JP5962011B2 - Method for producing toner for developing electrostatic image, method for producing developer for developing electrostatic image, method for producing toner cartridge, method for producing process cartridge, and image forming method - Google Patents

Description

  The present invention relates to an electrostatic charge image developing toner manufacturing method, an electrostatic charge image developing developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic latent image is formed on an image carrier by a charging and exposure process (latent image forming process), and an electrostatic charge image developing toner (hereinafter sometimes simply referred to as “toner”). The electrostatic latent image is developed with a developer for developing an electrostatic charge image (hereinafter sometimes referred to simply as “developer”) (development process), and visualized through a transfer process and a fixing process. The developer used here includes a two-component developer composed of a toner and a carrier, and a one-component developer using a magnetic toner or a nonmagnetic toner alone.

  The toner is usually prepared by melt-kneading a binder resin such as a thermoplastic resin together with a colorant such as a pigment, a charge control agent, a release agent such as a wax, cooling, pulverizing, and further classification. A grinding method is used.

  Further, as a means capable of intentionally controlling the toner shape, the toner surface structure, and the like in response to a demand for high image quality of the image, a toner manufacturing method by a wet manufacturing method has been proposed, and particularly aims for high image quality. Therefore, as a method for making the particle diameters as uniform as possible, for example, a suspension polymerization method, an emulsion polymerization aggregation method and the like are known.

  For example, Patent Document 1 discloses a magenta toner for developing electrostatic images containing a binder resin, a magenta pigment and a polar resin as C.I. I. Pigment violet 19 and C.I. I. Pigment red 122 or C.I. I. By using a solid solution pigment with Pigment Red 202, using a styrene polymer, a styrene copolymer, or the like as a binder resin, and using a resin having an acid value of 3 mgKOH / g or more and 20 mgKOH / g or less as a polar resin, Manufacturing is described. It is described that this toner has excellent triboelectric chargeability, an extremely clear color, excellent OHP transparency, and excellent manufacturing stability. Patent Document 2 includes an example in which the above solid solution is used in a kneading pulverization method, Patent Documents 3 to 5 illustrate an example in which a suspension polymerization method is used, and Patent Document 6 discloses an example in which an aggregation method is used. In both cases, magenta toner has been proposed.

JP-A-10-123760 JP 2007-094270 A Japanese Patent Laid-Open No. 2004-333892 JP 2004-333825 A Japanese Patent Application Laid-Open No. 11-084735 Japanese Patent Application Laid-Open No. 2011-215311

  An object of the present invention is to provide a method for producing a toner for developing an electrostatic image in which the release agent is less exposed on the toner surface and the decrease in fluidity of the toner is suppressed, and the electrostatic image containing the toner thus obtained The present invention provides a developing developer, a toner cartridge, a process cartridge using the developer, an image forming apparatus, and an image forming method.

The invention according to claim 1 includes a binder resin, a release agent, C.I. I. Pigment violet 19 and C.I. I. A solid solution with CI Pigment Red 122 or C.I. I. Pigment violet 19 and C.I. I. A mixed solution preparation step of preparing a mixed solution by dissolving or dispersing magenta pigment, which is a solid solution with Pigment Red 202, in an organic solvent, and preparing a suspension by dispersing and suspending the mixed solution in an aqueous medium a suspension preparation step of the solvent removal step of removing the solvent from said suspension, a drying step of drying the obtained toner particles, only including, the binder resin is a polyester having at least bisphenol skeleton This is a method for producing a toner for developing an electrostatic charge image, which is a resin .

The invention according to claim 2 is a method for producing a developer for developing an electrostatic image, wherein the developer for developing an electrostatic image is obtained by the method for producing toner for developing an electrostatic image according to claim 1. This is a method for producing a developer for developing an electrostatic image containing a toner for developing an electrostatic image.

According to a third aspect of the present invention, there is provided a toner cartridge manufacturing method, wherein the toner cartridge contains the electrostatic charge image developing toner obtained by the electrostatic charge image developing toner manufacturing method according to the first aspect. It is a manufacturing method of a cartridge.

Invention includes an image holding member, a developing means for forming a toner image by using a developer an electrostatic latent image formed on the surface of the image carrier, Ru with a process cartridge according to claim 4 The developer is a process cartridge manufacturing method which is an electrostatic charge image developing developer obtained by the electrostatic charge image developing developer manufacturing method according to claim 2.

The invention according to claim 5 is formed on the surface of the image carrier, a charging step for charging the surface of the image carrier, a latent image forming step for forming an electrostatic latent image on the surface of the image carrier. the electrostatic latent image is developed with a developer comprising a developing step of forming a toner image, and a transferring step of the transferring the developed toner image image to a transfer member, the developer, claim 2. An image forming method which is a developer for developing an electrostatic charge image obtained by the method for producing a developer for developing an electrostatic charge image according to 2.

  According to the first aspect of the present invention, there is provided an electrostatic charge image developing toner in which the exposure of the release agent to the toner surface is less and the decrease in the fluidity of the toner is suppressed as compared with the case without this configuration. can get.

According to the first aspect of the present invention, compared to the case where the binder resin does not have a bisphenol skeleton, the exposure of the release agent to the toner surface is less, and the electrostatic charge image in which the decrease in toner fluidity is suppressed. A developing toner is obtained.

According to the second aspect of the present invention, there is provided an electrostatic charge image developing toner in which the release agent is less exposed on the toner surface and the lowering of the toner fluidity is suppressed as compared with the case without this configuration. There is provided a method for producing a developer for developing an electrostatic charge image.

According to the third aspect of the present invention, there is provided an electrostatic image developing toner in which the release agent is less exposed on the toner surface and the lowering of the fluidity of the toner is suppressed as compared with the case without this configuration. A method of manufacturing a toner cartridge containing the toner cartridge is provided.

According to the fourth aspect of the present invention, there is provided an electrostatic charge image developing toner in which the release agent is less exposed on the toner surface and the lowering of the fluidity of the toner is suppressed as compared with the case without this configuration. A method of manufacturing a process cartridge containing the method is provided.

According to the fifth aspect of the present invention, there is provided an image forming method in which the exposure of the release agent to the toner surface is less than that in the case where the present configuration is not provided, and the decrease in toner fluidity is suppressed. .

It is a schematic structure figure showing an example of a process cartridge concerning an embodiment of the present invention. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an embodiment of the present invention.

  Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.

<Method for producing toner for developing electrostatic image>
A method for producing an electrostatic charge image developing toner according to an embodiment of the present invention includes a binder resin, a release agent, C.I. I. Pigment Violet 19 (hereinafter sometimes simply referred to as “PV19”) and C.I. I. Pigment Red 122 (hereinafter sometimes simply referred to as “PR122”) or C.I. I. Pigment violet 19 and C.I. I. A liquid mixture preparing step of preparing a liquid mixture by dissolving or dispersing magenta pigment, which is a solid solution with CI Pigment Red 202 (hereinafter sometimes simply referred to as “PR202”), in an organic solvent; A suspension preparation step of preparing a suspension by dispersing and suspending in a medium, a solvent removal step of removing the solvent from the suspension, and a drying step of drying the obtained toner particles are included. In general, such a method is called a “dissolution suspension method”.

