JP5162866B2 - Toner manufacturing method and toner - Google Patents

Description

  The present invention relates to a toner manufacturing method, toner, developer, developer-containing container, image forming method, image forming apparatus, and process cartridge.

  In general, an electrophotographic method is an electrostatic latent image forming process in which an electrostatic latent image is formed on a photoconductor using a photoconductive substance by using various means, and the electrostatic latent image is developed using toner to form a toner. Development process for forming an image, transfer process for transferring a toner image to a transfer medium such as paper, and fixing for fixing the toner image transferred to the transfer medium to the transfer medium by heating, pressure, thermal pressure, solvent vapor, etc. And a cleaning process for removing toner remaining on the photosensitive member.

  On the other hand, toner used in electrophotography is required to be manufactured using a method that saves energy and has little influence on the environment. As a method for producing a toner, a melt kneading and pulverizing method is known, but in recent years, a chemical method for producing a toner in a solvent (for example, an emulsion aggregation method, a suspension polymerization method, a dispersion polymerization method, a dissolution suspension method). , Dissolution suspension extension method, etc.) are becoming mainstream. The suspension polymerization method is a method for producing a toner by dispersing a toner material containing a monomer, a polymerization initiator and the like in an aqueous medium to form oil droplets, and then performing a polymerization reaction by raising the temperature. is there. The emulsion aggregation method is a method for producing a toner by mixing a toner material containing a polymer or the like and an aqueous medium, emulsifying and dispersing, and then aggregating the mixture (see Patent Document 1). Further, the dissolution suspension method comprises a step of preparing a suspension by suspending an oily component obtained by adding a binder resin in an organic solvent in which the binder resin can be dissolved in an aqueous component to form a suspension. And a step of removing the organic solvent from the turbid liquid. As a toner manufactured using such a chemical method, a toner having a form capable of effectively expressing a desired function, such as a capsule toner and a core-shell toner, from the viewpoint of considering environmental problems in recent years. Are known.

  In the melt-kneading pulverization method, it is important to uniformly disperse and pulverize each constituent material in order to ensure the uniformity of the toner shape. However, the shape of the toner by the melt-kneading pulverization method is basically indefinite, and the pulverized cross section becomes random, so that it is difficult to control the shape and structure. In addition, when a large amount of additives such as a colorant, a release agent, and a charge control agent are added, when crushing, the additive is easily cleaved on the crystal plane of the additive, and the additive is easily exposed on the surface. In the toner, chargeability bias occurs, and the quality of toner characteristics such as fluidity and chargeability is deteriorated.

In contrast, the chemical method can produce a toner having a small particle size and a narrow particle size distribution. However, since the toner is granulated in water or in a hydrophilic solvent, the surface of the toner becomes hydrophilic, causing a decrease in chargeability and destabilization of aging / environmental characteristics. Toner scattering, image quality degradation, etc. occur. Furthermore, the chemical method has problems such as a large amount of waste liquid and a large energy for drying the toner, which is not preferable from the viewpoint of environmental load.
Japanese Patent No. 3141784

  In view of the above-described problems of the prior art, the present invention can produce a toner having excellent chargeability and aging / environmental characteristics at a low cost. An object is to provide a toner having excellent environmental characteristics. It is another object of the present invention to provide a developer containing the toner, a developer-containing container in which the developer is stored, an image forming method, an image forming apparatus, and a process cartridge for developing using the developer.

（式中、Ｒ _１ は、水素原子又はメチル基であり、Ｒ _２ は、メチレン基、エチレン基又は２−ヒドロキシプロピレン基であり、Ｒ _ｆ は、炭素数が４以上１０以下であるパーフルオロアルキル基を表す。）
で表される化合物であり、該界面活性剤は、重量平均分子量が４．０×１０ ^３ 以上２．１×１０ ^６ 以下であり、該流体は、超臨界二酸化炭素又は亜臨界二酸化炭素であることを特徴とする。 The invention of claim 1 is a method of manufacturing a toner by polymerization of a fluorine-based vinyl monomer in a pressure vessel, a step of synthesizing the surfactant, and the surfactant in said pressure vessel, by polymerizing a radical polymerizable monomer in a fluid containing a coloring agent and / or mold release agents, have a step of synthesizing a polymer which is insoluble in the fluid, the fluorine-based vinyl monomer of the general formula

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a methylene group, an ethylene group or a 2-hydroxypropylene group, and R _f is a perfluoroalkyl having 4 to 10 carbon atoms. Represents a group.)
The surfactant has a weight average molecular weight of 4.0 × 10 ³ or more and 2.1 × 10 ⁶ or less, and the fluid is supercritical carbon dioxide or subcritical carbon dioxide . It is characterized by that .

The invention described in claim 2 is the method for producing a toner according to claim 1, wherein the radical polymerizable monomer is characterized by being soluble in the fluid.

According to a third aspect of the present invention, in the toner production method according to the first or second aspect , the surfactant is represented by the general formula.

（式中、Ｒ_１は、水素原子又はメチル基であり、Ｒ_２は、メチレン基、エチレン基又は２−ヒドロキシプロピレン基であり、Ｒ_ｆは、炭素数が４以上１０以下であるパーフルオロアルキル基を表す。）
で表される構成単位を有することを特徴とする。

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a methylene group, an ethylene group or a 2-hydroxypropylene group, and R _f is a perfluoroalkyl having 4 to 10 carbon atoms. Represents a group.)
It has the structural unit represented by these .

According to a fourth aspect of the present invention, in the toner production method according to the third aspect , the surfactant has a composition ratio of the structural unit represented by the general formula of 20 mol% or more and 100 mol% or less. It is characterized by that .

The invention of claim 5 is a method of manufacturing a toner according to any one of claims 1 to 4, characterized in that the polymerization of the fluorine-based vinyl monomers in supercritical carbon dioxide.

According to a sixth aspect of the present invention, in the method for producing a toner according to any one of the first to fourth aspects , the fluorinated vinyl monomer is bulk polymerized .

According to a seventh aspect of the present invention, in the toner production method according to any one of the first to sixth aspects, a weight ratio of the radical polymerizable monomer to the surfactant is 10 or more and 1.0 × 10 ^4. It is characterized by the following .

According to an eighth aspect of the present invention, a toner is manufactured using the toner manufacturing method according to any one of the first to seventh aspects .

The invention according to claim 9 is the toner according to claim 8 , further comprising a charge control agent. Thereby, the charging property can be further improved.

According to a tenth aspect of the present invention, the developer contains the toner according to the eighth or ninth aspect .

According to an eleventh aspect of the present invention, the developer according to the tenth aspect further includes a carrier .

A twelfth aspect of the present invention is a container containing a developer, wherein the developer according to the tenth or eleventh aspect is accommodated in the container. Thereby, it is possible to provide a developer-containing container in which toner having excellent chargeability, aging and environmental characteristics is accommodated.

The invention according to claim 13, in the image forming method, forming a toner image by developing with a developer according to an electrostatic latent image formed on an image bearing member to claim 10 or 11, said image a step of transferring the toner image formed on the bearing member to a transfer member, the fixing member該被transfer member roller shape the transferred toner image on or belt form, to have a heating pressure fixing to step Features .

