. For this reason, when image formation is performed, there is no fluctuation in image density or density unevenness, and a clear and excellent fixing toner can be obtained. In addition, there is no obstruction of heat conduction due to accumulated polymer deposits, and no clogging of pipes due to dropping of polymer deposits. Therefore, frequent removal of polymer deposits is essentially unnecessary, improving productivity. To do.

It is the schematic which shows an example of the superposition | polymerization apparatus used for the superposition | polymerization process of this invention. It is the schematic which shows another example of the superposition | polymerization apparatus used for the superposition | polymerization process of this invention.

  The present invention can be suitably used for a method for producing toner particles by suspension polymerization. In the suspension polymerization method, a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is added to an aqueous medium, the polymerizable monomer composition is granulated in the aqueous medium, and the polymerizable monomer composition is granulated. In this method, toner particles are obtained by forming particles of a monomer composition and polymerizing a polymerizable monomer contained in the particles of the polymerizable monomer composition.

  The method for producing the toner of the present invention by the suspension polymerization method will be described below.

(Polymerizable monomer composition preparation process)
A polymerizable monomer composition containing at least a polymerizable monomer and a colorant is prepared. The colorant may be dispersed in the polymerizable monomer in advance with a medium stirring mill or the like and then mixed with another composition, or may be dispersed after mixing all the compositions.

(Granulation process)
The polymerizable monomer composition is put into an aqueous medium containing a dispersion stabilizer, and granulated by dispersing the polymerizable monomer composition to form particles of the polymerizable monomer composition in the aqueous medium. A composition dispersion is obtained. The granulation step can be performed, for example, in a vertical stirring tank provided with a stirrer having a high shearing force. As a stirrer having a high shearing force, Ultra Tarrax (manufactured by IKA), T.I. K. Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) K. Commercially available products such as Philmix (manufactured by Special Machine Engineering Co., Ltd.) and Claremix (manufactured by M Technique Co., Ltd.) can be used.

(Polymerization process)
By polymerizing the polymerizable monomer in the polymerizable monomer composition dispersion obtained by the granulation step, a polymer fine particle dispersion is obtained. In the polymerization step in the present invention, a general polymerization vessel having a stirring means and adjustable in temperature can be used.

  The polymerization temperature is 40 ° C. or higher, generally 50 to 90 ° C. The polymerization temperature may be constant throughout, but may be raised in the latter half of the polymerization step for the purpose of obtaining a desired molecular weight distribution. Any stirring means may be used as the stirring means used in the polymerization vessel as long as the dispersed polymerizable monomer composition is floated without stagnation and the temperature in the tank can be kept uniform. As the stirring means, a stirring blade is suitable, and examples thereof include the following. General agitation blades such as paddle blades, inclined paddle blades, three retracted blades, propeller blades, disk turbine blades, helical ribbon blades, anchor blades, full zone (made by Shinko Pantech), twin star (made by Shinko Pantech) ), Max Blend (manufactured by Sumitomo Heavy Industries), Supermix (manufactured by Satake Chemical Machinery Co., Ltd.), Hi-F mixer (manufactured by Soken Chemical Co., Ltd.).

  As shown in FIG. 1, there are usually a liquid phase part and a gas phase part in the polymerization vessel 1 during the polymerization process, and a vapor mainly composed of an aqueous medium and a polymerizable monomer exists in the gas phase part. To do. In order to prevent the internal pressure from rising in the polymerization vessel gas phase during the polymerization process, it is common to provide a vent pipe 5 to open the atmosphere. However, if the vapor containing the polymerizable monomer is discharged to the outside as it is, the yield is lowered. Therefore, a condenser 6 is provided in the vent pipe to condense the vapor and return it to the polymerization vessel. . In addition, it is normal that no temperature adjusting means is installed in the gas phase part of the polymerization vessel, and since the surface temperature is lower than the temperature of the liquid phase part, the amount of vapor condensed in this part is large, Reflux to the liquid phase. A part of the polymerizable monomer condensed and 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. It moves to the inner wall of the polymerization vessel, the surface of the stirring blade, and the surface of the baffle plate, and undergoes a polymerization reaction on the spot to form a strong deposit. Therefore, in order to prevent the generation of deposits, it is necessary to suppress the condensation and reflux of the vapor in the gas phase part of the polymerization vessel.

  For this purpose, a carrier gas having a temperature of 40 ° C. or more and 120 ° C. or less is introduced into the gas phase part until the polymerization conversion rate of the polymerizable monomer reaches at least 80%. 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., it becomes lower than the general polymerization temperature, so that vapor condensation cannot be prevented. Moreover, since it is too large with respect to general polymerization temperature when it exceeds 120 degreeC, since it has a bad influence with respect to control of polymerization temperature, it is unpreferable. Furthermore, it is more preferable that the temperature difference between the polymerization temperature and the carrier gas is within 10 ° C., because condensation of vapor can be sufficiently prevented and the polymerization temperature is not affected. The introduction of the carrier gas can be performed continuously or intermittently. However, when the carrier gas is intermittently introduced, the time during which the carrier gas is introduced reaches 80% of the polymerization conversion rate of the polymerizable monomer. It is desirable that it does not become less than 90% of the entire time until. If this time is less than 90%, the time during which the vapor stays in the gas phase portion of the polymerization vessel becomes longer, and the possibility of condensation and reflux increases.

