JP5489865B2 - 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 method for producing polymerized toner particles in which a polymerizable monomer is dispersed in the form of droplets and polymerization is performed to directly obtain toner particles. For example, in the method for producing toner particles by suspension polymerization, a polymerizable monomer, a colorant, a release agent, a polymerization initiator, and a cross-linking agent, a charge control agent and other additives are uniformly added as necessary. A polymerizable monomer composition is prepared by dissolving or dispersing. Further, this is granulated in an aqueous medium containing a dispersion stabilizer by using a suitable stirrer or disperser, and a polymerization reaction is performed to obtain a suspension of polymerized toner particles having a desired particle size. obtain. If necessary, this polymerized toner particle suspension is treated with an acid or alkali to remove the dispersion stabilizer, and then the aqueous medium is separated in a solid-liquid separation step to obtain toner particles.

  In the conventional suspension polymerization method, the dispersion of additives such as a colorant and a charge control agent in the polymerizable monomer composition is insufficient, and thus there is a problem that image characteristics are likely to be deteriorated. there were. In particular, if the dispersion of the colorant in the polymerizable monomer composition is insufficient, the surface charge amount of the toner is reduced and fog is deteriorated or the image density is lowered due to uneven distribution of the colorant in the toner. To do.

  For fine and uniform dispersion of the colorant in the polymerizable monomer, there is generally a method of forcibly dispersing it in the polymerizable monomer using a media-type disperser using media such as beads. It has been. However, even when a colorant dispersion is obtained in this way, additional addition of a polymerizable monomer in the subsequent steps, or pigment shock (change in composition or viscosity of the dispersion, by mixing with other additives, Shock aggregation caused by temperature change, pH change and the like may occur. In such a case, the highly dispersed colorant once reaggregates, which adversely affects the toner properties.

  As a method for preventing pigment shock, when adding a solvent to a dispersion liquid of a colorant or the like, a method of suppressing a rapid concentration change of the colorant or the like by gradually adding the solvent in multiple times (patent) There are references 1, 2). In addition, there is a method (Patent Document 3) that suppresses a sudden change in viscosity at the time of addition by adjusting the ratio of the viscosity of the solvent and the viscosity of the colorant dispersion every time the solvent is added. However, these methods are not preferable because the efficiency of production is not expected from the point that the process of repeatedly adding the solvent is complicated and the process requires time.

JP 2008-091535 A JP 2008-101051 A Japanese Patent Laid-Open No. 08-167144

  The object of the present invention is to suppress the pigment shock generated in the production process of the polymerized toner particles as described above, the colorant is more finely and uniformly dispersed in the toner particles, and the image characteristics such as fog are better. Another object of the present invention is to provide a method for efficiently and stably producing toner particles.

As a result of intensive studies to solve the above problems, the present inventors have found the following method.
(1) A dispersion step in which at least a colorant is dispersed in a part of the polymerizable monomer to obtain a colorant dispersion, and the remaining polymerizable monomer is mixed with the colorant dispersion to obtain a polymerizable monomer. A method for producing polymer toner particles, comprising: a mixing step for obtaining a body mixture; and a dissolution step for dissolving at least a release agent in the polymerizable monomer mixture to obtain a polymerizable monomer composition. While preparing the polymerizable monomer mixed liquid by supplying the dispersion into the remaining polymerizable monomer, the colorant concentration in the polymerizable monomer mixed liquid during the preparation is The amount of colorant per 100 parts by mass of the polymerizable monomer contained in the mixed liquid is increased by a change amount of 1.67 parts by mass or less per unit time (minutes). A method for producing toner particles.
(2) A dispersion step in which at least a colorant is dispersed in a part of the polymerizable monomer to obtain a colorant dispersion, and the remaining polymerizable monomer is mixed with the colorant dispersion to obtain a polymerizable monomer. A method for producing polymerized toner particles, comprising a mixing step for obtaining a body mixture, and a dissolving step for obtaining a polymerizable monomer composition by dissolving at least a release agent in the polymerizable monomer mixture,
While preparing the polymerizable monomer mixture by supplying the remaining polymerizable monomer into the colorant dispersion, the colorant concentration in the polymerizable monomer mixture during the preparation is polymerizable. The colorant amount per 100 parts by mass of the polymerizable monomer contained in the monomer mixture is characterized by a decrease of 1.67 parts by mass or less per unit time (minute). A method for producing polymerized toner particles.
(3) The difference between the temperature of the colorant dispersion and the temperature of the remaining polymerizable monomer is within 10 ° C. The polymerized toner particles according to (1) or (2), Production method.
(4) The colorant concentration in the colorant dispersion at the end of the dispersion step is 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. The method for producing polymerized toner particles according to any one of (1) to (3).
(5) The colorant concentration in the polymerizable monomer composition is 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. (4) The method for producing polymerized toner particles according to any one of (4).
(6) The polymerized toner particle according to any one of (1) to (5), wherein the polymerizable monomer composition at 60 ° C. has a viscosity of 1 mPa · s to 25 mPa · s. Manufacturing method.

  According to the present invention, the pigment shock generated in the mixing step of mixing the colorant dispersion and the remaining polymerizable monomer to obtain the polymerizable monomer mixture is efficiently suppressed, and due to segregation of the colorant. It is possible to provide a new method for producing a polymerized toner that prevents deterioration of toner properties.

It is a flowchart which shows an example of the manufacturing method of this invention. It is a flowchart which shows another example of the manufacturing method of this invention. It is a graph which shows transition of the coloring agent density | concentration in a polymerizable monomer liquid mixture, and a coloring agent density | concentration variation | change_quantity (increase amount). It is a graph which shows transition of the coloring agent density | concentration in a polymerizable monomer liquid mixture, and a coloring agent density | concentration variation | change_quantity (decrease amount).

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

  FIG. 1 and FIG. 2 are an example of the manufacturing method of the present invention, and are flowcharts showing the entire manufacturing flow. In the dispersion step in the present invention, at least a colorant is dispersed in a part of the polymerizable monomer to prepare a colorant dispersion. The concentration of the colorant in the colorant dispersion is preferably 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. If the amount is less than 3 parts by mass, the primary particles of the colorant are crushed in the disperser and the surface activity is increased to cause re-aggregation, so that the dispersibility of the colorant is deteriorated and the toner has sufficient coloring power. I can't. On the other hand, when the amount exceeds 40 parts by mass, the viscosity of the colorant dispersion increases, and a uniform dispersion state of the colorant cannot be obtained.