  Conventionally, it has been difficult to control the structure of toner particles containing PV19 and PR122 as coloring agents or PV19 and PR202 as individual pigments, particularly the position of the release agent in the toner particles. Details are unknown, but because PV19 and PR122 or PV19 and PR202 are mixed crystals, the regularity of the crystal structure of the pigment is lower than that of each pigment alone, and the anisotropy is low. Although the dispersibility of the pigment in the binder resin contained in the toner is high, it is difficult to control the dispersion of other toner constituent materials, particularly the release agent inside the toner particles. Estimated to be easily exposed.

  The present inventors prepared a mixed liquid by dissolving or dispersing a binder resin, a release agent, and the solid solution in an organic solvent, using a solid solution of PV19 and PR122 or a solid solution of PV19 and PR202 as the composition of the pigment. A mixed liquid preparing step, a suspension preparing step of preparing a suspension by dispersing and suspending the mixed liquid in an aqueous medium, a solvent removing step of removing the solvent from the suspension, and the obtained toner particles It has been found that the structure of the toner particles, particularly the position of the release agent in the toner particles can be easily controlled by combining with a wet manufacturing method including a drying step of drying the toner. As a result, for example, there is little exposure of the release agent to the surface of the toner particles even under stress conditions, etc., and a decrease in toner fluidity is suppressed, and the powder transport in the transport path from the toner cartridge to the developing device or in the developing device Improves. Therefore, toner clogging in the conveyance path or the like is unlikely to occur, and a decrease in image density or the like is suppressed.

  The exposure amount of the release agent on the surface of the toner obtained by the toner manufacturing method according to the present embodiment is, for example, in the range of 1% to 10%.

  Hereinafter, an example of a toner manufacturing method according to the exemplary embodiment will be described.

[Mixed liquid preparation process]
First, a mixed solution is prepared by dissolving or dispersing a binder resin, a release agent, and a magenta pigment which is a solid solution of PV19 and PR122 or a solid solution of PV19 and PR202 as a colorant in an organic solvent (mixing) Liquid preparation step). In this mixed liquid preparation step, a toner material containing at least a binder resin, a colorant, and a release agent is dissolved or dispersed in an organic solvent to obtain a mixed liquid of toner materials.

  In addition to the binder resin, the colorant, and the release agent, the toner material may be appropriately mixed with a charge control agent or the like that is usually added to the toner particles as necessary. The mixed liquid of toner material may be prepared by kneading a binder resin with a colorant, a release agent, a charge control agent, or the like in advance in an organic solvent, or the binder resin may be dissolved in an organic solvent. After being dissolved therein, a colorant, a release agent, a charge control agent, etc. may be dispersed using a media-containing disperser such as a ball mill or a sand mill or a high-pressure disperser, or a colorant in an organic solvent in advance. The binder resin may be dissolved after the release agent or the charge control agent is dispersed using a media-containing disperser, a high-pressure disperser, an ultrasonic disperser, or the like. In this mixing step, any mixing method may be used as long as the binder resin and the release agent are dissolved in the organic solvent and the colorant is dissolved or dispersed.

  Organic solvents used for dissolving or dispersing the toner material include ester solvents such as methyl acetate and ethyl acetate, ketone solvents such as methyl ethyl ketone and methyl isopropyl ketone, aliphatic hydrocarbon solvents such as hexane and cyclohexane, dichloromethane and chloroform. And halogenated hydrocarbon solvents such as trichlorethylene. These organic solvents are those that dissolve the binder resin and have a ratio of dissolving in water of about 0 wt% or more and 30 wt% or less, and preferably have a boiling point of 100 ° C. or less. It is preferable not to use a polymerizable monomer such as styrene or acrylic acid. Further, in industrialization, it is particularly preferable to use ethyl acetate in consideration of work safety, cost, productivity, and the like. These organic solvents are preferably used so that the viscosity of the liquid mixture of toner materials is in the range of 1 mPa · s to 10,000 mPa · s at 20 ° C., and in the range of 1 mPa · s to 2,000 mPa · s. More preferably, it is used.

[Suspension preparation process]
Next, the liquid mixture obtained in the liquid mixture preparation step is dispersed and suspended in an aqueous medium to prepare a suspension (suspension preparation step).

  As the aqueous medium, it is preferable to use a medium in which an inorganic dispersant is dispersed in water. In order to make the particle size distribution of the toner particles as uniform as possible, it is preferable to disperse the inorganic dispersant in water and add a polymer dispersant that dissolves in water. The inorganic dispersant may be dispersed in water using a media-containing disperser such as a ball mill, a high-pressure disperser, an ultrasonic disperser, or the like. The polymer dispersant may be added by any method as long as it dissolves as uniformly as possible in water. The water used is usually ion exchange water, distilled water or pure water.

  As the inorganic dispersant, it is preferable to use a hydrophilic dispersant. Specific examples include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, clay, diatomaceous earth, bentonite, and the like. Calcium is preferred. Moreover, as for these inorganic dispersing agents, what the particle | grain surface is coat | covered with the polymer which has a carboxyl group is more preferable. In order to optimize the lipophilic hydrophilic balance, those coated with such a polymer have toner particles with a sharp particle size distribution, in which the dispersed particles hardly merge in the suspension preparation step of the toner material mixture. can get.

  As the polymer having a carboxyl group, the carboxyl group of an α, β-monoethylenically unsaturated carboxylic acid or α, β-monoethylenically unsaturated carboxylic acid is an alkali metal, alkaline earth metal, ammonium, amine, or the like. A copolymer of at least one selected from neutralized alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, and the like and α, β-monoethylenically unsaturated carboxylic acid ester, or α, Includes alkali metal salts, alkaline earth metal salts, ammonium salts or amine salts as described above of copolymers of β-monoethylenically unsaturated carboxylic acid and α, β-monoethylenically unsaturated carboxylic acid ester It is. These may be used alone or in combination of two or more.

  Representative α, β-monoethylenically unsaturated carboxylic acids include α, β-unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and α such as maleic acid, fumaric acid, and itaconic acid. , Β-unsaturated dicarboxylic acid. Representative examples of α, β-monoethylenically unsaturated carboxylic acid esters include acrylic acid, methacrylic acid and other alkyl esters, acrylates and methacrylates having alkoxy groups, and acrylates and methacrylates having cyclohexyl groups. , Acrylates and methacrylates having a hydroxy group, polyalkylene glycol monoacrylates, polyalkylene glycol monomethacrylates and the like. Those selected from α, β-monoethylenically unsaturated carboxylic acid esters represented by these are preferable.

  As the inorganic dispersant, those having a volume average particle diameter in the range of 1 nm to 1,000 nm are preferably used, more preferably in the range of 5 nm to 500 nm, and still more preferably in the range of 10 nm to 300 nm. . If the volume average particle diameter is less than 1 nm, it may be difficult to disperse the inorganic dispersant. If the volume average particle diameter exceeds 1,000 nm, the difference from the toner particle diameter becomes small, so that the oil phase component is stably dispersed and maintained. It may be difficult to do so. The amount of the inorganic dispersant used is preferably in the range of 1 to 300 parts by weight and more preferably in the range of 4 to 100 parts by weight with respect to 100 parts by weight of the toner. When the amount is less than 1 part by weight, the dispersibility and stability tend to be unstable, and when the amount exceeds 300 parts by weight, the viscosity of the aqueous phase component increases, and the stability of the dispersion suspension tends to decrease.