  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 accompanying the carrier gas and taken out of the polymerization vessel is condensed by a condenser in the middle of the vent pipe and recovered 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.

The relationship between the flow rate F (m ³ / h) at which the carrier gas is introduced into the polymerization vessel and the volume V (m ³ ) of the polymerization vessel gas phase portion preferably satisfies 0.002 ≦ V / F ≦ 0.100. . If V / F is less than 0.002, the carrier gas flow rate with respect to the volume of the polymerization vessel gas phase is too large, and the amount of heat introduced becomes too large, which may affect the polymerization temperature. On the other hand, when V / F is larger than 0.100, the carrier gas flow rate is not sufficient, so that it is impossible to prevent vapor condensation in the gas phase.

  In order to prevent vapor condensation in the polymerization vessel gas phase, it is also preferable to provide a jacket (7 in FIG. 1) that can be heated from the outside in the polymerization vessel gas phase. By heating from the outside with a jacket, the temperature of the inner wall of the polymerization vessel gas-phase part rises, and condensation of vapor in contact therewith can be prevented. It is more preferable that the temperature difference between the internal temperature of the outer jacket and the polymerization temperature is within 10 ° C., because condensation of vapor can be sufficiently prevented and the polymerization temperature is not affected.

(Distillation process)
If necessary, in order to remove volatile impurities such as unreacted polymerizable monomers and by-products, a part of the aqueous medium may be distilled off after the polymerization. The distillation step can be performed under normal pressure or reduced pressure.

(Washing process, solid-liquid separation process and drying process)
In order to remove the dispersion stabilizer adhering to the surface of the polymer particles, the polymer particle dispersion can be treated with an acid or an alkali. Thereafter, the polymer particles are separated from the liquid phase by a general solid-liquid separation method. However, in order to completely remove the acid or alkali and the dispersion stabilizer component dissolved therein, water is added again to remove the polymer particles. Wash. This washing 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 if necessary.

(Classification process)
The polymerized toner particles obtained in this way have a sufficiently sharp particle size compared to conventional pulverized toner, but when a sharper particle size is required, classification is performed with an air classifier or the like, Particles that deviate from the desired particle size distribution can be separated and removed.

  As the material of each member constituting the apparatus used in the above-described steps, those usually used such as stainless steel, glass, FRP, and ceramic can be used. Further, these surfaces may be subjected to electrolytic polishing, fluororesin coating, or glass lining treatment.

  The toner obtained by the production method of the present invention may be composed only of toner particles obtained by the polymerization method described above, or obtained by externally adding other additives to the toner particles as necessary. It may be. The toner particles and carrier may be mixed to form a two-component toner.

[Polymerizable monomer]
As the polymerizable monomer suitably used in the polymerized toner of the present invention, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional or polyfunctional monomer can be used. Examples of the monofunctional polymerizable monomer include the following.

  Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate , Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, -Acrylic monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl Methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate Ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as til methacrylate; Methylene aliphatic monocarboxylic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether Vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  The following are mentioned as a polyfunctional polymerizable monomer. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2 '-Bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene Glycol dimethacrylate, 1,3-buty Glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,2′-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether.

  In the present invention, the above monofunctional polymerizable monomers are used alone or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. . Among the above-described monomers, styrene or a styrene derivative is preferably used alone or in combination, or in combination with other monomers from the viewpoint of toner development characteristics and durability.

[Colorant]
The following are mentioned as a coloring agent used by this invention. Carbon black; I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modern Tread 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modern Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6; yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, hansa yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GTR, benzidine orange G, cadmium red, Permanent Red 4R, Watching Red Calcium Salt, Brilliant Carmine 3B, Fast Violet B, Methyl Violet Lake, Bitumen, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Quinacridone, Rhodamine Lake, Phthalocyanine Blue, Fast Sky Blue, Pigment Green B, Pigments such as Malachite Green Lake and Final Yellow Green G.

  In selecting a colorant, it is necessary to pay attention to the polymerization inhibitory property and water phase transferability of the colorant. In particular, since dyes and carbon black often have polymerization inhibiting properties, care must be taken when using them. Preferably, these should be subjected to surface modification, for example, a hydrophobic treatment with a substance that does not inhibit polymerization. Examples of the surface treatment of the dye include a method of polymerizing a polymerizable monomer in the presence of these dyes in advance, and the obtained colored polymer is added to a raw material for toner such as a polymerizable monomer composition. . In addition to carbon black, the carbon black may be grafted with a substance that reacts with the surface functional groups of the carbon black, such as polyorganosiloxane.

  These colorants are preferably used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

[Release agent]
As the release agent used in the present invention, a wax in a solid state at room temperature may be used in terms of toner blocking resistance, multi-sheet durability, low-temperature fixability, and offset resistance.