  The disperser used in the dispersion process is not particularly limited, such as Philmix (made by Special Machine Industries), SS5 (made by M Technique), Cavitron (made by Eurotech), Milder (made by Matsubo), etc. Medialess disperser, Apex mill (manufactured by Kotobuki Giken Kogyo), continuous attritor (manufactured by Mitsui Mining), handy mill (manufactured by Mitsui Mining), SC mill (manufactured by Mitsui Mining), star mill LMZ, star mill ZRS (Ashizawa)・ A media-type disperser such as (Finetech) can be used. Two or more dispersers may be used in combination.

  Moreover, since the heat generated during dispersion tends to adversely affect the polymerizable monomer, it is preferable to operate by performing heat exchange by installing a heat exchanger in the disperser. At that time, the liquid temperature of the colorant dispersion is preferably adjusted to 10 to 50 ° C. When the liquid temperature is lower than 10 ° C., moisture due to condensation may be mixed in the colorant dispersion liquid, which is not preferable because there is a fear of reducing the dispersion efficiency. On the other hand, when the liquid temperature exceeds 50 ° C., the polymerizable monomer may be deteriorated, which causes a problem in image characteristics.

  Next, in the mixing step, the colorant dispersion is supplied and mixed into the remaining polymerizable monomer to prepare a polymerizable monomer mixture (FIG. 1). In the remaining polymerizable monomer, additives such as a resin and a crosslinking agent may be dissolved in advance. While preparing the polymerizable monomer mixture by supplying the colorant dispersion into the remaining polymerizable monomer, the colorant concentration does not change abruptly in the polymerizable monomer mixture during the preparation. It is necessary to consider that. This is to prevent the colorant from aggregating due to a pigment shock that occurs due to an abrupt density change. For this purpose, the rate at which the colorant dispersion is fed into the remaining polymerizable monomer is controlled. Specifically, while supplying the colorant dispersion, the colorant concentration in the polymerizable monomer mixture during preparation is such that the polymerizable monomer 100 contained in the polymerizable monomer mixture is 100%. The amount of colorant per part by mass is gradually increased with a change amount of 1.67 parts by mass or less per unit time (minute). When mixing in a range exceeding 1.67 parts by mass, the colorant re-aggregates due to a large increase in the colorant concentration in the polymerizable monomer mixture during preparation, and the dispersion state of the colorant deteriorates. .

  When preparing the polymerizable monomer mixture by supplying the colorant dispersion into the remaining polymerizable monomer at a constant rate, the polymerizable monomer in the course of preparation is supplied as the colorant dispersion is supplied. The colorant concentration in the monomer mixture increases, and the amount of change in the colorant concentration per unit time (minutes) gradually decreases. Therefore, the amount of change per unit time (minute) of the colorant concentration in the polymerizable monomer mixture during preparation is maximized immediately after the start of the supply of the colorant dispersion. For this reason, what is necessary is just to make small the variation | change_quantity of the colorant density | concentration in the unit time (minute) from the supply start time of a colorant dispersion liquid. Specifically, the supply rate is limited so that the amount of the colorant per 100 parts by mass of the polymerizable monomer contained in the polymerizable monomer mixture during preparation is 1.67 parts by mass or less. .

  Further, if the amount of change in the colorant concentration in the polymerizable monomer mixture during preparation is within the above range, the supply rate of the colorant dispersion is increased from the middle or the colorant dispersion is intermittently It is also possible to supply.

  The polymerizable monomer mixed liquid may be prepared in a configuration in which the remaining polymerizable monomer is supplied into the colorant dispersion (FIG. 2). Also in this case, while supplying the remaining polymerizable monomer into the colorant dispersion and preparing the polymerizable monomer mixture, the concentration of the colorant in the polymerizable monomer mixture during preparation is rapidly increased. It is necessary to consider that there is no pigment shock associated with any change. Therefore, the rate at which the remaining polymerizable monomer is fed into the colorant dispersion is controlled. Specifically, while supplying the remaining polymerizable monomer, the concentration of the colorant in the polymerizable monomer mixture during preparation is such that the polymerizable monomer contained in the polymerizable monomer mixture is contained. The amount of colorant per 100 parts by mass of the mer is gradually decreased with a change amount of 1.67 parts by mass or less per unit time (minute). If the amount of change per unit time (minutes) exceeds 1.67 parts by mass, the colorant re-reacts because the rate of decrease in the colorant concentration in the polymerizable monomer mixture during preparation is large. Aggregates and the colorant is dispersed poorly.

  When preparing the polymerizable monomer mixture by supplying the remaining polymerizable monomer into the colorant dispersion at a constant rate, the remaining polymerizable monomer is being supplied as it is being prepared. The colorant concentration in the polymerizable monomer mixture decreases, and the amount of change in the colorant concentration per unit time (minute) gradually decreases. Therefore, the amount of change per unit time (minute) of the colorant concentration in the polymerizable monomer mixture during preparation is maximized immediately after the supply of the remaining polymerizable monomer is started. For this reason, what is necessary is just to make small the variation | change_quantity of the coloring agent density | concentration from the supply start time of the remaining polymerizable monomer until unit time (minute) passes. Specifically, the supply rate is limited so that the amount of the colorant per 100 parts by mass of the polymerizable monomer contained in the polymerizable monomer mixture during preparation is 1.67 parts by mass or less. .

  If the amount of change in the colorant concentration in the polymerizable monomer mixture during preparation is within the above range, the supply rate of the remaining polymerizable monomer can be increased from the middle, or the remaining polymerizable monomer can be increased. It is also possible to supply the meter intermittently.

  Furthermore, when mixing the colorant dispersion and the remaining polymerizable monomer, if the difference between the liquid temperature of the colorant dispersion and the liquid temperature of the remaining polymerizable monomer is reduced, the temperature difference is accompanied. Pigment shock can be suppressed, which is preferable. Specifically, it is preferable to control the temperature difference within 10 ° C.

  After the mixing step, an additive such as a release agent composed of a low softening point substance in the subsequent dissolving step, and in some cases toner particles having a particle size outside the predetermined range excluded by classification, are added and uniformly dissolved by a stirrer or the like. Alternatively, it is dispersed to obtain a polymerizable monomer composition. Toner particles having a non-predetermined particle size can be reused to improve the final yield. However, when toner particles that have already been polymerized are reused as raw materials, the polymerizable monomer composition may have a high viscosity. When the polymerizable monomer composition has a high viscosity, when dispersed in an aqueous dispersion medium in the subsequent granulation step, the droplets of the polymerizable monomer composition are difficult to be miniaturized and many coarse particles of 10 μm or more are generated. However, care must be taken because the particle size distribution becomes broad.