According to a fourteenth aspect of the present invention, in the image forming method according to the thirteenth aspect , an alternating electric field is applied when developing the electrostatic latent image formed on the image carrier. Features .

The invention according to claim 15, in the image forming apparatus is exposed and the image bearing member for bearing an electrostatic latent image, a charging unit that Ru charges the image carrier, the image carrier and the charging, electrostatic an exposure means for forming an electrostatic latent image, a developing means for forming a preparative toner image is developed with a developer according to an electrostatic latent image formed on the image bearing member to claim 10 or 11, the image bearing The image forming apparatus includes a transfer unit that transfers a toner image formed on the body to a transfer target , and a cleaning unit that cleans the image carrier on which the toner image is transferred to the transfer target .

The invention of claim 16 is the image forming apparatus according to claim 15, a heating body having a heating element, a film in contact with the heating body, pressurized to the heating member and pressure through the film The image forming apparatus further includes a fixing unit that includes a pressure member and heat-presses and fixes the transfer target body onto which the toner image is transferred between the film and the pressure member .

According to a seventeenth aspect of the present invention, in the process cartridge, a toner image is formed by developing the image carrier and the electrostatic latent image formed on the image carrier with the developer according to the tenth or eleventh aspect. the developing means integrally supported, and wherein the detachable der Turkey in the main body of the image forming apparatus.

  According to the present invention, it is possible to produce a toner having excellent chargeability and time / environmental characteristics at a low cost, and to provide a toner production method having a low environmental load and a toner having excellent chargeability, aging / environmental characteristics. be able to. In addition, it is possible to provide a developer containing the toner, a container containing a developer containing the developer, an image forming method, an image forming apparatus, and a process cartridge for developing using the developer.

  Next, the best mode for carrying out the present invention will be described with reference to the drawings.

  The toner production method of the present invention includes a synthesis step of synthesizing a surfactant in a pressure vessel and a fluid (supercritical fluid or subcritical fluid) containing the synthesized surfactant in the pressure vessel. It has at least a polymerization step for polymerizing the monomer, and may have other steps as necessary. At this time, in the polymerization step, particles containing a binder resin are formed. In the present invention, since the synthesis step and the polymerization step are performed in the same pressure vessel, the equipment can be saved and the toner can be manufactured at low cost.

  In the present invention, examples of the surfactant obtained in the synthesis step include a polymer (homopolymer or copolymer) obtained by polymerizing a fluorinated vinyl monomer. The fluorine-based vinyl monomer can be appropriately selected depending on the purpose, and examples thereof include acrylic acid derivatives and methacrylic acid derivatives having a perfluoroalkyl group.

  The polymer obtained by polymerizing the fluorinated vinyl monomer has the general formula (1)

で表される構成単位を有することが好ましい。このとき、重合体中の一般式（１）で表される構成単位の組成比は、２０〜１００モル％であることが好ましい。この組成比が２０モル％未満であると、超臨界流体又は亜臨界流体に対する界面活性能が不十分となることがある。また、フッ素系ビニルモノマーは、一般式（２）

It is preferable to have the structural unit represented by these. At this time, it is preferable that the composition ratio of the structural unit represented by General formula (1) in a polymer is 20-100 mol%. When the composition ratio is less than 20 mol%, the surface activity for the supercritical fluid or subcritical fluid may be insufficient. The fluorine-based vinyl monomer is represented by the general formula (2)

で表される化合物であることが好ましい。なお、一般式（１）及び（２）において、Ｒ_１は、水素原子又はメチル基であり、Ｒ_２は、メチレン基、エチレン基又は２−ヒドロキシプロピレン基であり、Ｒ_ｆは、炭素数が４以上１０以下であるパーフルオロアルキル基である。

It is preferable that it is a compound represented by these. In general formulas (1) and (2), R ₁ is a hydrogen atom or a methyl group, R ₂ is a methylene group, an ethylene group, or a 2-hydroxypropylene group, and R _f has a carbon number. It is a perfluoroalkyl group that is 4 or more and 10 or less.

  When the surfactant is synthesized in the synthesis step, it can be polymerized in a fluorinated solvent such as HCFC225, but it is preferably polymerized in supercritical carbon dioxide or bulk polymerized. Thereby, environmental load can be reduced.

The weight average molecular weight of the surfactant is preferably 4.0 × 10 ^{3 to} 2.1 × 10 ⁶ , more preferably 1.0 × 10 ^{4 to} 8.0 × 10 ⁶ , and 5.0 × 10 6. ^{4 to} 5.0 × 10 ⁶ is particularly preferable. When the weight average molecular weight is less than 4.0 × 10 ^{3 or} more than 2.1 × 10 ⁶ , the surface active ability may be insufficient.

  The number average molecular weight and weight average molecular weight of the surfactant can be measured under the following conditions using GPC (gel permeation chromatography).

Apparatus: HLC-8220-GPC (manufactured by Tosoh Corporation)
Column: TSK-gel GMH HR-M (manufactured by Tosoh Corporation)
Temperature: 40 ° C
Solvent: HFIP (hexafluoropropanol)
Flow rate: 0.2 ml / min Sample solution injection volume: 10 μl
The sample solution is prepared by dissolving the sample in a HFIP (hexafluoropropanol) solution prepared so that the concentration of CF ₃ COONa is 5 mM so that the concentration is 0.15% by weight. Next, GPC measurement is performed under the following measurement conditions. The molecular weight calibration curve is prepared using a monodisperse polystyrene standard sample.

  In the present invention, the monomer used in the polymerization step can be appropriately selected depending on the purpose as long as the binder resin obtained by polymerization can form an image, but vinyl monomer, styrene, etc. It is preferable that it is a radically polymerizable monomer. Such a monomer is preferably soluble in at least one of a supercritical fluid and a subcritical fluid. Moreover, it is preferable that the polymer obtained by polymerizing such a monomer is insoluble in at least one of a supercritical fluid and a subcritical fluid.

  A supercritical fluid exists as a non-condensable high-density fluid in a temperature and pressure range that exceeds the limit (critical point) at which gas and liquid can coexist, does not cause condensation even when compressed, is above the critical temperature, and is critical As long as the fluid is in a pressure or higher state, it can be appropriately selected according to the purpose, but a fluid having a low critical temperature is preferable. The subcritical fluid can be appropriately selected according to the purpose as long as it exists as a high-pressure liquid in the temperature / pressure region near the critical point.

  In the present invention, examples of the supercritical fluid include carbon monoxide, carbon dioxide, ammonia, nitrogen, water, methanol, ethanol, ethane, propane, 2,3-dimethylbutane, benzene, chlorotrifluoromethane, and dimethyl ether. It is done. Of these, carbon dioxide is preferred. Since carbon dioxide has a critical pressure of 7.3 MPa and a critical temperature of 31 ° C., it can easily be brought into a supercritical state, and is nonflammable, so that it is easy to handle. Also, since carbon dioxide is non-aqueous, the toner characteristics are good. A material that can be used as a supercritical fluid can also be used as a subcritical fluid. The supercritical fluid and subcritical fluid may be a single substance or a mixture.

  The critical temperature and critical pressure of the supercritical fluid are not particularly limited and may be appropriately selected depending on the intended purpose. The critical temperature is preferably −273 to 300 ° C., particularly 0 to 200 ° C. preferable.