  Examples of the wax include the following. Polymethylene waxes such as paraffin wax, polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, amide wax, higher fatty acid, long chain alcohol, ester wax and graft compounds thereof, and block compounds thereof. These are preferably removed from the low molecular weight component and have a sharp maximum endothermic peak in the endothermic curve obtained by a differential scanning calorimeter. In order to improve the translucency of the image fixed on the OHP, a linear ester wax is particularly preferably used. The linear ester wax may be contained in an amount of 1 to 40 parts by weight, more preferably 4 to 30 parts by weight, based on 100 parts by weight of the polymerizable monomer.

  In the present invention, a second release agent having a melting point lower than 80 ° C. can be used in combination in order to increase the plasticity of the toner particles and improve the fixability in the low temperature region. As the second release agent, a linear alkyl alcohol having 15 to 100 carbon atoms, a linear fatty acid, a linear acid amide, a linear ester or a montan derivative wax is preferably used. It is more preferable that impurities such as liquid fatty acid have been previously removed from these waxes.

[Charge control agent]
The toner produced according to the present invention may contain a charge control agent. Known charge control agents can be used. For example, the following are examples of toners that are controlled to be negatively charged. Organic metal compounds and chelate compounds are effective, monoazo dye metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, bisphenol and other phenol derivatives Kind. Furthermore, the following are mentioned. Urea derivatives, metal-containing salicylic acid compounds, quaternary ammonium salts, calixarene, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-acrylic-sulfonic acid copolymers, non-metallic carboxylic acids Compounds.

  Examples of controlling the toner to be positively charged include the following. Modified products with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate; onium salts such as phosphonium salts and lake pigments thereof, tri Phenylmethane dyes and their lake pigments (Laketungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, or ferrocyanide), higher fatty acid Metal salt. These can be used alone or in combination of two or more. Among these, charge control agents such as quaternary ammonium salts are particularly preferably used.

  These charge control agents are used in an amount of 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymerizable monomer.

[Polymerization initiator]
Examples of the polymerization initiator that can be used in the present invention include azo polymerization initiators. Examples of the azo polymerization initiator include the following. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis -4-methoxy-2,4-dimethylvaleronitrile, azobismethylbutyronitrile.

  An organic peroxide initiator can also be used. The following are mentioned as an organic peroxide type | system | group initiator. Benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1, 1-bis (t-butylperoxy) cyclododecane, t-butylperoxymaleic acid, bis (t-butylperoxy) isophthalate, methyl ethyl ketone peroxide, tert-butylperoxy-2-ethylhexanoate, diisopropyl Peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide.

  A redox initiator in which an oxidizing substance and a reducing substance are combined can also be used. Examples of the oxidizing substance include hydrogen peroxide, inorganic peroxides such as persulfates (sodium salts, potassium salts, ammonium salts, etc.), and oxidizing metal salts such as tetravalent cerium salts. Reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, trivalent chromium salts), ammonia, lower amines (amines having 1 to 6 carbon atoms such as methylamine and ethylamine), hydroxyl Amino compounds such as amines, sodium thiosulfate, sodium hydrosulfite, sodium hydrogen sulfite, sodium sulfite, reducing sulfur compounds such as sodium formaldehyde sulfoxylate, lower alcohols (1 to 6 carbon atoms), ascorbic acid or salts thereof, And lower aldehydes (having 1 to 6 carbon atoms). The initiator is selected with reference to the 10-hour half-life temperature, and is used alone or in combination. The addition amount of the polymerization initiator varies depending on the desired degree of polymerization, but generally 0.5 to 20 parts by mass is added to 100 parts by mass of the polymerizable monomer.

[Crosslinking agent]
Various cross-linking agents can also be used in the present invention. The following are mentioned as a crosslinking agent. Divinylbenzene, 4,4′-divinylbiphenyl, hexanediol diacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate.

[Aqueous medium]
Water is mainly used as the aqueous medium. In addition, a dispersion stabilizer can be used in order to satisfactorily disperse the polymerizable monomer composition in the aqueous medium. Examples of the dispersion stabilizer include the following. Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina , Titania. Examples of the organic compound include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch. The dispersion stabilizer is 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.

  Commercially available dispersion stabilizers may be used as they are, but when using the above-mentioned inorganic compound, in order to obtain dispersed particles having a fine uniform particle size, the inorganic compound is generated under stirring in a dispersion medium. You can also. For example, in the case of tricalcium phosphate, a dispersion stabilizer suitable for the suspension polymerization method can be obtained by introducing and mixing an aqueous calcium chloride solution into an aqueous sodium phosphate solution with sufficient stirring. At this time, the method of adding the calcium chloride aqueous solution is not particularly limited, but it is preferably performed under conditions such that a uniform mixed state can be obtained as quickly as possible. In the case of a device with a large scale, the time required for uniform mixing will increase, so for example, a device is introduced such that a spray nozzle, a shower nozzle, or a porous circular tube is used to diffuse the calcium chloride aqueous solution. May be.

[Polar resin]
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 a polymerizable monomer composition suspended in an aqueous medium, the polar resin tends to migrate to the vicinity of the interface between the aqueous medium and the polymerizable monomer composition due to the difference in affinity for water. Therefore, polar resin is unevenly distributed on the toner surface. 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.