  The colorant concentration in the polymerizable monomer composition is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. When the colorant concentration is less than 1 part by mass, the coloring power of the toner particles is lowered and the image density is lowered. On the other hand, if it exceeds 20 parts by mass, the viscosity of the polymerizable monomer composition increases, and the particle size distribution becomes broad in the subsequent granulation step. At this time, when the viscosity of the polymerizable monomer composition is adjusted to be 1 mPa · s or more and 25 mPa · s or less at 60 ° C., the particle size distribution becomes sharp and the yield of toner particles having a particle size within a predetermined range is obtained. Since it becomes favorable, it is preferable.

  After the dissolving step, the polymerizable monomer composition is transferred to a granulation tank. Here, it disperses | distributes in the aqueous phase containing a dispersion stabilizer using dispersers, such as a normal stirrer or CLEARMIX (made by M Technique), and Cavitron (made by Eurotech). Preferably, granulation is performed by adjusting the stirring speed and time so that the droplets of the polymerizable monomer composition have a desired toner particle size.

  The addition of the polymerization initiator can be performed at any time and required time after the granulation step, but the addition is preferably terminated before the polymerization conversion rate of the polymerizable monomer reaches 90%. If the polymerization initiator is added after the polymerization conversion rate of the polymerizable monomer composition exceeds 90%, the polymerization initiator added into the droplets of the dispersed polymerizable monomer composition is successfully incorporated. It becomes difficult to be. For this reason, toner particles having a desired molecular weight cannot be obtained, or a difference in molecular weight distribution occurs between the toner particles, which is not preferable.

  After the granulation step, the polymerizable monomer composition dispersion is transferred to the polymerization tank and the polymerization step is performed. In the polymerization step, stirring is performed while maintaining the polymerizable monomer composition dispersion at a predetermined temperature to obtain a polymer fine particle dispersion. The same stirring means as that used for the granulation tank can be used for the polymerization tank. The polymerization temperature is 40 ° C or higher, generally 50 to 90 ° C. The polymerization temperature may be constant from beginning to end, but may be raised in the latter half of the polymerization step for the purpose of obtaining a desired molecular weight distribution.

  In order to remove volatile impurities such as unreacted polymerizable monomers and by-products, a part of the aqueous medium may be distilled off by distillation step after the completion of the polymerization step. 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 general solid-liquid separation method, but in order to completely remove the acid or alkali and the dispersion stabilizer dissolved therein, water is added again to wash the polymer fine particles. To do. 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 non-predetermined particle group separated at this time may be reused to improve the final yield. However, as described above, if the predetermined outer particle group that has already been polymerized is reused as a raw material, the polymerizable monomer composition becomes highly viscous and the granulation property may be deteriorated. It is.

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

  As the polymerizable monomer suitably used in the present invention, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

Examples of the monofunctional polymerizable monomer include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and pn-. Butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, styrene derivatives such as p-phenylstyrene;
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 polymerizable monomers such as n-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 Methacrylic polymerizable monomers such as n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate;
Vinyl esters such as methylene aliphatic monocarboxylic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate;
Examples include vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

  Examples of the polyfunctional polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tripropylene. Glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tri Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethyleneglycol Rudimethacrylate, 1,3-butylene 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 and the like.

  In the present invention, the above-mentioned monofunctional polymerizable monomers are used alone or in combination of two or more, or the above-mentioned monofunctional polymerizable monomers and polyfunctional polymerizable monomers are combined, Or a polyfunctional polymerizable monomer is used individually or in combination of 2 or more types. 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.

  Examples of the colorant used in the present invention include C.I. I. Pigment blue 2,3,15: 1,15: 2,15: 3,16,17, C.I. I. Acid Blue 6, C.I. I. Examples thereof include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of the colorant for magenta toner include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 155, 163, 202, 206, 207, 209, 238, C.I. I. Pigment violet 19, C.I. I. And pigments such as Vat Red 1, 2, 10, 13, 15, 23, 29, and 35. Furthermore, C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1; I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,25,26,27,28 etc. basic dyes etc. are mentioned.

  Examples of the colorant for yellow toner include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 93, 94, 95, 97, 109,110,111,120,127,128,129,147,151,154,155,168,174,175,176,180,181,191,194, C.I. I. Examples thereof include pigments such as Vat Yellow 1, 3, 20, Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, and Permanent Yellow NCG. Furthermore, C.I. I. Examples thereof include dyes such as solvent yellow 9, 17, 24, 31, 35, 58, 93, 100, 102, 103, 105, 112, 162, and 163.

  As the colorant for black toner, carbon black, acetylene black, lamp black, graphite, iron black, aniline black, cyanine black, etc., or the yellow colorant, magenta colorant, cyan colorant, and the like exemplified above are further required. Accordingly, a black colorant mixed with the above-described black colorant is used.

  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 blacks often have polymerization inhibiting properties, care must be taken when using them. These are preferably subjected to surface modification, for example, a hydrophobic treatment with a substance that does not inhibit polymerization. Examples of the method for surface-treating the dye include a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the 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.

  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.

  As the wax, polymethylene wax such as paraffin wax, polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, linear alkyl alcohol having 15 to 100 carbon atoms, linear fatty acid, linear acid amide, linear And waxes of ester-like esters or montan derivatives and their derivatives such as graft compounds and block compounds. 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 is preferably contained in an amount of 1 to 40 parts by mass, more preferably 4 to 30 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  The toner produced according to the present invention may contain a charge control agent. Known charge control agents can be used. 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, organic metal compounds and chelate compounds are effective for controlling the toner to be negatively charged. In addition, monoazo dye metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and There are metal derivatives, anhydrides, esters, phenol derivatives such as bisphenol, and the like. Examples of toners that are negatively charged include urea derivatives, metal-containing salicylic acid compounds, quaternary ammonium salts, calixarene, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, Examples include styrene-acrylic-sulfonic acid copolymers and non-metallic carboxylic acid compounds.