In addition, other fluids can be used in combination with the supercritical fluid or the subcritical fluid. As the other fluid, a fluid that can easily control the solubility of the material constituting the toner is preferably used, and examples thereof include N ₂ O, ethane, propane, and ethylene.

  Moreover, an organic solvent can also be used together as an entrainer with a supercritical fluid or a subcritical fluid. This makes it easier to control the solubility of the material constituting the toner. The entrainer can be appropriately selected according to the purpose, and examples thereof include methanol, ethanol, propanol, ammonia, melamine, urea, thioethylene glycol and the like.

  In the present invention, a polymerization initiator can be used when the monomer is polymerized. The polymerization initiator can be appropriately selected in consideration of the reaction temperature and the 10-hour half-life. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero) Nitrile) and other azo polymerization initiators, and peroxide initiators such as lauryl peroxide, benzoyl peroxide, t-butyl peroctoate, and potassium persulfate. The polymerization initiator may be used in combination with sodium thiosulfate, amine or the like.

  The polymerization initiator is preferably added in an amount of 0.1 to 10% by weight based on the monomer. In order to polymerize the monomer at a high polymerization rate, the polymerization is preferably performed for 5 to 40 hours. However, in order to obtain a toner having a desired particle size distribution, the polymerization may be stopped halfway. Furthermore, in order to adjust the molecular weight, a compound having a large chain transfer constant may be added for polymerization. Examples of the compound having a large chain transfer constant include a low molecular compound having a mercapto group, carbon tetrachloride, carbon tetrabromide and the like.

  The pressurizing condition in the polymerization step is preferably 8 to 100 MPa, and more preferably 10 to 50 MPa. If the pressurization condition is less than 8 MPa, the amount of the surfactant dissolved decreases and the surface activity ability tends to be insufficient, so that it becomes impossible to stably obtain particles containing the binder resin, or the reaction. The monomer concentration in the system cannot be increased, resulting in inefficient production conditions. When it exceeds 100 MPa, the apparatus cost concerning a pressure | voltage resistant installation may become high, and the particle | grains containing binder resin may become easy to swell or melt | dissolve.

  Moreover, it is preferable that the heating conditions in a superposition | polymerization process are 10-180 degreeC, 30-150 degreeC is further more preferable, and 35-130 degreeC is especially preferable. When the heating condition is less than 10 ° C, the reaction time may be prolonged or the polymerization conversion rate may be lowered. When it exceeds 180 ° C, particles containing the binder resin can be stably obtained. It may disappear, and manufacturing energy and manufacturing cost may increase.

In the present invention, the smaller the addition amount of the surfactant in the polymerization step, the lower the production cost. Therefore, the weight ratio of the monomer to the surfactant is preferably 10 to 1.0 × 10 ⁴ . When this weight ratio exceeds 10,000, particles containing a binder resin may not be obtained. When the weight ratio is less than 10, the production cost increases and becomes impractical.

In the present invention, the weight average molecular weight of the binder resin obtained in the polymerization step is preferably 1000 or more, more preferably 2000 to 1.0 × 10 ⁷ , and particularly preferably 3000 to 1.0 × 10 ⁶ . When the weight average molecular weight of the binder resin is less than 1000, the hot offset resistance may be lowered.

  The number average molecular weight and the weight average molecular weight of the binder resin can be measured using GPC under the following conditions.

Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
Temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 ml / min Concentration of sample solution: 0.05 to 0.6% by weight
Sample solution injection volume: 0.1 ml
The molecular weight calibration curve is created using a monodisperse polystyrene standard sample.

  The glass transition temperature of the binder resin is preferably 30 to 85 ° C, and more preferably 40 to 75 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 85 ° C., the low-temperature fixability may be insufficient.

  The additive that can be added to the toner of the present invention can be appropriately selected according to the purpose. For example, a colorant, a release agent, inorganic particles, a charge control agent, a fluidity improver, and a cleaning property improvement. Agents and the like. In the polymerization step, when the monomer is polymerized, the fluid (supercritical fluid or subcritical fluid) preferably further contains at least one of a colorant and a release agent. Thereby, a toner having good dispersibility of at least one of the colorant and the release agent can be obtained.

  The colorant can be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium Yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG) , Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para red, phisa red, Lachloroorthonitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX , Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y , Alizarin lake, thioindigo red B, thioindigo maroon, oil red, quinacridone , Pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, Indanthrene blue (RS, BC), indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Tog Lean lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon and the like may be mentioned, and two or more kinds may be used in combination.

  The content of the colorant in the toner can be appropriately selected according to the purpose, but is preferably 0.1 to 15% by weight, and more preferably 1 to 10% by weight. When the content of the colorant is less than 0.1% by weight, the coloring power of the toner may be reduced. When the content exceeds 15% by weight, poor dispersion of the pigment in the toner occurs. Electrical characteristics may deteriorate.

  The colorant may be used as a master batch combined with a resin. The resin can be appropriately selected from known resins according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate, poly Vinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester resin, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral resin, polyacrylic acid, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, fat A cyclic hydrocarbon resin, an aromatic petroleum resin, chlorinated paraffin, paraffin, etc. are mentioned, and two or more kinds may be used in combination.

  Examples of the styrene or substituted polymer thereof include polystyrene, poly (p-chlorostyrene), and polyvinyl toluene. As the styrene copolymer, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate Copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile- Indene copolymer, styrene-mer Ynoic acid copolymer, styrene - maleic acid ester copolymers and the like.

  The master batch can be manufactured by mixing and kneading the resin and the colorant under high shearing force. At this time, it is preferable to add an organic solvent in order to improve the interaction between the colorant and the resin. Further, it is preferable to produce a master batch by the flushing method because a wet cake of a colorant can be used directly and it is not necessary to dry. The flushing method is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin to remove moisture and the organic solvent. For mixing and kneading, it is preferable to use a high shearing dispersion device such as a three-roll mill.

  In the present invention, the particles containing the binder resin obtained in the polymerization step can be dyed using an entrainer, but the entrainer is an organic solvent in which the binder resin does not dissolve or an organic solvent that swells slightly. It is preferable that Specifically, the difference in solubility parameter (hereinafter referred to as SP) between the entrainer and the binder resin is preferably 1.0 or more, and more preferably 2.0 or more. For example, for styrene-acrylic resins, methanol, ethanol, n-propanol or the like having a high SP, or n-hexane, n-heptane or the like having a low SP can be used. At this time, if the difference in SP exceeds 5, the wetness of the entrainer with respect to the particles containing the binder resin is deteriorated and the dispersibility is lowered.

  The dye used for dyeing may have a ratio (D1 / D2) of the solubility D1 in the entrainer and the solubility D2 in the organic solvent capable of dissolving the binder resin (D1 / D2) is 0.5 or less. In order to increase body resistance, it is preferable to use disperse dyes, oil-soluble dyes, vat dyes, and the like, and oil-soluble dyes are particularly preferable. Also, several kinds of dyes can be used depending on the coloring. Note that when the powder resistance is lowered, the transfer rate may be lowered.

  As a dyeing method, particles containing a binder resin, a dye and an entrainer are placed in a pressure vessel, and the treatment is performed in a supercritical fluid, or particles and a dye containing a binder resin are contained in a pressure vessel. There is a method in which a solution obtained by dissolving or dispersing in an entrainer is added and the treatment is performed in a supercritical fluid.