  As such a polar resin, a saturated or unsaturated polyester resin is particularly preferable because the fluidity of the polar resin itself can be expected when it is unevenly distributed on the toner surface to form a shell.

  As the polyester-based resin, those obtained by condensation polymerization of the following acid component monomers and alcohol component monomers can be used. The following are mentioned as an acid component monomer. Terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, camphoric acid, cyclohexanedicarboxylic acid, trimellit acid. Examples of alcohol component monomers include the following. Alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, and Polyalkylene glycols, bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, pentaerythritol.

[External additive]
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 the following. Metal oxides such as aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide; nitrides such as silicon nitride; carbides such as carbide silicon carbide; calcium sulfate, barium sulfate, Inorganic metal salts such as calcium carbonate; fatty acid metal salts such as zinc stearate and calcium stearate; carbon black, silica.

  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. The external additives may be used singly or in combination of two or more, but those subjected to hydrophobic treatment are more preferable.

  Furthermore, the production method of the present invention can also be applied to a production method of a magnetic toner containing a magnetic material.

[Magnetic material]
The magnetic material contained in the toner can also serve as a colorant. In the present invention, the magnetic material contained in the magnetic toner 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, tin, Alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof.

  These magnetic materials have a volume average particle diameter (Dv) of 0.5 μm or less, preferably about 0.1 to 0.5 μm.

  The volume average particle diameter (Dv) of the magnetic body is a circle of the same area as the projected area of 100 magnetic bodies in the field of view at a magnification of 10,000 to 40,000 times using a transmission electron microscope (TEM). The equivalent diameter is obtained, and the volume average particle diameter is calculated based on the equivalent diameter.

  The content of the magnetic substance in the toner is about 20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight with respect to 100 parts by weight of the polymerizable monomer. Good.

In addition, it is preferable that the magnetic material has a saturation magnetization (σs) of 50 to 200 Am ² / kg and a residual magnetization (σr) of 2 to 20 Am ² / kg when 800 kA / m is applied.

  The magnetic properties of the magnetic material are measured using an oscillating magnetometer VSM P-1-10 (manufactured by Toei Industry Co., Ltd.) at a room temperature of 25 ° C. and an external magnetic field of 79.6 kA / m.

[Hydrophobic agent]
In order to improve the dispersibility of these magnetic materials in the toner particles, it is also preferable to subject the surface of the magnetic material to a hydrophobic treatment. Coupling agents such as a silane coupling agent and a titanium coupling agent are used for the hydrophobic treatment. Of these, silane coupling agents are preferably used. The following are mentioned as a silane coupling agent. Vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxy Silane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane.

  As described above, the toner produced according to the present invention can be used as either a one-component or two-component developer.

  In the case of a magnetic toner containing a magnetic material in the toner as a one-component developer, a method of transporting or charging the magnetic toner using a magnet built in the developing sleeve is used. When non-magnetic toner containing no magnetic material is used, there is a method in which a blade and a fur brush are used to forcibly frictionally charge with a developing sleeve and the toner is attached to the sleeve to be conveyed.

  When the toner obtained by the production method of the present invention is used as a two-component developer, a carrier is used with the toner as a developer. Although it does not specifically limit as a carrier used for this invention, It is comprised by the single or composite ferrite state which mainly consists of iron, copper, zinc, nickel, cobalt, manganese, and a chromium atom.

  The carrier shape is also important from the viewpoint that the saturation magnetization and electric resistance can be controlled over a wide range. For example, it is preferable to select a spherical shape, a flat shape, or an indeterminate shape, and to control the fine structure of the carrier surface state, for example, the surface unevenness. In general, a method is used in which a carrier core particle is generated in advance by firing and granulating the above metal compound, and then a resin is coated. From the viewpoint of reducing the load on the toner of the carrier, a method of obtaining a low density dispersion carrier by kneading and classifying a metal compound and a resin, and further a kneaded product of a metal compound and a polymerizable monomer directly. A method of obtaining a polymer carrier dispersed in a spherical shape by suspension polymerization in an aqueous medium can also be used.

  The particle size of the carrier is measured based on the volume of the carrier using a laser diffraction particle size distribution measuring apparatus (Hellos <HELOS>) manufactured by SYNPATEC and equipped with a dry disperser (Rodos <RODOS>). Measured as 50% average particle size.

  The average particle size of these carriers is preferably 10 to 100 μm, more preferably 20 to 50 μm.

  When the two-component developer is prepared, the mixing ratio between the carrier and the toner in the present invention is usually 2 to 15% by weight, preferably 4 to 13% by weight as the toner concentration in the developer. Is obtained. If the toner concentration is less than 2% by mass, the image density is low and impractical, and if it exceeds 15% by mass, fog and in-machine scattering tend to increase, and image deterioration and developer consumption increase tend to occur.

  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.

In the examples, the following measuring methods were used.
(1) Measurement of weight average particle diameter (D4), volume and number-based median diameter of toner Each particle diameter of toner is a precise particle size distribution measuring device “Coulter Counter” by a pore electric resistance method equipped with an aperture tube of 100 μm. Using "Multisizer 3" (registered trademark, manufactured by Beckman Coulter) and attached dedicated software "Beckman Coulter Multisizer 3 version 3.51" (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and measuring data analysis The measurement was performed with 25,000 effective measurement channels, and the measurement data was analyzed and calculated.