  Examples of toners that are controlled to be positively charged include denatured products of nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, And onium salts such as phosphonium salts thereof and their lake pigments, triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid) , Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids, diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide, dibutyltin borate, dioctyl Rusuzuboreto, there is diorgano tin borate, and the like, such as dicyclohexyl tin borate, may be used alone or in combination of two or more. Among these, a charge control agent such as a nigrosine-based quaternary ammonium salt is particularly preferably used.

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

  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 azo polymerization initiators. As the azo polymerization initiator, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobismethylbutyronitrile, and the like.

  An organic peroxide initiator can also be used. Organic peroxide initiators include benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, bis (4-t-butyl) (Cyclohexyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclododecane, t-butylperoxymaleic acid, bis (t-butylperoxy) isophthalate, methyl ethyl ketone peroxide, tert-butylperoxy Examples include 2-ethylhexanoate, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and the like.

  The polymerization initiator is selected with reference to a 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. Moreover, when these polymerization initiators are solid at the temperature used, it is preferable to dissolve in an organic solvent or the like in advance to form a liquid from the viewpoints of handling and uniform mixing.

  In the present invention, 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 the dispersion medium, which is a continuous phase when the polymerizable monomer composition is dispersed, known ones used in various polymerization methods can be used, and the dispersion medium is appropriately determined depending on the polymerizable monomer or polymerization method used. It is selected and is not particularly limited. In suspension polymerization, an aqueous medium is used. The aqueous medium is a medium mainly composed of water or water containing a water-soluble component such as a water-soluble organic solvent or a water-soluble inorganic salt, and the polymerizable monomer composition is dispersed as droplets. If it does not specifically limit.

  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. As water-soluble polymers, for example, polyvinyl alcohol, methylcellulose, and gelatin are known. Examples of the hardly water-soluble inorganic compound include carbonates such as barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, and magnesium carbonate; and polyvalent metal phosphates such as aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate, and zinc phosphate. Inorganic salts such as calcium metasuccinate, calcium sulfate and barium sulfate; inorganic oxides such as silica, bentonite and alumina; inorganic hydroxides of calcium hydroxide, aluminum hydroxide, magnesium hydroxide and ferric hydroxide; Etc. These poorly water-soluble inorganic compounds can be used alone or in combination of two or more. Since many of the poorly water-soluble inorganic compounds are metal compounds, they may be referred to as poorly water-soluble metal compounds. These poorly water-soluble inorganic compounds exhibit a function as a dispersion stabilizer when present as fine particles in an aqueous medium.

  As the fine particles of the hardly water-soluble inorganic compound, those that dissolve when the liquid property is changed to acid or alkali are preferably used. Since it dissolves with an acid or alkali, it can be easily removed by washing with an acid or alkali after polymerization, and toner particles having excellent image characteristics can be obtained.

  Among these poorly 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.

  As said polyester-type resin, what carried out the condensation polymerization of the acid component monomer and alcohol component monomer which are mentioned below can be used. Acid monomers include 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, camphor An acid, cyclohexane dicarboxylic acid, trimellitic acid, etc. are mentioned.

  Examples of the alcohol component monomer include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxy Examples include alkylene glycols such as methyl) cyclohexane and polyalkylene glycols, bisphenol A, hydrogenated bisphenol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin, trimethylolpropane, pentaerythritol, and the like.

  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.

  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 alone or in combination, but it is more preferable to use those subjected to hydrophobization treatment.

  Furthermore, the production method of the present invention can also be applied to a production method of a magnetic toner containing a magnetic material. In this case, the magnetic material contained in the toner particles 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, these metals and aluminum, cobalt, copper, lead, magnesium, tin, Examples thereof include zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, alloys of vanadium, 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 material in the toner particles 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. Is good.

In addition, the magnetic material has magnetic properties when applied with 800 kA / m, such as a coercive force (Hc) of 1.6 to 24 kA / m, a saturation magnetization (σs) of 50 to 200 Am ² / kg, and a residual magnetization (σr) of 2. To ²⁰ Am ² / kg. These magnetic characteristics can be measured using a vibration type magnetometer, for example, VSM P-1-10 (manufactured by Toei Kogyo Co., Ltd.) under conditions of, for example, 25 ° C. and an external magnetic field of 800 kA / m.

  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. 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 described above, the toner produced according to the present invention can be used for either a one-component developer or a two-component developer. The toner produced in the present invention is used for image formation by an appropriate method according to the type. For example, in the case of a magnetic toner containing a magnetic material in a toner particle as a one-component developer, when forming an image using this magnetic toner, the magnetic toner is conveyed and charged using a magnet built in the developing sleeve. The method is used. Also, in the case of non-magnetic toner containing no magnetic material, when forming an image using this non-magnetic toner, for example, a blade and a fur brush are used to forcibly frictionally charge with the developing sleeve, and the toner adheres to the sleeve. The method of conveying with is used.

  On the other hand, when the toner obtained by the production method of the present invention is used as a commonly used two-component developer, it is used as a developer using a carrier together with the toner. The carrier used in the present invention is not particularly limited, but particles containing single or composite ferrite mainly composed of iron, copper, zinc, nickel, cobalt, manganese and chromium elements are used.

  The carrier shape is also important because the saturation magnetization and electric resistance can be controlled over a wide range. For example, it is preferable to select the shape of the carrier from spherical, flat, amorphous, etc., and to control the fine structure of the surface state of the carrier, for example, the surface unevenness.

  As the carrier, generally, a resin-coated carrier obtained by firing and granulating the metal compound to produce carrier core particles and coating the resin with the carrier core particles is used. From the viewpoint of reducing the load on the toner of the carrier, a low-density dispersion carrier obtained by kneading a magnetic material and a resin, then pulverizing and classifying, and a kneaded product of a metal compound and a monomer directly in an aqueous medium. It is also possible to use a polymerization carrier obtained by suspension polymerization and dispersion into a true sphere.

  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 produced in the present invention is usually 2 to 15% by mass, preferably 4 to 13% by mass as the toner concentration in the developer. Is obtained. When the toner concentration is less than 2% by mass, the image density is low and practical use is difficult. When the toner concentration exceeds 15% by mass, fogging and scattering in the apparatus increase, and image deterioration and developer consumption may 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. Each measurement and evaluation method is shown below.