  As the polymer dispersant, a hydrophilic one is preferably used, and among those having a carboxyl group, those having no lipophilic group such as a hydroxypropoxyl group and a methoxyl group are preferable. Specifically, water-soluble cellulose ethers such as carboxymethyl cellulose and carboxyethyl cellulose are used, and carboxymethyl cellulose is particularly preferable. These celluloses preferably have a degree of etherification in the range of 0.6 to 1.5 and an average degree of polymerization in the range of 50 to 3,000. Further, the carboxyl group may be a metal salt such as sodium, potassium or magnesium. In order to sharpen the particle size distribution of the toner particles, the amount of the polymer dispersant used may be changed depending on the viscosity of the mixed liquid of the toner material (which varies depending on the ratio of the toner material and the organic solvent). For example, when the viscosity of the mixture of toner materials is relatively low, the viscosity of the aqueous medium need not be increased, and the amount of the polymer dispersant added may be small. On the other hand, when the viscosity of the mixture of toner materials is high, the amount of the polymer dispersant may be increased to increase the viscosity of the aqueous medium. The viscosity of the aqueous medium is preferably adjusted to be in the range of approximately 1 mPa · s to 3,000 mPa · s at 20 ° C., and is adjusted to be in the range of 1 mPa · s to 1,000 mPa · s. More preferably.

  As an apparatus used for a suspension preparation process, what is generally marketed as an emulsifier and a disperser is mentioned, for example, It does not specifically limit. For example, batch type emulsifiers such as Ultra Tarrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homomixer (manufactured by Special Machine Industries), National Cooking Mixer (manufactured by Matsushita Electric Industrial Co., Ltd.), Hagiwara Seisakusho Co., Ltd.), TK Pipeline Homomixer, TK Homomic Line Flow (made by Koki Kogyo Kogyo Co., Ltd.), Colloid Mill (made by Shinko Pantech Co., Ltd.), Slasher, Trigonal Wet Fine Crusher (Mitsui Miike Chemical Co., Ltd.), Batch or continuous dual-use emulsification such as continuous emulsifier such as Cavitron (Eurotech), fine flow mill (Pacific Kiko), Claremix (Mtechnic), Philmix (Special Machine Industries) Machine, microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), nano maker, nanomizer (manufactured by Nanomizer), APV High pressure emulsifiers such as phosphorus (manufactured by Gourin), membrane emulsifiers such as membrane emulsifiers (manufactured by Chilling Industries), vibratory emulsifiers such as vibratory mixers (manufactured by Chilling Industries), ultrasonic homogenizers (Branson) For example, an ultrasonic emulsifier.

[Solvent removal step]
Next, the solvent is removed from the suspension obtained in the suspension preparation step (solvent removal step). In this solvent removal step, the organic solvent, water, and the like in the suspension obtained in the suspension preparation step are removed. The solvent removal of the suspension may be performed immediately after the suspension preparation step. However, in order to make the particle size distribution of the obtained toner particles more uniform, the suspension is prepared in order to stabilize the particle size distribution. It is preferable to remove the solvent after 1 minute or more after the completion of the process. In this solvent removal process, the solvent contained in the droplets of the suspension is removed by cooling or heating the suspension obtained in the suspension preparation process, for example, in the range of 0 ° C. to 100 ° C. It is preferable. As a specific method for removing the solvent, any one of the following methods is preferably performed.
(1) A gas stream is sprayed on the suspension to forcibly update the gas phase on the surface of the suspension. In this case, gas may be blown into the suspension.
(2) The pressure is reduced to, for example, 10 mmHg or more and less than 760 mmHg. In this case, the gas phase on the surface of the suspension may be forcibly updated by purging the gas, or a gas may be blown into the suspension.

  If the inorganic dispersion stabilizer or the above-mentioned organic dispersion stabilizer (polymer dispersion agent) remains on the toner particle surface in the toner particles thus obtained, the residual adhering matter may absorb moisture. In addition, the humidity dependency of the chargeability as a toner and the powder fluidity may deteriorate. Therefore, it is preferable to remove such inorganic and organic dispersion stabilizers as much as possible in order to minimize the influence on the chargeability and powder flowability of the toner. The obtained toner particles are preferably washed with an acid such as hydrochloric acid, nitric acid, formic acid, acetic acid or the like that makes the inorganic dispersion stabilizer water-soluble after removing a small amount of residual solvent by drying. As a result, the inorganic dispersion stabilizer remaining on the toner particle surface is removed. Further, the polymer dispersant may be removed by washing with water or the like. The toner particles after the acid treatment may be neutralized with an alkali such as sodium hydroxide if necessary. If necessary, it may be recovered by an appropriate method such as filtration, decantation, or centrifugation, and may be further washed with water if necessary.

[Drying process]
Next, the toner particles obtained in the solvent removal step are dried (drying step). In this drying step, moisture and the like of the toner particles obtained in the solvent removal step are removed. In this drying step, it is preferable that the time for removing the moisture of the toner particles to 3% by weight or less is less than 10 minutes. Such rapid drying prevents internal contamination from oozing out onto the toner particle surface. Moreover, it is more preferable to use an air dryer as a dryer and to dry within 30 seconds.

  As an apparatus used for a drying process, what is generally marketed as a dryer or a dryer is mentioned, for example, It does not specifically limit.

  Further, if necessary, a step of removing a component such as an organic solvent of a very small amount of remaining toner particles, and a step of preparing toner particles by sieving may be included. In the organic solvent removal and sieving steps, any method may be used, and it is preferable that the toner particles be agglomerated or pulverized as much as possible.

<Toner for electrostatic image development>
(Constituent components of toner)
The toner particles in the electrostatic image developing toner according to this embodiment contain a binder resin, a colorant, a release agent, etc., and contain a solid solution of PV19 and PR122 or PV19 and PR202 as the colorant as described above. To do. The toner particles contain other components as necessary.

  Examples of the binder resin include a polyester resin. The polyester resin is synthesized from an acid (polyhydric carboxylic acid) component and an alcohol (polyhydric alcohol) component. In the present embodiment, the “acid-derived constituent component” The component part which was an acid component is pointed out, and the "alcohol-derived component" refers to the component part which was an alcohol component before the synthesis of the polyester resin.

[Acid-derived components]
The acid-derived component is not particularly limited, and aliphatic dicarboxylic acids and aromatic carboxylic acids are preferably used. Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid. 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc. Or lower alkyl esters and acid anhydrides thereof, but are not limited thereto. Examples of the aromatic carboxylic acid include lower alkyl esters and acid anhydrides of aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, and naphthalenedicarboxylic acid. Moreover, alicyclic carboxylic acids, such as cyclohexane dicarboxylic acid, etc. are mentioned. In order to secure better fixing properties, it is preferable to use a trivalent or higher carboxylic acid (trimellitic acid or acid anhydride thereof) together with a dicarboxylic acid in order to form a crosslinked structure or a branched structure. Specific examples of the alkenyl succinic acid include dodecenyl succinic acid, dodecyl succinic acid, stearyl succinic acid, octyl succinic acid, octenyl succinic acid and the like.