  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.

  In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash 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 solution is placed in a 250 ml round bottom beaker made exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measuring instrument as a dispersant is added therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing (made by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass is added.
3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and a predetermined amount is placed in a water tank of an ultrasonic disperser “Ultrasonic Dissipation System Tetora150” (manufactured by Nikkiki Bios) with an electrical output of 120 W. Of ion-exchanged water, and about 2 ml of the above-mentioned Contaminone N is added to this 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) Into 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.

(2) Evaluation of sharpness of particle size distribution Using each median diameter calculated by measuring the particle size in the previous section, the sharpness of the particle size distribution was determined by the following formula.

Sharpness of particle size distribution = volume-based median diameter ÷ number-based median diameter The closer the value of the above formula is to 1, the sharper the particle size distribution is.

(3) Presence rate of irregularly shaped particles The toner particles were observed using a scanning electron microscope, and the abundance rate of irregularly shaped particles derived from particle coalescence and adhering contamination was calculated. The abundance (%) of irregularly shaped particles is calculated as follows:
Atypical particle abundance (%) = number of irregular particles / total number of particles × 100

(4) Measurement of the amount of unreacted styrene in the toner particles The amount of unreacted styrene in the toner particles is measured by gas chromatography (GC) as follows.

  About 500 mg of toner is precisely weighed and placed in a sample bottle. About 10 g of acetone precisely weighed is added to the lid and mixed well, and then 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 using a calibration curve prepared in advance using styrene.

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) Increase to 200 ° C at 10 ° C / min, (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)

(5) Image quality evaluation To 100 parts by mass of toner particles, a hydrophobic silica fine powder having a specific surface area measured by the BET method of 300 m ² / g is externally added to 1.5 parts by mass, and one-component development is performed. An agent was obtained. The developer was subjected to an image printing endurance test by continuous paper passing under a non-fluctuating environment using a Canon laser printer LBP-2160, and image density fluctuation, image unevenness, and the like were visually evaluated.

In addition, the reflectance of plain paper before printing and the reflectance of a solid white image were measured with a reflectometer (TC-6DS manufactured by Tokyo Denshoku Co., Ltd.), and the fog (%) was calculated by the following formula. did.
Fog (%) = reflectance of plain paper-reflectance of solid white image

The obtained fog value was evaluated in five steps according to the following evaluation criteria.
A: Very good level (less than 0.5%)
B: Good level (0.5% or more and less than 1.0%)
C: No problem level (1.0% or more and less than 2.0%)
D: Acceptable level (2.0% or more and less than 3.0%)
E: Bad level (3.0% or more)

<Example 1>
Toner particles composed of polymer particles were produced by the following procedure.

(Polymerizable monomer preparation process)
Styrene 50.0 parts by mass Salicylic acid compound aluminum complex (Bontron E-88 manufactured by Orient Chemical Industries)
0.95 parts by mass Carbon black 10.0 parts by mass The above components were charged into a temperature-controllable stirring tank, and after stirring, the mixture was sufficiently evenly blended, and then an SC mill (Mitsui Mining Co., Ltd.) was incorporated in the middle. A colorant dispersion was prepared by circulating 90 minutes in the circulation line using a pump. Zirconia beads having a diameter of 0.5 mm were used for the SC mill, and the rotor peripheral speed in the SC mill was 10.0 m / s.
Next, the following components were put into a stirring tank capable of adjusting the temperature, and stirred and mixed at room temperature, and then heated to 60 ° C.

Styrene 33.0 parts by weight Colorant dispersion 60.95 parts by weight n-butyl acrylate 17.0 parts by weight Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 0 parts by mass

  13.75 parts by mass of behenyl behenate (melting point: 73 ° C.) was added to the agitation tank described above, and stirring was continued to obtain a polymerizable monomer composition.

(Aqueous medium preparation process)
Water 97.8 parts by weight Trisodium phosphate 1.4 parts by weight 10% by weight Hydrochloric acid 2.2 parts by weight The above ingredients were put into another temperature-adjustable stirring tank and heated to 60 ° C. Stir until the sodium is completely dissolved.

  A solution prepared by dissolving 0.8 parts by mass of calcium chloride in 5 parts by mass of water was added thereto, and maintained at 60 ° C. at a rotation speed of 83.3 (1 / s) using CLEARMIX (manufactured by M Technique). Stirring was continued for 30 minutes to obtain an aqueous medium which was an aqueous suspension of hydroxyapatite fine particles.

(Granulation process)
While stirring the aqueous medium at 60 ° C. with CLEARMIX (M Technique Co., Ltd.) at a rotational speed of 83.3 (1 / s), the above-mentioned polymerizable monomer composition was added thereto and stirred for 3 minutes. After continuing, 7.0 parts by mass of t-butyl peroxypivalate as a polymerization initiator is added to 100 parts by mass of the polymerizable monomer, and the mixture is further stirred for 7 minutes to be dispersed in the polymerizable monomer composition. Got.