(1) Viscosity measurement of polymerizable monomer composition A polymerizable monomer composition having a liquid temperature adjusted to 60 ± 1 ° C. was subjected to the following conditions using Viscocotter VT550 (manufactured by HAAKE). Measurements were made.
Sensor: MV-DIN
Shear rate: 1.075 (1 / s) <1 min> → 1.29 (1 / s) <1 min> → 4.3 (1 / s) <1 min> → 12.9 (1 / s) <1 min> → 21.5 (1 / s) <1 min>

  In addition, the measured value when 1 min passed at a shear rate of 12.9 (1 / s) was taken as the representative viscosity.

(2) 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.

(3) Evaluation of dispersibility of colorant in toner particles The dispersibility of the colorant in the toner particles was determined by a visual test using an optical microscope. That is, after the polymerization step is completed, a dispersion of the colorant is obtained at a magnification of 200 times using an optical microscope BH2-UMA (Olympus Optical Co., Ltd.) obtained by applying one or two drops of the obtained polymer fine particle dispersion to a slide glass. Were evaluated in three stages according to the following evaluation criteria.
The dispersion of the colorant in the toner particles is uniform .... A The dispersion of the colorant in the good toner particles is uneven .... B The segregation of the colorant is observed in the slightly inferior toner particles .... C bad

(4) 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. This developer was subjected to an image endurance test by continuous paper passing under a normal temperature and humidity environment (23 ° C., 60% RH) using a Canon laser printer LBP-2160 to form a solid image portion. The obtained image was measured for reflection density using an SPI filter of Macbeth RD918 type. The obtained Macbeth concentration value was evaluated in three stages according to the following evaluation criteria.
Concentration value: 1.2 or more ··· A Good: 1.0 or more and less than 1.2 ··· B B

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 1.5%)
D: Acceptable level (1.5% or more and less than 2.5%)
E: Bad level (2.5% or more)

<Example 1>
Based on the production flow shown in FIG. 1, toner particles were produced according to the following procedure.

(Dispersion process)
Styrene 50.00 parts by mass Salicylic acid type compound aluminum complex (Bontron E-88 manufactured by Orient Chemical Co., Ltd.)
0.95 parts by mass Carbon black 10.00 parts by mass The above ingredients were charged into a temperature-controllable stirring tank (stirring tank A), stirred and thoroughly evenly blended, and then SC mill (Mitsui Mining Co., Ltd.) A colorant dispersion was prepared by circulating for 90 minutes using a pump in a circulation line incorporating the product (manufactured). 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. The liquid temperature of the obtained colorant dispersion was 27 ° C.

(Mixing process)
Styrene 33.00 parts by weight n-Butyl acrylate 17.00 parts by weight Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 5.00 parts by weight The above components can be temperature controlled Into a stirring tank (referred to as stirring tank B) and stirred to dissolve sufficiently. The solution temperature after dissolution was 28 ° C. Further, 60.95 parts by mass of the colorant dispersion liquid was supplied into the stirring tank B while stirring was continued to prepare a polymerizable monomer mixed liquid. At this time, the concentration of the colorant in the polymerizable monomer mixture during preparation is determined as the amount of the colorant per 100 parts by mass of the polymerizable monomer contained in the polymerizable monomer mixture. The feed rate of the colorant dispersion was controlled so as to increase with a change amount of 0.65 parts by mass at maximum. Specifically, 609.5 kg of the colorant dispersion was supplied into the stirring tank B (550 kg of a solution in which the additive was dissolved in the remaining polymerizable monomer was existing) over 30 minutes and mixed. Table 1 shows the mixing conditions at this time. Further, FIG. 3 shows the transition of the colorant concentration (colorant amount relative to 100 parts by mass of the polymerizable monomer) in the polymerizable monomer mixture during preparation and the colorant concentration change amount per unit time (minute). Shown in

(Dissolution process)
The temperature of the prepared polymerizable monomer mixture is raised to 60 ° C., and then behenyl behenate is 13.75 parts by mass with respect to 100 parts by mass of the polymerizable monomer in the polymerizable monomer mixture. In this manner, the mixture was put into the stirring tank B, and stirring was continued to obtain a polymerizable monomer composition.

  Table 1 shows the physical property values of the obtained polymerizable monomer composition.

(Preparation of aqueous medium)
Water 97.80 parts by weight Trisodium phosphate 1.40 parts by weight The above ingredients are provided with CLEARMIX (M Technique Co., Ltd.) and equipped with end plates at the top and bottom, and a granulated tank that is temperature-adjustable and temperature-adjustable. The mixture was stirred at 1600 rpm while raising the temperature to 60 ° C. to completely dissolve the trisodium phosphate. Thereafter, an aqueous solution in which 2.50 parts by mass of calcium chloride was dissolved in water was added. After the addition of the aqueous calcium chloride solution, the treatment liquid was further circulated and dispersed for 30 minutes to obtain an aqueous medium that was a suspension of fine tricalcium phosphate particles.

(Granulation process)
The aqueous medium in the above-mentioned granulation tank is maintained at 60 ° C., and the polymerizable monomer composition at 60 ° C. is also contained therein so that the mass ratio of the aqueous medium and the polymerizable monomer composition is 2: 1. It was thrown into. 100 mass of polymerizable monomer in the polymerizable monomer composition granulated with Clairemix at 1600 rpm for 10 minutes and charged with t-butyl peroxypivalate as a polymerization initiator in the granulation tank It added so that it might become 7.00 mass part with respect to a part. Subsequently, a polymerizable monomer composition dispersion was obtained by granulating for 10 minutes.

(Polymerization process)
The polymerizable monomer composition dispersion is transferred to a polymerization tank equipped with a full zone blade (manufactured by Shinko Pantech Co., Ltd.), and the liquid temperature is adjusted while stirring the polymerizable monomer composition in the polymerization tank with the full zone blade. The temperature was raised to 67 ° C. and polymerization was carried out for 5 hours. Thereafter, the liquid temperature was further raised to 80 ° C., and the polymerization process was continued for 4 hours to obtain a polymer fine particle dispersion.

(Particle cleaning / solid-liquid separation / drying process)
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.

(Evaluation of toner image quality)
The hydrophobic silica fine powder was externally added to 100 parts by mass of the obtained toner particles so as to be 1.5 parts by mass to obtain a toner (one-component developer). Using this toner, the image quality was evaluated by continuously printing 20000 sheets.

  Table 1 shows the results of measurement and evaluation of the toner particles obtained.