  The weight ratio of the dye to the binder resin can be appropriately selected according to the degree of coloring, but is usually 1 to 50%.

  Examples of the dye include C.I. I. SOLVENT YELLOW (6, 9, 17, 31, 35, 100, 102, 103, 105), C.I. I. SOLVENT ORANGE (2, 7, 13, 14, 66), C.I. I. SOLVENT RED (5, 16, 17, 18, 19, 22, 23, 143, 145, 146, 149, 150, 151, 157, 158), C.I. I. SOLVENT VIOLET (31, 32, 33, 37), C.I. I. SOLVEN BLUE (22, 63, 78, 83-86, 191, 194, 195, 104), C.I. I. SOLVEN GREEN (24, 25), C.I. I. SOLVENT BROWN (3, 9) and the like.

  Commercially available dyes include Aizen SOT dyes Yellow-1,3,4, Orange-1,2,3, Scallet-1, Red-1,2,3, Brown-2, Blue-1, 2, Violet-1, Green-1, 2, 3, Black-1, 4, 6, 8 (above, manufactured by Hodogaya Chemical Co., Ltd.), Sudan dye Yellow-146, 150, Orange-220, Red-290, 380, 460, Blue-670 ( Above, manufactured by BASF), Dialresin Yellow-3G, F, H2G, HG, HC, HL, Orange-HS, G, Red-GG, S, HS, A, K, H5B, Violet-D, Blue-J, G, N, K, P, H3G, 4G, Green-C, Brown-A (above, manufactured by Mitsubishi Kasei), oil color Yellow-3G, G -S, # 105, Orange-PS, PR, # 201, Scarlet- # 308, Red-5B, Brown-GR, # 416, Green-BG, # 502, Blue-BOS, IIN, Black-HBB, # 803 , EB, EX (above, manufactured by Orient Chemical Industries), Sumiplast Blue GP, OR, Red FB, 3B, Yellow FL7G, GC (above, manufactured by Sumitomo Chemical Co., Ltd.), Kayalon Polyester Black EX-SF300, Kaya Set Red -B, blue A-2R (manufactured by Nippon Kayaku Co., Ltd.) and the like.

  The release agent can be appropriately selected from known release agents according to the purpose, and for example, waxes can be used. Examples of waxes include low molecular weight polyolefin waxes, synthetic hydrocarbon waxes, natural waxes, petroleum waxes, higher fatty acids and their metal salts, higher fatty acid amides, and various modified waxes thereof. May be.

  Examples of the low molecular weight polyolefin wax include a low molecular weight polyethylene wax and a low molecular weight polypropylene wax. Examples of the synthetic hydrocarbon wax include Fischer-Tropsch wax. Examples of natural waxes include beeswax, carnauba wax, candelilla wax, rice wax, and montan wax. Examples of petroleum waxes include paraffin wax and microcrystalline wax. Examples of higher fatty acids include stearic acid, palmitic acid, myristic acid and the like.

  The melting point of the release agent is preferably 40 to 160 ° C, more preferably 50 to 120 ° C, and particularly preferably 60 to 90 ° C. If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability. If it exceeds 160 ° C., cold offset is likely to occur during low-temperature fixing, and paper wrapping around the fixing machine may occur. is there.

  The content of the release agent in the toner is preferably 0 to 40% by weight, and more preferably 3 to 30% by weight. When the content of the release agent exceeds 40% by weight, the low-temperature fixability may be deteriorated or the image quality may be deteriorated due to excessive glossiness.

  The inorganic particles can be appropriately selected from known inorganic particles according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide , Tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride 2 or more may be used in combination.

The average primary particle size of the inorganic particles is preferably 5 nm to 2 μm, more preferably 5 to 500 nm. Moreover, it is preferable that the specific surface area by BET method of an inorganic particle is 20-500 m < ² > / g.

  The content of inorganic particles in the toner is preferably 0.01 to 5.0% by weight, more preferably 0.01 to 2.0% by weight.

  The inorganic particles can be used as an external additive for the toner.

  The charge control agent can be appropriately selected from known charge control agents according to the purpose. However, when a colored material is used, the color tone may change. Therefore, a colorless or nearly white material is preferable. Such materials include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts). , Alkylamide, simple substance or compound of phosphorus, simple substance or compound of tungsten, fluorine-based surfactant, metal salt of salicylic acid, metal salt of salicylic acid derivative, and the like. In addition, although a metal can be suitably selected according to the objective, aluminum, zinc, titanium, strontium, boron, silicon, nickel, iron, chromium, zirconium etc. are mentioned.

  Commercially available charge control agents include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (above, Orient TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, copy charge NEG VP2036, copy charge NX VP434 , Copy blue PR of a triphenylmethane derivative (above, manufactured by Hoechst), LRA-901, LR-147 (above, made by Nippon Carlit), quinacridone, azo pigment, other sulfonic acid, carboxylic acid, Examples thereof include a polymer compound having a quaternary ammonium salt.

  The content of the charge control agent in the toner can be appropriately selected depending on the type of binder resin, the type of additive, the dispersion method, and the like, but is 0.1 to 10% by weight with respect to the binder resin. 1 to 5% by weight is more preferable. When the content of the charge control agent is less than 0.1% by weight, the chargeability of the toner may be lowered. On the other hand, if it exceeds 10% by weight, the chargeability of the toner becomes too high, the effect of the main charge control agent may be reduced, and the electrostatic attractive force with the developing roller may increase. As a result, the fluidity of the developer is lowered and the image density is lowered.

  Examples of the fluidity improver include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. It is done. When surface treatment is performed using a fluidity improver, the hydrophobicity of the toner can be improved, and a decrease in fluidity and chargeability can be suppressed even under high humidity.

  Examples of the cleaning improver include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, and resin particles obtained by soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles. The resin particles preferably have a narrow particle size distribution, and preferably have a weight average particle size of 0.01 to 1 μm. When a cleaning property improving agent is added to the toner, it becomes easy to remove the toner after transfer remaining on the photoreceptor or the primary transfer medium.

  Methods for adding the additive include a method of adding in the polymerization step, a method of melt kneading with the master batch and then adding in the polymerization step, a method of fixing to the surface of the particles containing the binder resin after the polymerization step, and the like. Can be mentioned.

  The toner of the present invention is not particularly limited with respect to shape, size, etc., and can be appropriately selected according to the purpose. However, the following thermal characteristics, image density, average circularity, weight average particle diameter, etc. The number average particle diameter is preferred.

  Thermal characteristics are also called flow tester characteristics, and are evaluated as softening temperature, outflow start temperature, 1/2 method softening point, and the like. These thermal characteristics can be measured by an appropriately selected method, and can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).

  The softening temperature of the toner is preferably 50 ° C. or higher, and more preferably 80 to 120 ° C. When the softening temperature is less than 50 ° C., the heat resistant storage stability and the low temperature storage stability may be deteriorated.

  The toner flow start temperature is preferably 60 ° C. or higher, and more preferably 70 to 150 ° C. When the outflow start temperature is less than 60 ° C., the heat resistant storage stability and the low temperature storage stability may be deteriorated.