[Alcohol-derived components]
The alcohol-derived constituent component is not particularly limited, and examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like can be mentioned. In addition, diethylene glycol, triethylene glycol, neopentyl glycol, glycerin, alicyclic diols such as cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A Aromatic diols such as are used. Further, in order to ensure good fixability, a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane, pentaerythritol) may be used in combination with the diol in order to take a crosslinked structure or a branched structure.

  The method for producing the polyester resin is not particularly limited, and may be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. What is necessary is just to produce it properly according to a kind. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The polyester resin may be produced, for example, at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower, and may be reacted while removing the water and alcohol generated during condensation by reducing the pressure in the reaction system as necessary. . When the monomer is not dissolved or compatible at the reaction temperature, the polymerization reaction may be partially accelerated or delayed, and many uncolored particles may be generated. It may be added and dissolved as a solubilizer. The polycondensation reaction may be carried out while distilling off the solubilizing solvent. If there is a monomer with poor compatibility in the copolymerization reaction, the monomer with poor compatibility is preliminarily condensed with the acid or alcohol to be polycondensed and then polymerized together with the main component. It may be condensed.

  Catalysts that may be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metals such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium Compound; Phosphorous acid compound, phosphoric acid compound, amine compound and the like. Among these, for example, it is preferable to use a tin-containing catalyst such as tin, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, and diphenyltin oxide.

  In the present embodiment, a compound having a hydrophilic polar group may be used as long as it is copolymerizable as a resin for an electrostatic charge image developing toner. Specific examples include dicarboxylic acid compounds in which an aromatic ring such as sulfonyl-terephthalic acid sodium salt or 3-sulfonylisophthalic acid sodium salt is directly substituted when the resin used is a polyester.

  The weight average molecular weight Mw of the polyester resin is preferably 5,000 or more, and more preferably 5,000 or more and 50,000 or less. When this polyester resin is included, it is excellent in rubbing property. When the weight average molecular weight Mw of the polyester resin is less than 5,000, it may be easily separated in some cases, and thus problems derived from the released resin (filming, increase in fine powder due to brittleness, deterioration in powder fluidity, etc.) May occur.

  In the toner according to the exemplary embodiment, the resin other than the polyester resin is not particularly limited. Specifically, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, acrylic acid acrylic monomers such as n-propyl, butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc. Methacrylic monomers; Ethylene unsaturated acid monomers such as acrylic acid, methacrylic acid and sodium styrenesulfonate; Vinyl nitriles such as acrylonitrile and methacrylonitrile; Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether Tells; Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl isopropenyl ketone; Homopolymers of olefin monomers such as ethylene, propylene, and butadiene; Copolymers combining two or more of these monomers Or a mixture thereof, and further, an epoxy resin, a polyester resin, a polyurethane resin, a polyamide resin, a cellulose resin, a polyether resin, etc., a non-vinyl condensation resin, or a mixture of them with the vinyl resin, these Examples thereof include a graft polymer obtained by polymerizing a vinyl monomer in the coexistence. These resins may be used alone or in combination of two or more.

  In the present embodiment, the binder resin preferably has at least a bisphenol skeleton. Examples of the binder resin having a bisphenol skeleton include polyester resins using aromatic diols having a bisphenol skeleton such as ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A as alcohol-derived constituent components. .

  As the colorant, as described above, a solid solution of PV19 and PR122 or a solid solution of PV19 and PR202 is used. For example, as described in U.S. Pat. No. 3,160,510, the solid solution can be obtained by a method in which a solid solution component is simultaneously recrystallized from sulfuric acid or a suitable solvent and then solvent-treated, or German Patent Application Publication No. 1,217. No. 333, and may be obtained by a known method such as solvent treatment after cyclization of a suitably substituted diaminoterephthalic acid mixture. The mixing ratio of PV19 and PR122 or PV19 and PR202 in the solid solution may be appropriately determined according to the target color. For example, the weight ratio is 5:95 or more and 95: 5 or less. In addition to the solid solution of PV19 and PR122 or the solid solution of PV19 and PR202, other colorants such as PR48, PR57, PR170, PR221, and PR238 may be contained depending on the target color. What is necessary is just to determine suitably content of another coloring agent according to the target color. The content of these colorants is preferably from 0.1 to 40 parts by weight, more preferably from 1 to 30 parts by weight, based on 100 parts by weight of the binder resin.

  The toner according to the exemplary embodiment includes a release agent. Specific examples of the release agent include low molecular weight polyolefins such as polyethylene, polypropylene, polybutene, silicones having a softening point by heating, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, etc. Fatty acid amides, plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, fisher Examples thereof include minerals such as Tropsch wax, petroleum waxes, and modified products thereof. Among these, when the release agent is at least one of paraffin wax and ester wax such as carnauba, the effect of the method for producing an electrostatic charge image developing toner according to the present embodiment is more exhibited.

  These mold release agents can be used alone or in combination of two or more. The content of these release agents is preferably 1 part by mass or more and 10 parts by mass or less, and more preferably 5 parts by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the binder resin.

  There is no restriction | limiting in particular as another component, What is necessary is just to select suitably according to the objective, For example, well-known various additives, such as an inorganic particle and a charge control agent, etc. are mentioned.

  If necessary, inorganic particles may be added to the toner of this embodiment. As the inorganic particles, known inorganic particles such as silica particles, titanium oxide particles, alumina particles, cerium oxide particles, or those whose surfaces have been subjected to a hydrophobic treatment may be used alone or in combination of two or more types. Silica particles having a refractive index smaller than that of the binder resin are preferable from the viewpoint of not impairing transparency and transparency such as overhead projector (OHP) transparency. Further, the silica particles may be subjected to various surface treatments, and for example, those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, silicone oil or the like are preferable.

  By adding these inorganic particles, the viscoelasticity of the toner may be adjusted, and the glossiness of the image and the penetration into the paper may be adjusted. The inorganic particles are preferably contained in an amount of 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less based on 100 parts by mass of the toner raw material.

  A charge control agent may be added to the toner of the exemplary embodiment as necessary. As the charge control agent, a chromium-based azo dye, an iron-based azo dye, an aluminum azo dye, a salicylic acid metal complex, or the like may be used.

<Physical properties of toner for developing electrostatic image>
The volume average particle size of the toner for developing an electrostatic charge image according to the exemplary embodiment is preferably in the range of 3 μm to 10 μm, and more preferably in the range of 4 μm to 8 μm.

  The volume average particle diameter and the number average particle diameter are measured by measuring with an aperture diameter of 100 μm using a Coulter Multisizer II type (manufactured by Beckman-Coulter). At this time, the measurement is performed after the toner is dispersed in an electrolyte aqueous solution (isoton aqueous solution) and dispersed by ultrasonic waves for 30 seconds.

  The volume average particle size distribution index GSDv of the electrostatic image developing toner according to this embodiment is 1.27 or less, preferably 1.25 or less. When GSDv exceeds 1.27, the particle size distribution is not sharp, resolution is deteriorated, and image defects such as toner scattering and fogging may be caused.