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

(Mixing process)
Styrene 31.10 parts by mass n-butyl acrylate 16.00 parts by mass Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 4.70 parts by mass The mixture was stirred and sufficiently dissolved. The solution temperature after dissolution was 28 ° C. Furthermore, 57.38 parts by mass of the colorant dispersion was supplied into the stirring tank B while continuing the stirring to prepare a polymerizable monomer mixture. Specifically, 573.8 kg of the colorant dispersion liquid was supplied into the stirring tank B (518.0 kg of a solution in which the additive was dissolved in the remaining polymerizable monomer was existing) over 30 minutes and mixed. Table 1 shows the mixing conditions at this time.

(Dissolution process)
The temperature of the prepared polymerizable monomer mixture is raised to 60 ° C., and then behenyl behenate is 13.75 parts by mass with respect to 100 parts by mass of the polymerizable monomer in the polymerizable monomer mixture. Was added to the stirring tank B. Furthermore, toner particles having a particle size outside the predetermined range are prepared for the purpose of adjusting the viscosity of the polymerizable monomer composition, and 8.00 parts by mass with respect to 100 parts by mass of the polymerizable monomer in the polymerizable monomer mixture. The polymerizable monomer composition was obtained by adding to the stirring tank B so as to be part by mass and continuing stirring.

  Table 1 shows the physical property values of the polymerizable monomer composition and the measurement and evaluation results of the obtained toner particles and toner.

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

(Mixing process)
Styrene 30.60 parts by mass n-butyl acrylate 15.80 parts by mass Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 4.60 parts by mass The mixture was stirred and sufficiently dissolved. The solution temperature after dissolution was 28 ° C. Furthermore, 56.49 parts by mass of the colorant dispersion was supplied into the stirring tank B while continuing the stirring, thereby preparing a polymerizable monomer mixture. Specifically, 564.9 kg of the colorant dispersion liquid is supplied into the stirring tank B (the liquid (501.0 kg) in which the additive is dissolved in the remaining polymerizable monomer is existing) over 30 minutes and mixed. It was. Table 1 shows the mixing conditions at this time.

(Dissolution process)
The temperature of the prepared polymerizable monomer mixture is raised to 60 ° C., and then behenyl behenate is 13.75 parts by mass with respect to 100 parts by mass of the polymerizable monomer in the polymerizable monomer mixture. Was added to the stirring tank B. Further, toner particles having a particle diameter outside the predetermined range for the purpose of adjusting the viscosity of the polymerizable monomer composition are added in an amount of 10.00 with respect to 100 parts by mass of the polymerizable monomer in the polymerizable monomer mixture. The polymerizable monomer composition was obtained by adding to the stirring tank B so as to be part by mass and continuing stirring.

  Table 1 shows the physical property values of the polymerizable monomer composition and the measurement and evaluation results of the obtained toner particles and toner.

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

(Mixing process)
Styrene 78.00 parts by mass n-butyl acrylate 17.00 parts by mass Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 5.00 parts by mass Salicylic acid compound aluminum complex (Orient) Bontron E-88 manufactured by Chemical Industry Co., Ltd.
0.86 mass part Said component was prepared to the stirring tank B, was stirred, and was fully dissolved. The solution temperature after dissolution was 28 ° C. Further, 6.10 parts by mass of the colorant dispersion liquid was supplied into the stirring tank B while continuing the stirring to prepare a polymerizable monomer mixed liquid. Specifically, 61.0 kg of the colorant dispersion was supplied into the stirring tank B (1008.6 kg of a solution obtained by dissolving an additive in the remaining polymerizable monomer) over 16 minutes and mixed. Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

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

(Mixing process)
Styrene 80.50 parts by mass n-butyl acrylate 17.00 parts by mass Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 5.00 parts by mass Salicylic acid compound aluminum complex (Orient Bontron E-88 manufactured by Chemical Industry Co., Ltd.
0.90 parts by mass The above ingredients were charged into the stirring tank B and stirred to dissolve sufficiently. The solution temperature after dissolution was 28 ° C. Further, 3.05 parts by mass of the colorant dispersion was supplied into the stirring tank B while continuing the stirring to prepare a polymerizable monomer mixture. Specifically, 30.5 kg of the colorant dispersion liquid was supplied into the stirring tank B (the existing solution of 1034.0 kg in which the additive was dissolved in the polymerizable monomer) over 8 minutes and mixed. Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

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

(Dispersion 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 20.0 parts by mass The above components were charged into the stirring tank A and treated in the same manner as in Example 1 to prepare a colorant dispersion. The liquid temperature of the obtained colorant dispersion was 27 ° C.

(Mixing process)
Styrene 58.00 parts by mass n-butyl acrylate 17.00 parts by mass Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 5.00 parts by mass Salicylic acid compound aluminum complex (Orient) Bontron E-88 manufactured by Chemical Industry Co., Ltd.
0.48 parts by mass The above ingredients were charged into the stirring tank B and stirred to dissolve sufficiently. The solution temperature after dissolution was 28 ° C. Furthermore, 35.48 parts by mass of the colorant dispersion was supplied into the stirring tank B while continuing the stirring to prepare a polymerizable monomer mixture. Specifically, 354.8 kg of the colorant dispersion liquid was fed into the stirring tank B (804.8 kg of the existing polymerizable monomer in which the additive was dissolved) was supplied over 20 minutes and mixed. Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

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

(Dispersion process)
Styrene 50.00 parts by mass Salicylic acid type compound aluminum complex (Bontron E-88 manufactured by Orient Chemical Co., Ltd.)
0.95 parts by mass Carbon black 20.00 parts by mass The above components were charged in the stirring tank A and treated in the same manner as in Example 1 to prepare a colorant dispersion. The liquid temperature of the obtained colorant dispersion was 27 ° C.

(Mixing process)
Styrene 33.00 parts by mass n-butyl acrylate 17.00 parts by mass Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 5.00 parts by mass The mixture was stirred and sufficiently dissolved. The solution temperature after dissolution was 28 ° C. Furthermore, 70.95 parts by mass of the colorant dispersion liquid was supplied into the stirring tank B while continuing the stirring to prepare a polymerizable monomer mixed liquid. Specifically, 709.5 kg of the colorant dispersion liquid was supplied into the stirring tank B (505.0 kg of a solution in which an additive was dissolved in the remaining polymerizable monomer was existing) over 61 minutes and mixed. Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

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

(Dispersion process)
Styrene 50.00 parts by mass Salicylic acid type compound aluminum complex (Bontron E-88 manufactured by Orient Chemical Co., Ltd.)
0.90 parts by mass Carbon black 20.00 parts by mass The above components were charged in the stirring tank A and treated in the same manner as in Example 1 to prepare a colorant dispersion. The liquid temperature of the obtained colorant dispersion was 27 ° C.