  The 1/2 method softening point of the toner is preferably 60 ° C. or higher, and more preferably 80 to 170 ° C. When the 1/2 method softening point is less than 60 ° C., the heat-resistant storage stability and the low-temperature storage stability may deteriorate.

  The average circularity of the toner is a value obtained by dividing the circumference of an equivalent circle having the same projected area as the shape of the toner by the circumference of the actual toner, and is preferably 0.90 to 0.98, preferably 0.95. -0.975 is more preferable. In addition, it is preferable that the particle | grains whose circularity is less than 0.94 are 15% or less. If the average circularity is less than 0.90, transferability may be deteriorated or image quality may be deteriorated. On the other hand, if it exceeds 0.98, in an image forming system that employs blade cleaning or the like, defective cleaning of the photoreceptor, transfer belt, or the like may occur.

  The average circularity can be measured by an optical detection band method in which a suspension containing toner is passed through an imaging unit detection band on a flat plate, a particle image is optically detected by a CCD camera, and analyzed. It is possible to measure using a flow particle image analyzer or the like.

The measurement method using the flow type particle image analyzer will be described below. The toner and the external additive can be measured using, for example, a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). The measurement removes fine dust through a filter, and as a result, water having a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) in water of 10 ⁻³ cm ³ is used. Do it. A few drops of nonionic surfactant (preferably Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.) is added to 10 ml of water, and 5 mg of a measurement sample is further added. Next, a dispersion treatment is performed for 1 minute with an ultrasonic disperser UH-50 (manufactured by STM) at 20 kHz and 50 W / 10 cm ³ , and further a dispersion treatment is performed for a total of 5 minutes. The particle size distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is measured using a sample dispersion of ˜8000 / 10 ⁻³ cm ³ (targeting particles in the equivalent circle diameter range). .

  The sample dispersion is passed through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, a strobe and a CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter. In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.

  The weight average particle diameter Dw of the toner is preferably 3 to 10 μm. When Dw is less than 3 μm, when used as a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. Further, when used as a one-component developer, toner filming on the developing roller may occur, or the toner may be thinned to cause toner fusion to a member such as a blade. . When Dw exceeds 10 μm, it becomes difficult to form a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle size may increase.

  The ratio Dw / Dn of the weight average particle diameter Dw to the number average particle diameter Dn of the toner is preferably 1.00 to 1.25, and more preferably 1.10 to 1.25. When Dw / Dn exceeds 1.25, when used as a two-component developer, the toner may be fused to the surface of the carrier during long-term stirring in the developing device, and the charging ability of the carrier may be reduced. . Further, when used as a one-component developer, toner filming on the developing roller may occur, or the toner may be thinned to cause toner fusion to a member such as a blade. . Further, it becomes difficult to form a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle size may increase.

  Dw and Dw / Dn can be measured using a Coulter counter method. As an apparatus for measuring the particle size distribution of toner by the Coulter Counter method, there are Coulter Counter TA-II and Coulter Multisizer II (manufactured by Coulter, Inc.). The measurement method is described below.

  First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% by weight NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Next, 2 to 20 mg of a measurement sample is added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toners are measured with the above measuring apparatus using a 100 μm aperture, and the volume distribution and number are measured. Calculate the distribution. From the obtained distribution, the weight average particle diameter and the number average particle diameter of the toner can be obtained.

  As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

  The image formed using the toner of the present invention preferably has a density value measured using a spectrometer 938 spectrodensitometer (manufactured by X-Light) of 1.90 or more, and 2.00 or more. More preferred is 2.10 or more. If the density value is less than 1.90, the image density may be low and high image quality may not be obtained.

The image density is imagio Neo 450 (manufactured by Ricoh Co., Ltd.), and a solid image with a toner adhesion amount of 1.00 ± 0.05 mg / cm ² is placed on a copy paper TYPE6000 <70W> (manufactured by Ricoh Co., Ltd.). The surface temperature is 160 ± 2 ° C., and the image density at any six positions of the solid image is measured using a spectrometer 938 spectro-densitometer, and the average value can be calculated. .

  The toner of the present invention can be used for electrophotography, electrostatic recording method, electrostatic printing method and the like.

  The developer of the present invention contains the toner of the present invention and can contain appropriately selected components such as a carrier. The developer may be a one-component developer or a two-component developer, but when used in a high-speed printer or the like corresponding to the recent improvement in information processing speed, In view of this, a two-component developer is preferable.

  When the toner of the present invention is used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle size is small, so that the toner filming on the developing roller and the toner thinning are performed. The fusion of toner to a member such as a blade is suppressed, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time.

  Further, when the toner of the present invention is used for a two-component developer, even if the balance of the toner for a long period of time is performed, the variation in the particle size of the toner in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

  The carrier can be appropriately selected according to the purpose, but preferably has a core material and a resin layer covering the core material.

  The material of the core material can be appropriately selected from known materials, and examples thereof include 50 to 90 emu / g manganese-strontium-based material, manganese-magnesium-based material, etc., in order to ensure image density. Highly magnetized materials such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g are preferable. Further, since it is possible to weaken the hitting of the photoconductor in which the toner is in a flashing state and it is advantageous for high image quality, a weakly magnetized material such as a copper-zinc-based material of 30 to 80 emu / g is used. preferable. Two or more of these may be used in combination.

  The weight average particle diameter D50 of the core material is preferably 10 to 150 μm, and more preferably 40 to 100 μm. If D50 is less than 10 μm, the amount of fine powder increases, the magnetization per particle becomes low and the carrier may be scattered, and if it exceeds 150 μm, the specific surface area may decrease and the toner may be scattered. In a full-color image, the reproducibility of the solid image portion may be deteriorated.

  The material of the resin layer can be appropriately selected from known resins according to the purpose. For example, amino resin, polyvinyl resin, polystyrene resin, halogenated olefin resin, polyester resin, polycarbonate resin , Polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride Polymers, fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride, and non-fluorinated monomers, silicone resins, and the like may be used, and two or more types may be used in combination.

  Examples of amino resins include urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins, and epoxy resins. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. Examples of polystyrene resins include polystyrene and styrene-acrylic copolymers. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate.

  The resin layer may contain conductive powder or the like as necessary. Examples of such conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The number average particle diameter of the conductive powder is preferably 1 μm or less. When the number average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

  For the resin layer, after preparing a coating solution in which a silicone resin or the like is dissolved or dispersed in a solvent, the coating solution is uniformly applied to the surface of the core material by a known coating method, dried, and then baked. Can be formed. Examples of the application method include a dipping method, a spray method, and a brush coating method. The solvent can be appropriately selected according to the purpose, and examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and cellosol butyl acetate. Baking may be either an external heating method or an internal heating method. As an external heating method, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or the like, and as an internal heating method, a micro Examples include a method using waves.

  The content of the resin layer in the carrier is preferably 0.01 to 5.0% by weight. If the content of the resin layer is less than 0.01% by weight, a uniform resin layer may not be formed on the surface of the core material. If the content exceeds 5.0% by weight, the resin layer becomes too thick. As a result, agglomeration of the carriers may occur, and the uniformity of the carrier particle size may decrease.

  The content of the carrier in the two-component developer can be appropriately selected according to the purpose, but is preferably 90 to 98% by weight, and more preferably 93 to 97% by weight.