(Polymerization process)
The polymerizable monomer composition dispersion obtained by the above steps is introduced into the polymerization vessel 1 shown in FIG. 1, the temperature of the solution is raised to 67 ° C., and polymerization is carried out for 5 hours. The temperature was raised to 80 ° C. and the polymerization process was continued for 4 hours to obtain a polymer particle dispersion. From the carrier gas introduction pipe 4, nitrogen gas adjusted to 67 ° C. is supplied to the gas phase in the polymerization vessel until the polymerization conversion rate of the polymerizable monomer reaches 80% so that the V / F becomes 0.050. Introduced. As a result, the vapor in the polymerization vessel was entrained with nitrogen and exhausted outside the polymerization vessel through the vent pipe. The exhausted steam was condensed by the condenser 6 in the middle of the vent pipe and recovered so as not to return to the polymerization vessel. Hot water was circulated through the outer jacket 7 installed in the gas phase part of the polymerization vessel, and the internal temperature was set to 67 ° C.

(Solid-liquid separation process, washing process and drying process)
Hydrochloric acid was added to the obtained polymer particle dispersion and stirred to dissolve the hydroxyapatite covering the polymer particles, followed by solid-liquid separation with a pressure filter to obtain polymer 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 the polymer particles in water and solid-liquid separation are repeated until the hydroxyapatite is sufficiently removed, the solid-liquid separated polymer particles are sufficiently dried by an airflow dryer. Thus, toner particles were obtained.

(Repeated production of toner particles)
The steps so far were repeated 10 times without cleaning the polymerization vessel. When the particle size distribution of the toner particles obtained at the 10th time was measured, the weight average particle size (D4) was 5.8 μm, and the sharpness of the particle size distribution was 1.12. The abundance of irregularly shaped particles was 0.6%, and the amount of unreacted styrene in the toner particles was 950 ppm based on the toner particle mass. During this time, there was no abnormality in temperature control or clogging of piping, and the operation state of the apparatus was stable from start to finish.

(Evaluation of toner image quality)
The obtained toner particles were externally added with the hydrophobic silica fine powder to obtain a toner (one-component developer). When image quality evaluation was performed by continuously printing 20000 sheets using this toner, the image density was not changed from time to time, and the image was not uneven, and a clear image was stably obtained. The fog evaluation was A.

<Example 2>
Toner particles were produced in exactly the same manner as in Example 1 except that the internal temperature of the external jacket installed in the gas phase part of the polymerization vessel during the polymerization process was 77 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 5.9 μm, and the sharpness of the particle size distribution was 1.13, which was a very sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 0.7%, and the amount of unreacted styrene in the toner particles was 1010 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was no unevenness in the image, and a clear image was stably obtained. The fog evaluation was A.

<Example 3>
Toner particles were produced in exactly the same manner as in Example 1 except that the internal temperature of the outer jacket installed in the gas phase portion of the polymerization vessel during the polymerization step was 57 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 5.8 μm, and the sharpness of the particle size distribution was 1.14. The abundance of irregularly shaped particles after repeated production was 0.7%, and the amount of unreacted styrene in the toner particles was 1150 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was no unevenness in the image, and a clear image was stably obtained. The fog evaluation was A.

<Example 4>
Toner particles were produced in exactly the same manner as in Example 1 except that the internal temperature of the outer jacket installed in the gas phase part of the polymerization vessel during the polymerization step was 79 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.1 μm, and the sharpness of the particle size distribution was 1.15, which was a sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 0.9%, and the amount of unreacted styrene in the toner particles was 980 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was no unevenness in the image, and a clear image was stably obtained. The fog was evaluated as B.

<Example 5>
Toner particles were produced in exactly the same manner as in Example 1 except that the internal temperature of the external jacket placed in the gas phase part of the polymerization vessel during the polymerization step was 55 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.0 μm, and the sharpness of the particle size distribution was 1.15, which was a sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 1.0%, and the amount of unreacted styrene in the toner particles was 1080 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was no unevenness in the image, and a clear image was stably obtained. The fog was evaluated as B.

<Example 6>
As shown in FIG. 2, toner particles were produced in exactly the same manner as in Example 1 except that a polymerization vessel having no external jacket was used in the gas phase portion. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.0 μm, and the sharpness of the particle size distribution was 1.16, which was a relatively sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 1.1%, and the amount of unreacted styrene in the toner particles was 1190 ppm with respect to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was almost no unevenness in the image, and a clear image was stably obtained. The fog was evaluated as B.

<Example 7>
Toner particles were produced in the same manner as in Example 1 except that the ratio V / F of the volume V of the gas phase portion of the polymerization vessel to the flow rate F of nitrogen introduced during the polymerization step was 0.002. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 5.7 μm, and the sharpness of the particle size distribution was 1.14. The abundance of irregularly shaped particles after repeated production was 0.8%, and the amount of unreacted styrene in the toner particles was 910 ppm with respect to the toner particle mass. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was no unevenness in the image, and a clear image was stably obtained. The fog evaluation was A.