The volume average particle diameter D50v and the volume average particle size distribution index GSDv are obtained as follows. Draw a cumulative distribution from the small diameter side for the volume and number of the particle size range (channel) divided based on the particle size distribution of the toner measured by the above-mentioned Coulter Multisizer II (manufactured by Beckman-Coulter). In addition, the particle diameter that is accumulated 16% is defined as volume D16v and several D16p, the particle diameter that is accumulated 50% is defined as volume D50v and several D50p, and the particle diameter that is accumulated 84% is defined as volume D84v and several D84p. At this time, D50v represents the volume average particle diameter, and the volume average particle size distribution index (GSDv) is obtained as (D84v / D16v) ^1/2 . In addition, (D84p / D16p) ^1/2 represents a number average particle size distribution index (GSDp).

In addition, the shape factor SF1 represented by the following formula of the toner for developing an electrostatic charge image according to the exemplary embodiment is preferably in the range of 110 to 140, more preferably in the range of 115 to 130.
SF1 = (ML ² / A) × (π / 4) × 100
[Where, ML represents the maximum length (μm) of toner, and A represents the projected area (μm ² ) of toner. ]
When the toner shape factor SF1 is smaller than 110 or exceeds 140, excellent chargeability, cleaning properties, and transferability may not be obtained over a long period of time.

The shape factor SF1 is measured as follows using a Luzex image analyzer (FT manufactured by Nireco Corporation). First, an optical microscopic image of toner spread on a slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length (ML) and projection area (A) of 50 toners are measured. ML ² / A) × (π / 4) × 100 is calculated, and a value obtained by averaging is calculated as the shape factor SF1.

<Developer for developing electrostatic image>
In this embodiment, the developer for developing an electrostatic image is not particularly limited except that it contains the toner for developing an electrostatic image obtained by the method for producing a toner for developing an electrostatic image according to the present embodiment. Accordingly, an appropriate component composition may be taken. The electrostatic charge image developing developer in the present embodiment is a one-component electrostatic charge image developing developer when the electrostatic charge image developing toner is used alone, or a two-component developer when used in combination with a carrier. It becomes a developer for developing an electrostatic image.

  For example, in the case of using a carrier, the carrier is not particularly limited, and examples thereof include known carriers. For example, resins described in JP-A Nos. 62-39879 and 56-11461 are disclosed. Known carriers such as a coated carrier can be used.

  Specific examples of the carrier include the following resin-coated carriers. Examples of the core particles of the carrier include normal iron powder, ferrite, and magnetite molding, and the volume average particle size is in the range of about 30 μm to 200 μm.

  Examples of the coating resin for the resin-coated carrier include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, acrylic acid 2 -Α-methylene fatty acid monocarboxylic acids such as ethylhexyl, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; nitrogen-containing acrylics such as dimethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, etc. Vinyl nitriles; vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl Homopolymers such as vinyl ketones such as ketones; olefins such as ethylene and propylene; vinyl-based fluorine-containing monomers such as vinylidene fluoride, tetrafluoroethylene and hexafluoroethylene; and copolymers composed of two or more types of monomers Furthermore, silicone resins containing methyl silicone, methyl phenyl silicone, etc., polyesters containing bisphenol, glycol, etc., epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins and the like can be mentioned. These resins may be used alone or in combination of two or more. The coating amount of the coating resin is preferably in the range of about 0.1 to 10 parts by weight and more preferably in the range of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the core particles. preferable.

  For the production of the carrier, a heating type kneader, a heating type Henschel mixer, a UM mixer or the like may be used. Depending on the amount of the coating resin, a heating type fluidized rolling bed, a heating type kiln or the like may be used.

  The mixing ratio of the electrostatic image developing toner of the present embodiment and the carrier in the developer for developing an electrostatic image is not particularly limited and may be appropriately selected according to the purpose.

<Toner cartridge>
The toner cartridge according to the present embodiment is not particularly limited as long as it contains the electrostatic image developing toner obtained by the method for producing the electrostatic image developing toner according to the present embodiment. For example, the toner cartridge is attached to and detached from an image forming apparatus including a developing unit, and as a toner to be supplied to the developing unit, a toner obtained by the method for manufacturing an electrostatic charge image developing toner according to the present embodiment is used. It is what is stored.

<Developer cartridge>
As long as the developer cartridge according to the present embodiment contains an electrostatic charge image developing developer including the electrostatic charge image developing toner obtained by the method of manufacturing an electrostatic charge image developing toner according to the present embodiment. Well, there are no particular restrictions. For example, the developer cartridge is attached to and detached from an image forming apparatus including a developing unit, and is obtained by the method for manufacturing an electrostatic charge image developing toner according to the present embodiment as a developer to be supplied to the developing unit. A developer for developing an electrostatic image containing toner is contained.

<Process cartridge>
The process cartridge according to the present embodiment only needs to contain an electrostatic charge image developing developer including the electrostatic charge image developing toner obtained by the method of manufacturing an electrostatic charge image developing toner according to the present embodiment. There is no particular limitation. The process cartridge includes, for example, an image carrier and a developing unit that develops an electrostatic latent image formed on the surface of the image carrier using a developer to form a toner image. The process cartridge according to the present embodiment includes a charging unit that charges the surface of the image holding member, a latent image forming unit that forms a latent image on the surface of the charged image holding member, and a surface of the image holding member, as necessary. Transfer means for transferring the formed toner image to the transfer body, image holding body cleaning means for removing residual toner remaining on the surface of the image holder after transfer, and cleaning, and transferred to the transfer body You may provide at least 1 selected from the group which consists of a fixing means for fixing a toner image.

  A schematic configuration of an example of a process cartridge according to an embodiment of the present invention is shown in FIG. 1, and the configuration will be described. The process cartridge 1 includes a photoconductor (electrophotographic photoconductor) 14 as an image carrier on which an electrostatic latent image is formed, a charging device 10 as a charging unit that charges the surface of the photoconductor 14, and a photoconductor 14. A developing device 16 as a developing means for forming a toner image by attaching toner to the electrostatic latent image formed on the surface, and the surface of the photoconductor 14 are contacted, and the residual remaining on the surface of the photoconductor 14 after transfer A cleaning blade 20 as an image carrier cleaning means that removes toner and cleans it is integrally supported, and is detachable from the image forming apparatus. When mounted on the image forming apparatus, an exposure device 12 as a latent image forming means for forming an electrostatic latent image on the surface of the photosensitive member 14 around the photosensitive member 14 by the charging device 10, laser light or reflected light of the document. The developing device 16, the transfer roll 18 serving as transfer means for transferring the toner image on the surface of the photoreceptor 14 to the recording paper 24 as a transfer target, and the cleaning blade 20 are arranged in this order. In FIG. 1, description of functional units normally required in other electrophotographic processes is omitted.

  The operation of the process cartridge 1 according to this embodiment will be described.