  Since the developer of the present invention contains the toner of the present invention, it is possible to stably form a high-quality image with excellent chargeability during image formation. The developer of the present invention can be used for image formation using various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be used in a container, a process cartridge, an image forming apparatus, and an image forming method.

  The developer-containing container of the present invention is a container in which the developer of the present invention is accommodated. Although a container can be suitably selected from well-known containers, the container etc. which have a container main body and a cap are mentioned. The size, shape, structure, material and the like of the container body can be appropriately selected according to the purpose, but the shape is preferably cylindrical. In addition, spiral irregularities are formed on the inner peripheral surface, and the developer as the contents can be transferred to the discharge port side by rotating, and it is particularly preferable that part or all of the spiral portion has a bellows function. preferable. The container body is preferably made of a material with good dimensional accuracy. Specifically, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, Examples thereof include resin materials such as polyacetal resin.

  The developer-containing container of the present invention can be easily stored and transported, has excellent handleability, can be attached to and detached from the process cartridge and image forming apparatus of the present invention described later, and can be replenished with the developer.

  The process cartridge of the present invention is detachable from the main body of the image forming apparatus, and integrally supports at least one of a charging unit, a developing unit, a cleaning unit, and an image carrier, and further includes other units as necessary. You may support integrally. The developing means develops the electrostatic latent image formed on the image carrier with the developer of the present invention to form a toner image. Further, the developing means preferably has at least a developer carrying member that can detachably attach the developer-containing container of the present invention and carries and conveys the developer. Further, the developing unit may further include a layer thickness regulating member that regulates the layer thickness of the toner carried on the developer carrying member.

  The image forming method of the present invention comprises a step of developing a latent electrostatic image formed on an image carrier with a developer of the present invention to form a toner image, and the toner image formed on the image carrier is applied to a transferred material. At least a process for transferring and a toner image transferred to the transfer medium by a heat or pressure fixing process using a roller-like or belt-like fixing member, and an electrostatic latent image forming process, a charge eliminating process, a cleaning process, and a recycling process. Further, a process such as a control process may be further included. In the development step, it is preferable to develop the electrostatic latent image carried on the image carrier by applying an alternating electric field. Thereby, a high-quality image can be formed.

  The image forming apparatus of the present invention includes an image carrier that carries an electrostatic latent image, a charging unit that charges the image carrier, an exposure unit that exposes the charged image carrier to form an electrostatic latent image, and an image carrier. The electrostatic latent image formed on the body is developed with the developer of the present invention to form a toner image, a transfer unit for transferring the toner image formed on the image carrier to the transfer target, and the toner image It may have at least a cleaning unit that cleans the transferred image carrier, and may further include a fixing unit, a neutralizing unit, a recycling unit, a control unit, and the like. The image carrier is an organic photoreceptor or an amorphous silicon photoreceptor.

  An image forming apparatus according to the present invention includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the transfer target body onto which the toner image has been transferred is a film. Preferably, the image forming apparatus further includes a fixing unit that heat-presses and fixes between the pressure member and the pressure member. Thereby, a high-quality image can be fixed at a low temperature.

  The material, shape, structure, size, etc. of the image carrier can be appropriately selected from known image carriers, but the shape is preferably drum-like, for example, amorphous silicon, selenium, etc. Examples include inorganic photoreceptors, organic photoreceptors such as polysilane and phthalopolymethine. Among these, an amorphous silicon photoreceptor is preferable because of its long life.

  The electrostatic latent image forming step is a step of forming an electrostatic latent image on the surface of the image carrier. At this time, the electrostatic latent image is formed by charging the surface of the image carrier uniformly with the charging unit, and then exposing the surface of the image carrier to the surface of the image carrier based on the image data.

  Charging can be performed by applying a voltage to the surface of the image carrier using a charging means. The charging means can be appropriately selected according to the purpose, but uses a known contact charger equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc., corona discharge such as corotron, scorotron, etc. Non-contact chargers and the like.

  The exposure can be performed by exposing the surface of the image carrier using an exposure unit. The exposure means can be appropriately selected according to the purpose, and examples thereof include various exposure apparatuses such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. In addition, you may use the light back system which exposes from the back surface of an image carrier.

  The development step is a step of developing the electrostatic latent image formed on the image carrier using the developer of the present invention to form a toner image. At this time, the developing unit develops the electrostatic latent image using a developer, whereby a toner image can be formed. The developing means can be appropriately selected from known developing means, and has a developing device that contains the developer of the present invention and can apply toner to the electrostatic latent image in contact or non-contact. Is preferred. At this time, the developing device preferably includes the developer-containing container of the present invention.

  The developing device may be either a dry developing method or a wet developing method, and may be either a single color developing device or a multi-color developing device, and a stirrer for charging the developer by frictional stirring. And a developing device having a rotatable magnet roller.

  When a two-component developer is used, the toner and carrier are mixed and agitated in the developing unit, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. Is done. Since the magnet roller is disposed in the vicinity of the image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a toner image is formed on the surface of the image carrier.

  The developer of the present invention accommodated in the developing unit contains the toner of the present invention, but may be either a one-component developer or a two-component developer.

  The transfer step is a step of transferring the toner image to the transfer target, but it is preferable to primarily transfer the toner image onto the transfer target after first transferring the toner image onto the intermediate transfer transfer. At this time, it is preferable to use toner of two or more colors, and a full-color toner is more preferable. In this case, the transfer process includes a primary transfer process in which the toner image is transferred onto the intermediate transfer body to form a composite transfer image, and a secondary transfer process in which the composite transfer image is transferred onto the transfer target.

  The transfer can be performed by charging a toner image on the image carrier using a transfer unit. The transfer unit preferably includes a primary transfer unit that transfers the toner image onto the intermediate transfer member to form a composite transfer image, and a secondary transfer unit that transfers the composite transfer image onto the transfer target. The intermediate transfer member can be appropriately selected from known transfer members according to the purpose, and examples thereof include a transfer belt.

  The transfer means (primary transfer means and secondary transfer means) preferably has a transfer unit that peels and charges the toner image formed on the image carrier to the transfer target side. There may be a single transfer device or a plurality of transfer devices. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The transferred material can be appropriately selected from known recording media (recording paper).

  The fixing step is a step of fixing the toner image transferred to the transfer target using a fixing unit, and may be fixed each time the toner of each color is transferred to the transfer target, or the toner of each color is laminated. You may fix at once in the state. The fixing unit can be appropriately selected according to the purpose, but a known heating and pressing unit can be used. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. At this time, it is preferable that heating temperature is 80-200 degreeC. In the present invention, a known optical fixing device may be used together with the fixing unit or in place of the fixing unit depending on the purpose.

  The neutralization step is a step of neutralizing by applying a neutralization bias to the image carrier using a neutralization unit. The neutralizing means can be appropriately selected from known neutralizers, and examples thereof include a neutralizing lamp.

  The cleaning step is a step of removing toner remaining on the surface of the image carrier after the toner image is transferred, using a cleaning unit. The cleaning means can be appropriately selected from known cleaners, and examples thereof include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.

  The recycling process is a process in which the toner removed in the cleaning process is transported to the developing unit using the recycling unit and recycled. Examples of the recycling means include known transport means.

  A control process is a process of controlling each process using a control means. The control means can be appropriately selected according to the purpose, and examples thereof include devices such as sequencers and computers.