<Example 8>
Toner particles were produced in the same manner as in Example 1 except that the ratio V / F of the volume V of the gas phase portion of the polymerization vessel to the flow rate F of nitrogen introduced during the polymerization step was 0.100. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 5.8 μm, and the sharpness of the particle size distribution was 1.14. The abundance of irregularly shaped particles after repeated production was 0.7%, and the amount of unreacted styrene in the toner particles was 1200 ppm based on the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was no unevenness in the image, and a clear image was stably obtained. The fog evaluation was A.

<Example 9>
Toner particles were produced in exactly the same manner as in Example 1, except that the ratio V / F of the volume V of the vapor phase portion of the polymerization vessel to the flow rate F of nitrogen introduced during the polymerization step was 0.001. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.2 μm, and the sharpness of the particle size distribution was 1.15, which was a relatively sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 1.2%, and the amount of unreacted styrene in the toner particles was 970 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was almost no unevenness in the image, and a clear image was stably obtained. The fog was evaluated as B.

<Example 10>
Toner particles were produced in exactly the same manner as in Example 1 except that the ratio V / F of the volume V of the vapor phase of the polymerization vessel to the flow rate F of nitrogen introduced during the polymerization step was 0.110. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.1 μm, and the sharpness of the particle size distribution was 1.15, which was a relatively sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 1.1%, and the amount of unreacted styrene in the toner particles was 1160 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was almost no unevenness in the image, and a clear image was stably obtained. The fog was evaluated as B.

<Example 11>
Toner particles were produced in exactly the same manner as in Example 1 except that the temperature of nitrogen introduced into the gas phase portion of the polymerization vessel during the polymerization step was 77 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 5.7 μm, and the sharpness of the particle size distribution was 1.13. The abundance of irregularly shaped particles after repeated production was 0.7%, and the amount of unreacted styrene in the toner particles was 1010 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was no unevenness in the image, and a clear image was stably obtained. The fog evaluation was A.

<Example 12>
Toner particles were produced in exactly the same manner as in Example 1 except that the temperature of nitrogen introduced into the gas phase portion of the polymerization vessel during the polymerization step was 57 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 5.9 μm, and the sharpness of the particle size distribution was 1.13, which was a very sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 0.7%, and the amount of unreacted styrene in the toner particles was 1210 ppm relative to the toner particle mass. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was no unevenness in the image, and a clear image was stably obtained. The fog evaluation was A.

<Example 13>
Toner particles were produced in exactly the same manner as in Example 1 except that the temperature of nitrogen introduced into the gas phase part of the polymerization vessel during the polymerization step was 79 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.0 μm, and the sharpness of the particle size distribution was 1.15, which was a relatively sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 0.9%, and the amount of unreacted styrene in the toner particles was 990 ppm with respect to the toner particle mass. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was almost no unevenness in the image, and a clear image was stably obtained. The fog was evaluated as B.

<Example 14>
Toner particles were produced in exactly the same manner as in Example 1 except that the temperature of nitrogen introduced into the gas phase part of the polymerization vessel during the polymerization step was 55 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.1 μm, and the sharpness of the particle size distribution was 1.16, which was a relatively sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 1.1%, and the amount of unreacted styrene in the toner particles was 1000 ppm with respect to the toner particle mass. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was almost no unevenness in the image, and a clear image was stably obtained. The fog was evaluated as B.

<Example 15>
Toner particles were produced in the same manner as in Example 1 except that air was used as the gas introduced into the gas phase portion of the polymerization vessel during the polymerization step. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 5.8 μm, and the sharpness of the particle size distribution was 1.14. The abundance of irregularly shaped particles after repeated production was 0.8%, and the amount of unreacted styrene in the toner particles was 1190 ppm with respect to the toner particle mass. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was no unevenness in the image, and a clear image was stably obtained. The fog evaluation was A.

<Example 16>
Toner particles were produced in exactly the same manner as in Example 1 except that the gas introduced into the gas phase part of the polymerization vessel during the polymerization process was water vapor at 100 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.2 μm, and the sharpness of the particle size distribution was 1.16, which was a relatively sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 1.2%, and the amount of unreacted styrene in the toner particles was 910 ppm with respect to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was almost no unevenness in the image, and a clear image was stably obtained. The fog was evaluated as B.

<Example 17>
Toner particles were produced in exactly the same manner as in Example 1 except that the gas introduced into the gas phase part of the polymerization vessel in the polymerization step was a mixed gas having a 1: 1 ratio of air to nitrogen. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 5.9 μm, and the sharpness of the particle size distribution was 1.13, which was a very sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 0.8%, and the amount of unreacted styrene in the toner particles was 1110 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was no unevenness in the image, and a clear image was stably obtained. The fog evaluation was A.

<Example 18>
Toner particles were produced in the same manner as in Example 1 except that oxygen was used as the gas introduced into the gas phase part of the polymerization vessel during the polymerization process. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.3 μm, and the sharpness of the particle size distribution was 1.15, which was a relatively sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 1.2%, and the amount of unreacted styrene in the toner particles was 2040 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was almost no unevenness in the image, and a clear image was stably obtained. The fog was evaluated as B.