(Mixing process)
Styrene 29.70 parts by mass n-butyl acrylate 15.30 parts by mass Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 4.75 parts by mass The mixture was stirred and sufficiently dissolved. The solution temperature after dissolution was 28 ° C. Furthermore, 70.90 parts by mass of the colorant dispersion was supplied into the stirring tank B while continuing the stirring, thereby preparing a polymerizable monomer mixture. Specifically, 709.0 kg of the colorant dispersion liquid was supplied to the stirring tank B (497.5 kg of a solution in which an additive was dissolved in the remaining polymerizable monomer was existing) over 67 minutes and mixed. Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

<Example 9>
Toner particles were produced in the same manner as in Example 1 except that the dispersion step and the mixing step were performed under the following composition and mixing conditions.

(Dispersion process)
Styrene 50.00 parts by mass Salicylic acid type compound aluminum complex (Bontron E-88 manufactured by Orient Chemical Co., Ltd.)
0.95 parts by mass Carbon black 1.50 parts by mass The above components were charged into the stirring tank A and treated in the same manner as in Example 1 to prepare a colorant dispersion. The liquid temperature of the obtained colorant dispersion was 27 ° C.

(Mixing process)
Styrene 49.67 parts by mass n-butyl acrylate 17.00 parts by mass Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 5.00 parts by mass Salicylic acid compound aluminum complex (Orient) Bontron E-88 manufactured by Chemical Industry Co., Ltd.
0.32 parts by mass The above ingredients were charged into the stirring tank B and stirred to dissolve sufficiently. The solution temperature after dissolution was 28 ° C. Furthermore, 34.97 parts by mass of the colorant dispersion liquid was supplied into the stirring tank B while continuing the stirring to prepare a polymerizable monomer mixed liquid. Specifically, 349.7 kg of the colorant dispersion liquid was supplied to the stirring tank B (719.9 kg of a solution in which an additive was dissolved in the remaining polymerizable monomer was existing) over 5 minutes and mixed. At this time, the supply speed of the colorant dispersion was an upper limit speed in view of the inner diameter of the piping required for supply. Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

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

(Dispersion process)
Styrene 50.00 parts by mass Salicylic acid type compound aluminum complex (Bontron E-88 manufactured by Orient Chemical Co., Ltd.)
0.95 parts by mass Carbon black 22.50 parts by mass The above components were charged in the stirring tank A and treated in the same manner as in Example 1 to prepare a colorant dispersion. The liquid temperature of the obtained colorant dispersion was 27 ° C.

(Mixing process)
Styrene 60.78 parts by mass n-butyl acrylate 17.00 parts by mass Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 5.00 parts by mass Salicylic acid compound aluminum complex (Orient Bontron E-88 manufactured by Chemical Industry Co., Ltd.
0.53 mass part Said component was prepared to the stirring tank B, was stirred, and was fully dissolved. The solution temperature after dissolution was 28 ° C. Further, 32.64 parts by mass of the colorant dispersion was supplied into the stirring vessel B while continuing the stirring, thereby preparing a polymerizable monomer mixture. Specifically, 326.4 kg of the colorant dispersion was supplied into the stirring tank B (833.1 kg of a solution in which an additive was dissolved in the remaining polymerizable monomer was existing) over 20 minutes and mixed. Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

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

(Dispersion process)
Styrene 50.00 parts by mass Salicylic acid type compound aluminum complex (Bontron E-88 manufactured by Orient Chemical Co., Ltd.)
0.95 parts by mass Carbon black 1.00 parts by mass The above components were charged into the stirring tank A and treated in the same manner as in Example 1 to prepare a colorant dispersion. The liquid temperature of the obtained colorant dispersion was 27 ° C.

(Mixing process)
Styrene 33.00 parts by mass n-butyl acrylate 17.00 parts by mass Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 5.00 parts by mass The mixture was stirred and sufficiently dissolved. The solution temperature after dissolution was 28 ° C. Furthermore, 51.95 parts by mass of the colorant dispersion was supplied into the stirring tank B while continuing the stirring to prepare a polymerizable monomer mixture. Specifically, 519.5 kg of the colorant dispersion liquid was supplied into the stirring tank B (550 kg of an additive dissolved in the remaining polymerizable monomer is existing) over 8 minutes and mixed. At this time, the supply speed of the colorant dispersion was an upper limit speed in view of the inner diameter of the piping required for supply. Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

<Example 12>
In the mixing step, before supplying the colorant dispersion, the liquid temperature in the stirring tank B (existing liquid in which the additive is dissolved in the remaining polymerizable monomer) is 37 ° C., Toner particles were produced in the same manner as in Example 1. Table 1 shows mixing conditions in the mixing step, physical property values of the obtained polymerizable monomer composition, and measurement / evaluation results of toner particles and toner.

<Example 13>
In the mixing process, before supplying the colorant dispersion liquid, the liquid temperature in the stirring tank B (the liquid in which the additive is dissolved in the remaining polymerizable monomer is existing) is adjusted to 38 ° C. In the same manner as in Example 1, toner particles were produced.

  Table 1 shows mixing conditions in the mixing step, physical property values of the obtained polymerizable monomer composition, and measurement / evaluation results of toner particles and toner.

<Example 14>
In the mixing step, toner particles were produced in the same manner as in Example 1 except that the supply rate of the colorant dispersion was changed as follows.

  When preparing the polymerizable monomer mixture by supplying the colorant dispersion into the stirring tank B (the solution in which the additive is dissolved in the remaining polymerizable monomer is already present), The colorant concentration in the monomer mixture is a maximum of 1.67 parts by mass per unit time (min) as the amount of colorant per 100 parts by mass of the polymerizable monomer contained in the polymerizable monomer mixture. The feeding rate of the colorant dispersion was controlled so as to increase with the amount of change. Specifically, 609.5 kg of the colorant dispersion was supplied into the stirring tank B (550 kg of an additive in which the remaining polymerizable monomer was dissolved) over 11 minutes and mixed. Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

<Example 15>
Based on the production flow of FIG. 2, a polymerizable monomer mixture was prepared in a mixing step with a configuration in which the remaining polymerizable monomer was supplied into the colorant dispersion. Toner particles were produced in the same manner as in Example 1 except that the mixing step was as follows.