  FIG. 1 shows an example of an image forming apparatus of the present invention. The image forming apparatus 100A includes a photosensitive drum 10 as an image carrier (hereinafter referred to as a “photosensitive member 10”), a charging roller 20 as a charging unit, an exposure device 30 as an exposure unit, and a developing device 40 as a developing unit. And an intermediate transfer member 50, a cleaning device 60 as a cleaning means having a cleaning blade, and a static elimination lamp 70 as a static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. A cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer body 50, and a transfer bias (secondary transfer bias) for transferring a toner image to a transfer sheet 95 as a transfer target is applied. A transfer roller 80 serving as a transfer unit capable of performing the transfer is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is a contact portion between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. Between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as a developer carrier, and a black developing device 45K, a yellow developing device 45Y, a magenta developing device 45M, and a cyan developing device 45C provided around the developing belt 41. ing. The black developing device 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing device 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller. 44Y, the magenta developer 45M includes a developer container 42M, a developer supply roller 43M, and a developer roller 44M. The cyan developer 45C includes a developer container 42C and a developer supply roller. 43C and a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100A, the charging roller 20 charges the photoreceptor 10 uniformly. Next, the exposure apparatus 30 performs imagewise exposure on the photoreceptor 10 to form an electrostatic latent image. Further, the electrostatic latent image formed on the photoconductor 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  FIG. 2 shows another example of the image forming apparatus of the present invention. In FIG. 2, the same components as those of the image forming apparatus shown in FIG. The image forming apparatus 100B does not include the developing belt 41, and the black developing device 45K, the yellow developing device 45Y, the magenta developing device 45M, and the cyan developing device 45C are directly opposed to each other around the photoreceptor 10. Except for being arranged, the image forming apparatus 100A has the same configuration as that of the image forming apparatus 100A and exhibits the same operational effects.

  FIG. 3 shows another example of the image forming apparatus of the present invention. The image forming apparatus 100C is a tandem color image forming apparatus. The image forming apparatus 100 </ b> C includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400. The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16 and can be rotated clockwise in FIG. 3. A cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. An image forming unit 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem image forming unit 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem image forming unit 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.

  In the image forming apparatus 100C, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25.

  Next, formation of a full color image (color copy) by the tandem type image forming unit 120 will be described. First, a document is set on a document table 130 of an automatic document feeder (ADF) 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35. A color original (color image) is read and becomes black, yellow, magenta, and cyan image information.

  The image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image forming unit) in the tandem image forming unit 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, as shown in FIG. 4, each image forming unit 18 includes a photoconductor 10 (a black photoconductor 10K, a yellow photoconductor 10Y, a magenta photoconductor 10M, and a cyan photoconductor 10C) and a photoconductor. The charger 59 that uniformly charges the photoconductor 10 and the photoconductor 10 is exposed like an image corresponding to each color image based on each color image information (L in FIG. 4), and each color image is supported on the photoconductor 10. An exposure device 21 that forms an electrostatic latent image, and development that develops the electrostatic latent image with each color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner. And 61, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a static eliminator 64. Each single color toner image based (black toner image, yellow toner image, magenta toner image and cyan toner image) can be formed. Thus, the black toner image formed on the black photoconductor 10K, the yellow toner image formed on the yellow photoconductor 10Y, the magenta toner image formed on the magenta photoconductor 10M, and the cyan photoconductor. The cyan toner image formed on 10 </ b> C is sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is rotationally moved by the support rollers 14, 15, and 16. Then, a black toner image, a yellow toner image, a magenta toner image, and a cyan toner image are superimposed on the intermediate transfer member 50 to form a color toner image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 48 is rotated to feed out the sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.

  Then, the registration roller 49 is rotated in synchronization with the color toner image (color transfer image) formed on the intermediate transfer member 50, and a sheet (recording paper) is placed between the intermediate transfer member 50 and the secondary transfer device 22. The color toner image (color transfer image) is transferred onto the sheet (recording paper) by being sent and transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device 22. Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the cleaning device 17.

  The sheet (recording paper) onto which the color toner image (color transfer image) has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the color toner image (color toner image ( Color transfer image) is fixed on a sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56, and is stacked on the discharge tray 57. Alternatively, the sheet (recording paper) is switched by the switching claw 55, reversed by the sheet reversing device 28, and again led to the transfer position. After recording an image on the back surface in the same manner as described above, the sheet is discharged by the discharge roller 56. Are stacked on the paper discharge tray 57.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, a part means a weight part.
( Reference Example 1)
1000 parts of 1,1-dihydroperfluorooctyl acrylate and 10 parts of V-65 (2,2′-azobis (2,4-dimethylvaleronitrile)) (manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a pressure-resistant container. Critical carbon dioxide was supplied into the pressure vessel by a supply cylinder, adjusted to 25 MPa and 65 ° C. with a pressure pump and a temperature controller, and polymerized for 24 hours to obtain a surfactant. Here, when a part was sampled and GPC (gel permeation chromatography) measurement was performed using HFIP (hexafluoroisopropanol) as an eluent, the weight average molecular weight was 8.7 × 10 ⁴ and the number average molecular weight. Was 3.0 × 10 ⁴ . Next, the temperature of the pressure vessel is lowered to 25 ° C., and a mixture of 20000 parts of styrene and 200 parts of AIBN (azobisisobutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) is introduced under pressure, and a temperature controller and a pressure pump For 40 hours at 65 ° C. and 25 MPa. After completion of the reaction, 100 parts of oil black HBB (manufactured by Orient Chemical Co., Ltd.) and 4 parts of oil orange 201 (manufactured by Orient Chemical Co., Ltd.) were added under pressure, and dyeing was performed for 1 hour. Next, after the temperature of the pressure vessel was cooled to 5 ° C., the pressure was gradually reduced to normal pressure to obtain a toner.
( Reference Examples 2-7)
A toner was obtained in the same manner as in Reference Example 1 except that the surfactant was synthesized by changing the fluorine-based monomer, copolymerization monomer, polymerization initiator, reaction temperature, and reaction pressure shown in Table 1.

（参考例８）
フッ素系モノマーとして、アクリル酸１，１−ジハイドロパーフルオロオクチル２部及びＡＩＢＮ（２，２'−アゾビスイソブチロニトリル）０．０２部を耐圧容器に入れ、−６０℃にした後、真空ポンプで脱気を行った。次に、常温に戻し、再度、−６０度に冷却して、真空ポンプで脱気を行った後、６５℃で２４時間重合を行って界面活性剤を得た。ここで、一部サンプリングし、参考例１と同様にして、ＧＰＣ測定を行ったところ、重量平均分子量が２．１×１０^６、数平均分子量が１．６×１０^５であった。次に、耐圧容器の温度を２５℃まで下げ、超臨界二酸化炭素を供給ボンベにより耐圧容器内に供給し、スチレン２００００部とＡＩＢＮ（２，２'−アゾビスイソブチロニトリル）２００部の混合物を加圧導入し、温度調整器と加圧ポンプを使用して、６５℃、２５ＭＰａで４０時間重合を行った。反応終了後、オイルブラックＨＢＢ（オリエント化学社製）１００部及びオイルオレンジ２０１（オリエント化学社製）４部を加圧添加し、１時間染色を行った。次に、耐圧容器の温度を５℃まで冷却した後、徐々に常圧まで減圧して、トナーを得た。
（参考例９）
表２に示すフッ素系モノマー及び重合開始剤及び反応温度に変更して界面活性剤を合成した以外は、参考例８と同様にして、トナーを得た。