<Example 19>
Toner particles were produced in exactly the same manner as in Example 1 except that the temperature of nitrogen introduced into the gas phase part of the polymerization vessel during the polymerization step was 40 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.2 μm, and the sharpness of the particle size distribution was 1.15, which was a relatively sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 0.9%, and the amount of unreacted styrene in the toner particles was 1290 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was almost no unevenness in the image, and a clear image was stably obtained. The fog was evaluated as B.

<Example 20>
Toner particles were produced in exactly the same manner as in Example 1 except that the temperature of nitrogen introduced into the gas phase part of the polymerization vessel during the polymerization step was 120 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.3 μm, and the sharpness of the particle size distribution was 1.16, which was a relatively sharp particle size distribution. The abundance of irregularly shaped particles after repeated production was 1.0%, and the amount of unreacted styrene in the toner particles was 960 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, the image density was not changed from beginning to end, and there was almost no unevenness in the image, and a clear image was stably obtained. The fog was evaluated as B.

<Comparative Example 1>
Toner particles were produced in the same manner as in Example 1 except that the introduction of nitrogen gas was stopped when the polymerization conversion rate reached 70% during the polymerization step. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.4 μm, and the sharpness of the particle size distribution was 1.18, which was a slightly broader particle size distribution than in Example 1. . The abundance of irregularly shaped particles after repeated production was 2.1%, and the amount of unreacted styrene in the toner particles was 1090 ppm relative to the mass of the toner particles. When the image quality of the toner was evaluated, white streaks and density unevenness were observed from a relatively early period. The fog evaluation was D.

<Comparative example 2>
Toner particles were produced in exactly the same manner as in Example 1 except that the temperature of the nitrogen gas introduced into the gas phase part of the polymerization vessel during the polymerization step was 130 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.3 μm, and the sharpness of the particle size distribution was 1.17, which was slightly broader than that of Example 1. . The abundance of irregularly shaped particles after repeated production was 1.7%, and the amount of unreacted styrene in the toner particles was 1010 ppm relative to the toner particle mass. When the image quality of the toner was evaluated, white streaks and density unevenness were observed from a relatively early period. The fog evaluation was D.

<Comparative Example 3>
Toner particles were produced in exactly the same manner as in Example 1 except that the temperature of the nitrogen gas introduced into the gas phase part of the polymerization vessel during the polymerization step was 30 ° C. When the particle size distribution of the obtained toner particles was measured, the weight average particle size (D4) was 6.5 μm, and the sharpness of the particle size distribution was 1.19, which was slightly broader than that of Example 1. . The abundance of irregularly shaped particles after repeated production was 2.3%, and the amount of unreacted styrene in the toner particles was 1130 ppm with respect to the toner particle mass. When the image quality of the toner was evaluated, white streaks and density unevenness were observed from a relatively early period. The fog evaluation was D.

1, 11: Polymerization vessel, 2, 12: Temperature control jacket, 3, 13: Stirring blade, 4, 14: Carrier gas introduction pipe, 5, 15: Vent pipe, 6, 16: Condenser, 7: Gas phase section External jacket

Claims (6)

Polymerizable monomer and a polymerizable monomer composition having containing a colorant is added to the aqueous medium, the particles of the polymerizable monomer composition is formed in aqueous medium, the polymerizable monomer composition a manufacturing method of the toner particles to obtain toner particles by polymerizing a polymerizable monomer contained in the particles of the object,
The polymerization temperature when polymerizing the polymerizable monomer is 50 ° C. or more and 90 ° C. or less,
A polymerization apparatus in which polymerization of the polymerizable monomer is performed has a polymerization container,
In the polymerization vessel,
A liquid phase part of an aqueous medium having particles of the polymerizable monomer composition;
The gas phase ,
Formed,
In the polymerization vessel ,
Vent pipe for evacuating the gas phase portion, and,
Carrier gas introduction piping is provided,
Until the polymerization conversion of the polymerizable monomers reaches at least 80%, in the gas phase portion, the temperature is introducing a carrier gas is 120 ° C. or less 40 ° C. or higher, and, in the polymerization vessel A method for producing a polymerized toner, characterized in that gas is exhausted from a vent pipe. The carrier gas, air, nitrogen and method for producing a polymerized toner according to 請 Motomeko 1 Ru one gas or a mixture of two or more gases der of the gas selected from the group consisting of water vapor. And the temperature at which the carrier gas is introduced into the polymerization vessel,
And the polymerization temperature of the polymerizable monomer,
Method for producing a polymerized toner of the temperature difference, according to 請 Motomeko first or 2 Ru der within 10 ° C.. A flow rate F (m ³ / h) of the carrier gas introduced into the polymerization vessel,
And the volume V (m ³⁾ of the gas phase portion,
To the relationship, less than the 0.002 ≦ (V / F) ≦ 0.100
Method for producing a polymerized toner according to any one of 請 Motomeko 1-3. Method for producing polymerized toner according to the polymerization the gas phase portion formed in the container in any one of 請 Motomeko 1 to 4 you heated by an external jacket. And the internal temperature of the external jacket,
And the polymerization temperature of the polymerizable monomer,
The method of producing polymerized toner of the temperature difference, according to Der Ru請 Motomeko 5 within 10 ° C..

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