  First, the surface of the photoreceptor 14 is charged by the charging device 10 (charging process). Next, light is applied to the surface of the photoconductor 14 by the exposure device 12, and the charged charges in the exposed portion are removed, and an electrostatic latent image (electrostatic charge image) is formed according to the image information ( Latent image forming step). Thereafter, the electrostatic latent image is developed by the developing device 16, and a toner image is formed on the surface of the photoreceptor 14 (developing step). For example, in the case of a digital electrophotographic copying machine using an organic photosensitive member as the photosensitive member 14 and using a laser beam as the exposure device 12, the surface of the photosensitive member 14 is given a negative charge by the charging device 10, and the laser beam A digital latent image is formed in the form of dots by light, and toner is applied to the portion irradiated with the laser beam by the developing device 16 to be visualized. In this case, a negative bias is applied to the developing device 16. Next, a recording sheet 24 as a transfer object is superimposed on the toner image by the transfer roll 18, and the charge opposite in polarity to the toner is given to the recording sheet 24 from the back side of the recording sheet 24, and the toner image is formed by electrostatic force. It is transferred onto the recording paper 24 (transfer process). The transferred toner image is subjected to heat and pressure in a fixing device having a fixing roll 22 as fixing means, and is fused and fixed to the recording paper 24 (fixing step). On the other hand, the residual toner such as toner remaining on the surface of the photoconductor 14 without being transferred is removed by the cleaning blade 20 (image carrier cleaning step). One cycle is completed in a series of processes from the charging step to the image carrier cleaning step. In FIG. 1, the toner image is directly transferred to the recording paper 24 by the transfer roll 18, but may be transferred via an intermediate transfer member such as an intermediate transfer belt.

  As the charging device 10 that is a charging means, for example, a charger such as a corotron as shown in FIG. 1 is used, but a conductive or semiconductive charging roll may be used. A contact charger using a conductive or semiconductive charging roll may apply a direct current to the photoreceptor 14 or may apply an alternating current superimposed thereon. For example, the charging device 10 charges the surface of the photoconductor 14 by generating a discharge in a minute space near the contact portion with the photoconductor 14. Normally, it is charged to −300V or more and −1000V or less. The conductive or semiconductive charging roll may have a single layer structure or a multiple structure. Further, a mechanism for cleaning the surface of the charging roll may be provided.

  The photoreceptor 14 has a function of forming at least an electrostatic latent image (electrostatic charge image). In the electrophotographic photosensitive member, an undercoat layer, a charge generation layer containing a charge generation material, and a charge transport layer containing a charge transport material are formed in this order on the outer peripheral surface of a cylindrical conductive substrate as necessary. It is a thing. The order of stacking the charge generation layer and the charge transport layer may be reversed. These are laminated photoconductors in which a charge generation material and a charge transport material are contained in separate layers (charge generation layer, charge transport layer), but both the charge generation material and the charge transport material are the same. A single-layer type photoreceptor included in the above layer may be used, and a laminated photoreceptor is preferable. Further, an intermediate layer may be provided between the undercoat layer and the photosensitive layer. Further, a protective layer may be provided on the photosensitive layer. In addition, other types of photosensitive layers such as an amorphous silicon photosensitive film may be used in addition to the organic photoreceptor.

  The exposure apparatus 12 is not particularly limited. For example, a laser optical system that exposes a light source such as semiconductor laser light, LED (Light Emitting Diode) light, and liquid crystal shutter light on the surface of the photoconductor 14 in a desired image manner, Examples include optical system devices such as LED arrays.

  The developing unit has a function of developing the electrostatic latent image formed on the photoreceptor 14 with a one-component developer or a two-component developer containing an electrostatic charge image developing toner to form a toner image. Such a developing device is not particularly limited as long as it has the above-described functions, and may be appropriately selected depending on the purpose. Even a system in which the toner layer is in contact with the photoconductor 14 is not in contact with the system. It may be a thing. For example, as shown in FIG. 1, a developing device having a function of attaching toner for developing an electrostatic image to the photosensitive member 14 using the developing device 16, or developing having a function of attaching the toner to the photosensitive member 14 using a brush or the like. And a known developing device.

  As a transfer device as a transfer means, for example, a charge opposite in polarity to the toner is applied to the recording paper 24 from the back side of the recording paper 24, and the toner image is transferred to the recording paper 24 by electrostatic force, or as shown in FIG. A transfer roll and a transfer roll pressing device using a conductive or semiconductive roll or the like that directly transfers to the surface of the recording paper 24 via the recording paper 24 may be used. A direct current may be applied to the transfer roll as a transfer current applied to the image carrier, or an alternating current may be applied in a superimposed manner. The transfer roll may be arbitrarily set according to the width of the image area to be charged, the shape of the transfer charger, the opening width, the process speed (circumferential speed), and the like. Further, a single layer foam roll or the like is suitably used as a transfer roll for cost reduction. The transfer method may be a method of transferring directly to the recording paper 24 or a method of transferring to the recording paper 24 via an intermediate transfer member.

  A known intermediate transfer member may be used as the intermediate transfer member. Materials used for the intermediate transfer member include polycarbonate resin (PC), polyvinylidene fluoride (PVDF), polyalkylene phthalate, PC / polyalkylene terephthalate (PAT) blend material, ethylene tetrafluoroethylene copolymer (ETFE) / PC, ETFE / PAT, PC / PAT blend materials, and the like can be mentioned. From the viewpoint of mechanical strength, an intermediate transfer belt using a thermosetting polyimide resin is preferable.

  The image carrier cleaning means may be selected as appropriate as long as it removes residual toner on the image carrier and cleans it, and employs a blade cleaning method, a brush cleaning method, a roll cleaning method, or the like. . Among these, it is preferable to use a cleaning blade. Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber. Among them, it is particularly preferable to use a polyurethane elastic body because of its excellent wear resistance.

  The fixing device as the fixing unit is not particularly limited as long as the toner image transferred onto the recording paper 24 is fixed by heating, pressing, or heating and pressing. For example, a fixing device including a heating roll and a pressure roll is used.

  Examples of the recording paper 24 that is a transfer target to which the toner image is transferred include plain paper, an OHP sheet, and the like used in electrophotographic copying machines and printers. In order to further improve the smoothness of the image surface after fixing, it is preferable that the surface of the transfer material is as smooth as possible. For example, coated paper in which the surface of plain paper is coated with resin, art paper for printing, etc. Preferably used.

<Image forming apparatus>
As long as the image forming apparatus according to the present exemplary embodiment includes an electrostatic charge image developing developer including the electrostatic charge image developing toner obtained by the method of manufacturing the electrostatic charge image developing toner according to the present exemplary embodiment. Well, there are no particular restrictions. The image forming apparatus includes, for example, an image carrier, a charging unit that charges the surface of the image carrier, a latent image forming unit that forms an electrostatic latent image on the surface of the image carrier, and a surface formed on the surface of the image carrier. A developing unit that develops the electrostatic latent image using a developer to form a toner image; and a transfer unit that transfers the developed toner image to a transfer target. The image forming apparatus according to the present exemplary embodiment removes residual toner and the like remaining on the surface of the image holding member after transfer, and a fixing unit for fixing the toner image transferred to the transfer target, as necessary. And at least one selected from the group consisting of an image carrier cleaning means for cleaning. The image forming apparatus according to the present embodiment may use the process cartridge.