(Mixing process)
Styrene 33.00 parts by weight n-Butyl acrylate 17.00 parts by weight Terephthalic acid-propylene oxide modified bisphenol A polymer (average molecular weight: 7500, acid value: 10 mg KOH / g) 5.00 parts by weight The above components can be temperature controlled Into a stirring tank (referred to as stirring tank B) and stirred to dissolve sufficiently. The solution temperature after dissolution was 28 ° C.

  The liquid in the above stirring tank B (the one in which the additive is dissolved in the remaining polymerizable monomer) is supplied to the stirring tank A (the colorant dispersion is existing) and mixed, and the polymerizable monomer mixture is mixed. Was prepared. At this time, the concentration of the colorant in the polymerizable monomer mixture during preparation is determined as the amount of the colorant per 100 parts by mass of the polymerizable monomer contained in the polymerizable monomer mixture. The feed rate of the solution in which the additive was dissolved in the remaining polymerizable monomer was controlled so as to decrease by a maximum amount of change of 0.65 parts by mass. Specifically, 550.0 kg of a solution in which an additive was dissolved in the remaining polymerizable monomer was supplied into the stirring tank A (coloring agent dispersion 609.5 kg is existing) over 30 minutes and mixed.

  Table 1 shows the mixing conditions at this time. Further, FIG. 4 shows the transition of the colorant concentration (the amount of the colorant relative to 100 parts by mass of the polymerizable monomer) in the polymerizable monomer mixture during preparation and the amount of change in the colorant concentration per unit time (min). Shown in

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

<Example 16>
Based on the production flow of FIG. 2, a polymerizable monomer mixture was prepared in a mixing step with a configuration in which the remaining polymerizable monomer was supplied into the colorant dispersion. Toner particles were produced in the same manner as in Example 15 except that the mixing conditions were as follows.

  When preparing the polymerizable monomer mixture, the colorant concentration in the polymerizable monomer mixture during preparation is based on 100 parts by mass of the polymerizable monomer contained in the polymerizable monomer mixture. The supply rate of the liquid in which the additive was dissolved in the remaining polymerizable monomer was controlled so that the amount of the colorant was decreased by a maximum amount of 1.67 parts by mass per unit time (minute). Specifically, 550.0 kg of a solution in which an additive was dissolved in the remaining polymerizable monomer was supplied into the stirring tank A (coloring agent dispersion 609.5 kg is existing) over 11 minutes and mixed. . Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

<Comparative Example 1>
In the mixing step, toner particles were produced in the same manner as in Example 1 except that the supply rate of the colorant dispersion was changed as follows.

  When preparing the polymerizable monomer mixture by supplying the colorant dispersion into the stirring tank B (the solution in which the additive is dissolved in the remaining polymerizable monomer is already present), The colorant concentration in the monomer mixture is a maximum of 1.82 parts by mass per unit time (min) as the amount of colorant per 100 parts by mass of the polymerizable monomer contained in the polymerizable monomer mixture. The feeding rate of the colorant dispersion was controlled so as to increase with the amount of change. Specifically, 609.5 kg of the colorant dispersion was supplied into the stirring tank B (550 kg of a solution in which the additive was dissolved in the remaining polymerizable monomer was existing for 10 minutes) and mixed. Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

<Comparative example 2>
Based on the production flow of FIG. 2, a polymerizable monomer mixture was prepared in a mixing step with a configuration in which the remaining polymerizable monomer was supplied into the colorant dispersion. Toner particles were produced in the same manner as in Example 15 except that the mixing conditions were as follows.

  When preparing the polymerizable monomer mixture, the colorant concentration in the polymerizable monomer mixture during preparation is based on 100 parts by mass of the polymerizable monomer contained in the polymerizable monomer mixture. The supply rate of the remaining polymerizable monomer was controlled so that the amount of the coloring agent was decreased at a maximum amount of 1.82 parts by mass per unit time (minute). Specifically, 550.0 kg of the solution in which the additive was dissolved in the remaining polymerizable monomer was supplied into the stirring tank A (coloring agent dispersion 609.5 kg is existing) over 10 minutes and mixed. . Table 1 shows the mixing conditions at this time.

  In addition, Table 1 shows the physical property values of the obtained polymerizable monomer composition and the measurement and evaluation results of the toner particles and the toner.

Claims (6)

A dispersion step of dispersing a colorant in at least a part of the polymerizable monomer to obtain a colorant dispersion, and mixing the colorant dispersion with the remaining polymerizable monomer to obtain a polymerizable monomer mixture A method for producing polymerized toner particles, comprising a mixing step for obtaining a polymerizable monomer composition by dissolving at least a release agent in the polymerizable monomer mixture.
While preparing the polymerizable monomer mixture by supplying the colorant dispersion into the remaining polymerizable monomer, the colorant concentration in the polymerizable monomer mixture during the preparation is polymerizable. The colorant amount per 100 parts by mass of the polymerizable monomer contained in the monomer mixture is increased by a change amount of 1.67 parts by mass or less per unit time (minute). A method for producing polymerized toner particles. A dispersion step of dispersing a colorant in part of the polymerizable monomer to obtain a colorant dispersion, and mixing the remaining polymerizable monomer in the colorant dispersion, A method for producing polymerized toner particles, comprising a mixing step for obtaining a polymerizable monomer composition by dissolving at least a release agent in the polymerizable monomer mixture.
While preparing the polymerizable monomer mixture by supplying the remaining polymerizable monomer into the colorant dispersion, the colorant concentration in the polymerizable monomer mixture during the preparation is polymerizable. The colorant amount per 100 parts by mass of the polymerizable monomer contained in the monomer mixture is characterized by a decrease of 1.67 parts by mass or less per unit time (minute). A method for producing polymerized toner particles.   The method for producing polymerized toner particles according to claim 1 or 2, wherein the difference between the temperature of the colorant dispersion and the temperature of the remaining polymerizable monomer is within 10 ° C.   The colorant concentration in the colorant dispersion at the end of the dispersion step is 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. The method for producing polymerized toner particles according to any one of the above.   The colorant concentration in the polymerizable monomer composition is 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. The method for producing polymerized toner particles according to claim 1.   6. The method for producing polymerized toner particles according to claim 1, wherein the viscosity of the polymerizable monomer composition at 60 ° C. is 1 mPa · s or more and 25 mPa · s or less. .

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