  FIG. 2 shows a schematic configuration of an example of the image forming apparatus according to the present embodiment, and the configuration will be described. The image forming apparatus 3 includes a photosensitive member 14 as an image carrier on which an electrostatic latent image is formed, a charging device 10 as a charging unit that charges the surface of the photosensitive member 14, and laser light or reflected light of a document. An exposure device 12 as a latent image forming unit that forms an electrostatic latent image on the surface of the photoconductor 14 and a developing unit that forms a toner image by attaching toner to the electrostatic latent image formed on the surface of the photoconductor 14. A developing device 16, a transfer roll 18 as a transfer means for transferring the toner image on the surface of the photoconductor 14 to a recording paper 24 as a transfer target, and the surface of the photoconductor 14, and the photoconductor after transfer. And a cleaning blade 20 as an image carrier cleaning means for removing residual toner and the like remaining on the surface of the image 14 for cleaning. In the image forming apparatus 3, a charging device 10, an exposure device 12, a developing device 16, a transfer roll 18, and a cleaning blade 20 are arranged around the photoconductor 14 in this order. In addition, a fixing device having a fixing roll 22 is provided as fixing means. In FIG. 2, functional units normally required in other electrophotographic processes are omitted. Each configuration of the image forming apparatus 3 and the operation during image formation are the same as those of the process cartridge 1 of FIG.

  The configurations of the process cartridge and the image forming apparatus according to the present embodiment are not limited to these, and conventionally known configurations may be applied as the configurations of the electrophotographic process cartridge and the image forming apparatus. That is, conventionally known ones are appropriately employed as necessary for the charging unit, latent image forming unit, developing unit, transfer unit, image carrier cleaning unit, charge eliminating unit, sheet feeding unit, transport unit, image control unit, and the like. The These configurations are not particularly limited in the present embodiment.

  Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.

(Preparation of magenta pigment solid solution 1)
2,5-Di- (4-methylphenylamino) terephthalic acid was cyclized in phosphoric acid to synthesize 2,9-dimethylquinacridone (CI Pigment Red 122). Water was added to the obtained phosphoric acid dispersion of 2,9-dimethylquinacridone, filtered through a filter, and further washed with water. Water was added again to the washed 2,9-dimethylquinacridone to obtain an aqueous dispersion having a solid content of 20% by mass. Similarly, an aqueous dispersion of quinacridone (CI Pigment Violet 19) having a solid content of 20% by mass was prepared using 2,5-di-phenylaminoterephthalic acid. 250 parts by mass of an aqueous dispersion of dimethylquinacridone (CI Pigment Red 122) having a solid content of 20% by mass and 250 parts by mass of an aqueous dispersion of quinacridone (CI Pigment Violet 19) having a solid content of 20% by mass 250 parts by mass of ethanol was added to prepare a pigment mixture. This mixed liquid was transferred to a container equipped with a condenser, and reacted for 4 hours under heating and reflux at 125 ° C. while grinding the pigment. After completion of the reaction, the pigment was filtered off from the reaction solution, washed, dried, and then pulverized to prepare a solid solution of PV19 and PR122.

(Preparation of magenta pigment solid solution 2)
PV19 and PR202 were prepared in the same manner as in the preparation of the magenta pigment solid solution 1, except that 2,5-di- (4-methylphenylamino) terephthalic acid was changed to 2,5-di- (3-chlorophenylamino) terephthalic acid. A solid solution was prepared.

<Example 1>
(Preparation of oil phase A-1)
As a release agent, 30 parts by weight of carnauba wax (manufactured by Toa Kasei Co., Ltd., RC160) was dissolved in 250 parts by weight of ethyl acetate, and then rapidly cooled and precipitated with liquid nitrogen to obtain an ethyl acetate dispersion of the release agent. The volume average particle size of the release agent was 0.1 μm as measured with a laser diffraction / scattering particle size distribution analyzer LA-700 (manufactured by Horiba, Ltd.). Polyester resin composed of bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, and terephthalic acid derivative (weight average molecular weight Mw: 20,000, glass transition temperature Tg: 66 ° C., melting temperature Tm: 106 ° C.) 100 6 parts by mass and 6 parts by mass of magenta pigment solid solution 1 and 80 parts by mass of ethyl acetate were mixed and dispersed in a ball mill for 10 hours, and then 36 parts by mass of an ethyl acetate dispersion of a release agent was added and stirred well until it was as uniform as possible. Let this liquid be A-1.

(Preparation of aqueous phase B-1)
On the other hand, 60 parts by mass of calcium carbonate and 40 parts by mass of water were mixed and dispersed with a ball mill for 10 hours to obtain a calcium carbonate dispersion. 7 parts by mass of this calcium carbonate dispersion and 100 parts by mass of a 2% aqueous solution of the polymer dispersant Serogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.) were added to a cooking mixer MX-915C (Matsushita Electric Co., Ltd.). And stirred for 5 minutes. This liquid is designated as B-1.

(Emulsification)
Using a stirrer, 50 parts by mass of the B-1 liquid and 50 parts by mass of the A-1 liquid were stirred and mixed to obtain a suspension. Thereafter, the solvent was removed at 35 ° C. under reduced pressure. Next, after adding 100 parts by mass of 6N hydrochloric acid to dissolve and remove calcium carbonate, washing with 5,000 parts by mass of water, drying at 45 ° C., and classification using an elbow jet classifier (manufactured by Matsuzaka Trading Co., Ltd.) Thus, toner particles having a volume average particle diameter of 6.8 μm were obtained.

(Toner preparation)
To 100 parts by mass of the toner particles prepared above, 1.2 parts by mass of hexamethyldisilazane-treated silica having a volume average particle diameter of 100 nm was added, and the mixture was added to a 5 L Henschel mixer agitator / mixer (Mitsui Miike Processing Co., Ltd.). Then, the mixture was further sieved with a wind sieving machine Hibolter NR300 (manufactured by Tokyo Kikai Co., Ltd.) (mesh opening: 45 μm) to obtain a toner. It was confirmed by a powder X-ray diffraction method that the toner contains a solid solution of PV19 and PR122 or a solid solution of PV19 and PR202.

(Preparation of developer)
4 parts by mass of toner and 96 parts by mass of Carrier A described below were stirred for 5 minutes with a V-type blender to prepare a developer. The carrier A used was prepared as follows. 1,000 parts by mass of Mn—Mg ferrite (volume average particle size: 50 μm, manufactured by Powder Tech Co., Ltd., shape factor SF1: 120) was added to a kneader, and a perfluorooctylmethyl acrylate-methyl methacrylate copolymer (polymerization ratio: 20). / 80, Tg: 72 ° C., weight average molecular weight: 72,000, manufactured by Soken Chemical Co., Ltd.) A solution prepared by dissolving 150 parts by mass in 700 parts by mass of toluene was added, mixed at room temperature for 20 minutes, and then heated to 70 ° C. After drying under reduced pressure, it was taken out to obtain a coat carrier. Furthermore, the obtained coated carrier was sieved with a mesh having an opening of 75 μm, and coarse powder was removed to obtain a carrier.

<Example 2>
(Preparation of aqueous phase B-2)
An aqueous phase B-2 was produced in the same manner as in Example 1 except that the calcium carbonate was changed to 0.4 parts by mass of sodium dodecylphenyl ether disulfonate.

(Emulsification)
Using a stirrer, 50 parts by mass of the B-2 liquid and 50 parts by mass of the A-1 liquid were stirred and mixed to obtain a suspension. Thereafter, the solvent was removed at 35 ° C. under reduced pressure. Washed with 5,000 parts by weight of water, washed with 10 parts by weight of 1N hydrochloric acid (pH 4.0), dried at 45 ° C., and classified using an elbow jet classifier (manufactured by Matsuzaka Trading Co., Ltd.). 6.8 μm toner particles 2 were obtained.

  In the same manner as in Example 1, a toner and a developer were prepared.

<Example 3>
Toner particles, toner, and developer were prepared in the same manner as in Example 1 except that the magenta pigment solid solution 2 was used instead of the magenta pigment solid solution 1.

<Example 4>
Toner particles, toner, and developer were prepared in the same manner as in Example 2 except that the magenta pigment solid solution 2 was used instead of the magenta pigment solid solution 1.

< Comparative Example 7 >
Similar to Example 1 except that a styrene-butyl acrylate copolymer resin (styrene-acrylic ratio 71:29, weight average molecular weight Mw: 22,000, glass transition temperature Tg: 60 ° C.) was used instead of the polyester resin. Thus, toner particles, toner and developer were prepared.

< Comparative Example 8 >
Similar to Example 2 except that a styrene-butyl acrylate copolymer resin (styrene-acrylic ratio 71:29, weight average molecular weight Mw: 25,000, glass transition temperature Tg: 62 ° C.) was used instead of the polyester resin. Thus, toner particles, toner and developer were prepared.

<Comparative Example 1>
Toner particles, toner, and developer were prepared in the same manner as in Example 1 except that 3 parts by mass of PV19 and 3 parts by mass of PR122 were used as pigments instead of the magenta pigment solid solution 1, respectively.

<Comparative example 2>
Toner particles, a toner, and a developer were prepared in the same manner as in Example 1 except that 3 parts by mass of PV19 and 3 parts by mass of PR202 were used as individual pigments instead of the magenta pigment solid solution 1.

<Comparative Example 3>
Toner particles, toner, and developer were prepared in the same manner as in Example 2 except that 3 parts by mass of PV19 and 3 parts by mass of PR122 were used as individual pigments in place of the magenta pigment solid solution 1.

<Comparative example 4>
Toner particles, toner, and developer were prepared in the same manner as in Example 2 except that 3 parts by mass of PV19 and 3 parts by mass of PR202 were used as pigments in place of the magenta pigment solid solution 1, respectively.

<Comparative Example 5>
The resin, mold release agent, and magenta pigment solid solution 1 used in Example 1 were put in a Banbury mixer (manufactured by Kobe Steel), pressure was applied so that the internal temperature became 110 ± 5 ° C., and kneading was performed at 80 rpm. 10 minutes. The obtained kneaded product is cooled, coarsely pulverized with a hammer mill, finely pulverized to 7.5 μm with a jet mill, and then classified with an elbow jet classifier (manufactured by Matsuzaka Trading Co., Ltd.). Toner and developer were prepared.

<Comparative Example 6>
The resin, mold release agent, and magenta pigment solid solution 2 used in Example 2 were put into a Banbury mixer (manufactured by Kobe Steel), pressure was applied so that the internal temperature became 110 ± 5 ° C., and kneading was performed at 80 rpm. 10 minutes. The obtained kneaded product is cooled, coarsely pulverized with a hammer mill, finely pulverized to 7.5 μm with a jet mill, and then classified with an elbow jet classifier (manufactured by Matsuzaka Trading Co., Ltd.). Toner and developer were prepared.

<Evaluation>
(Measurement of release agent exposure)
Using XPS (manufactured by JEOL Ltd.), the amount of release agent exposure on the toner surface (toner particle surface) was measured. The XPS conditions were photoelectron excitation: MgKα ray (10 kv, 30 mA), and photoelectron energy analyzer pass energy: 30 V. The results are shown in Table 1.

(Evaluation of toner fluidity)
After the developer thus obtained is set in a developing device of DocuCentreColor500 manufactured by Fuji Xerox Co., Ltd., toner for replenishment is set in each toner cartridge, and the developing toner amount of each single-color solid image on the paper is adjusted to 4.0 g / m ^2. A solid image corresponding to the tertiary color was output as a solid image having a size of 5 cm × 5 cm. As the paper, the product name “C2r paper” manufactured by Fuji Xerox Office Supply Co., Ltd. was used. Toner fluidity was evaluated according to the following criteria. The developing cartridge portion of the DocuCenterColor 500 manufactured by Fuji Xerox Co., Ltd. was taken out so that the cartridge motor could be operated by an external power source. The toner cut-out weight with respect to the driving time was measured. Based on the weight of toner cut out in 1 minute, it was marked as ◎ to ×. The results are shown in Table 1.
◎: 200 g or more ○: 150 g or more and less than 200 g Δ: 100 g or more and less than 150 g ×: less than 100 g

  With the toner of the example, when 50,000 continuous images with an area coverage of 100% (high density solid) were output continuously, the dispensing property from the toner cartridge and the toner supply to the developing device were made smooth. On the other hand, with the toner of the comparative example, when a document with the above area coverage of 100% (high density solid image) is continuously output, toner clogging occurs in the transport path supplied from the cartridge to the developing device within 100 sheets, and the image density A decrease in noise and noise due to the idle rotation of the gear between the developing machine gear and the dispense gear occurred.

  As described above, when the toner obtained by the method of the example was used, the exposure of the release agent to the toner surface was small, and the decrease in the fluidity of the toner was suppressed.

  DESCRIPTION OF SYMBOLS 1 Process cartridge, 3 Image forming apparatus, 10 Charging apparatus, 12 Exposure apparatus, 14 Photoconductor, 16 Developing apparatus, 18 Transfer roll, 20 Cleaning blade, 22 Fixing roll, 24 Recording paper.

Claims (5)

A binder resin, a release agent, and C.I. I. Pigment violet 19 and C.I. I. A solid solution with CI Pigment Red 122 or C.I. I. Pigment violet 19 and C.I. I. A mixed solution preparation step of preparing a mixed solution by dissolving or dispersing a magenta pigment which is a solid solution with Pigment Red 202 in an organic solvent;
A suspension preparation step of preparing a suspension by dispersing and suspending the mixed solution in an aqueous medium; and
A solvent removal step of removing the solvent from the suspension;
A drying step of drying the obtained toner particles;
Including
A method for producing a toner for developing an electrostatic charge image, wherein the binder resin is a polyester resin having at least a bisphenol skeleton. A method for producing a developer for developing an electrostatic image,
The developer for developing an electrostatic charge image, wherein the developer for developing an electrostatic charge image contains the toner for developing an electrostatic charge image obtained by the method for producing a toner for developing an electrostatic charge image according to claim 1 . Manufacturing method . A toner cartridge manufacturing method comprising:
The toner cartridge, the manufacturing method of the toner cartridge, characterized by containing a toner for developing electrostatic images obtained by the production method of the electrostatic image developing toner according to claim 1. An image holding member, a developing means for forming a toner image by an electrostatic latent image formed on the surface of the image carrier using a developer, a process for the preparation of a process cartridge Ru provided with,
3. The process cartridge manufacturing method according to claim 2, wherein the developer is an electrostatic image developing developer obtained by the method for manufacturing an electrostatic image developing developer according to claim 2. A charging step for charging the surface of the image carrier;
A latent image forming step of forming an electrostatic latent image on the surface of the image carrier;
A developing step of developing the electrostatic latent image formed on the surface of the image carrier using a developer to form a toner image;
A transfer step of transferring the developed toner image image to a transfer member,
With
The image forming method according to claim 2, wherein the developer is an electrostatic image developing developer obtained by the method for producing an electrostatic image developing developer according to claim 2.

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