( Reference Example 8)
As a fluorine-based monomer, 2 parts of 1,1-dihydroperfluorooctyl acrylate and 0.02 part of AIBN (2,2′-azobisisobutyronitrile) were placed in a pressure vessel and brought to −60 ° C., Deaeration was performed with a vacuum pump. Next, after returning to normal temperature and again cooling to −60 ° C. and deaeration with a vacuum pump, polymerization was performed at 65 ° C. for 24 hours to obtain a surfactant. Here, when a part was sampled and GPC measurement was performed in the same manner as in Reference Example 1, the weight average molecular weight was 2.1 × 10 ⁶ and the number average molecular weight was 1.6 × 10 ⁵ . Next, the temperature of the pressure vessel is lowered to 25 ° C., supercritical carbon dioxide is supplied into the pressure vessel by a supply cylinder, and a mixture of 20000 parts of styrene and 200 parts of AIBN (2,2′-azobisisobutyronitrile). Then, polymerization was carried out at 65 ° C. and 25 MPa for 40 hours using a temperature controller and a pressure pump. After completion of the reaction, 100 parts of oil black HBB (manufactured by Orient Chemical Co., Ltd.) and 4 parts of oil orange 201 (manufactured by Orient Chemical Co., Ltd.) were added under pressure, and dyeing was performed for 1 hour. Next, after the temperature of the pressure vessel was cooled to 5 ° C., the pressure was gradually reduced to normal pressure to obtain a toner.
( Reference Example 9)
A toner was obtained in the same manner as in Reference Example 8 except that the surfactant was synthesized by changing the fluorine-based monomer, polymerization initiator, and reaction temperature shown in Table 2.

（実施例１０）
アクリル酸１，１−ジハイドロパーフルオロオクチル１０００部及びＡＩＢＮ（２，２'−アゾビスイソブチロニトリル）１０部を耐圧容器に入れ、超臨界二酸化炭素を供給ボンベにより耐圧容器内に供給し、加圧ポンプと温度調節器で３０ＭＰａ、８５℃に調節し、２４時間重合を行って界面活性剤を得た。ここで、一部サンプリングし、参考例１と同様にして、ＧＰＣ測定を行ったところ、重量平均分子量が１．１５×１０^５、数平均分子量が４．５×１０^４であった。次に、耐圧容器の温度を２５℃まで下げ、超臨界二酸化炭素を供給ボンベにより耐圧容器内に供給し、スチレン１１０００部、アクリル酸メチル９０００部、ジビニルベンゼン６０部、ペンタエリスリトールテトラステアレート（ステアリン酸純度約６０％）２０００部、融点が９２℃の天然ガス系フィッシャートロプシュワックスＦＴ＆＃８７２２；１００（Ｄシェル・ＭＳ社製）４００部及びＡＩＢＮ（２，２'−アゾビスイソブチロニトリル）２００部の混合物を加圧導入し、温度調整器と加圧ポンプを使用して、６５℃、２５ＭＰａで４０時間重合を行った。反応終了後、オイルブラックＨＢＢ（オリエント化学社製）１００部及びオイルオレンジ２０１（オリエント化学社製）４部を加圧添加し、１時間染色を行った。次に、耐圧容器の温度を５℃まで冷却した後、徐々に常圧まで減圧して、トナーを得た。
（比較例１）
撹拌翼、冷却コンデンサー、窒素ガス導入管を取り付けた密閉可能な反応容器を恒温水槽内に取り付け、反応容器内に、エタノール７０部、蒸留水３０部及びポリビニルピロリドン４部を仕込み、撹拌翼を回転させポリビニルピロリドンを完全に溶解させた。次に、反応容器内に、スチレン２８部、アクリル酸エチル１０部、メタクリル酸ｎ−ブチル２部、エチレングリコールジメタクリレート０．２部、四塩化炭素０．０３部及び過酸化ベンゾイル０．６部を容器内に仕込んだ。引き続き、撹拌翼を回転させながら、反応容器内に窒素ガスを吹き込み、酸素を追い出したところで、水槽内を５０±０．１℃に昇温して重合を開始させた。２時間後に水槽内を６５±０．１℃に昇温し、反応速度を上げた。

(Example 10)
1000 parts of 1,1-dihydroperfluorooctyl acrylate and 10 parts of AIBN (2,2′-azobisisobutyronitrile) are put in a pressure vessel, and supercritical carbon dioxide is supplied into the pressure vessel by a supply cylinder. Then, the pressure was adjusted to 30 MPa and 85 ° C. with a pressure pump and a temperature controller, and polymerization was performed for 24 hours to obtain a surfactant. Here, when a part was sampled and GPC measurement was performed in the same manner as in Reference Example 1, the weight average molecular weight was 1.15 × 10 ⁵ and the number average molecular weight was 4.5 × 10 ⁴ . Next, the temperature of the pressure vessel is lowered to 25 ° C., and supercritical carbon dioxide is supplied into the pressure vessel by a supply cylinder, and 11000 parts of styrene, 9000 parts of methyl acrylate, 60 parts of divinylbenzene, pentaerythritol tetrastearate (stearinate). Acid purity of about 60%) 2000 parts, natural gas Fischer-Tropsch wax FT &# 8722 with melting point of 92 ° C .; 400 parts (manufactured by D Shell MS) and AIBN (2,2′-azobisisobutyronitrile) 200 parts of the mixture was introduced under pressure, and polymerization was carried out at 65 ° C. and 25 MPa for 40 hours using a temperature controller and a pressure pump. After completion of the reaction, 100 parts of oil black HBB (manufactured by Orient Chemical Co., Ltd.) and 4 parts of oil orange 201 (manufactured by Orient Chemical Co., Ltd.) were added under pressure, and dyeing was performed for 1 hour. Next, after the temperature of the pressure vessel was cooled to 5 ° C., the pressure was gradually reduced to normal pressure to obtain a toner.
(Comparative Example 1)
A sealable reaction vessel equipped with a stirring blade, a cooling condenser, and a nitrogen gas introduction tube is installed in a constant temperature water tank. In the reaction vessel, 70 parts of ethanol, 30 parts of distilled water and 4 parts of polyvinylpyrrolidone are charged, and the stirring blade is rotated. The polyvinylpyrrolidone was completely dissolved. Next, in a reaction vessel, 28 parts of styrene, 10 parts of ethyl acrylate, 2 parts of n-butyl methacrylate, 0.2 part of ethylene glycol dimethacrylate, 0.03 part of carbon tetrachloride and 0.6 part of benzoyl peroxide Was charged in a container. Subsequently, while rotating the stirring blade, nitrogen gas was blown into the reaction vessel, and when oxygen was expelled, the temperature in the water tank was raised to 50 ± 0.1 ° C. to initiate polymerization. After 2 hours, the temperature in the water tank was raised to 65 ± 0.1 ° C. to increase the reaction rate.

  After 12 hours from the start of the reaction, the mixture was cooled to room temperature to obtain a dispersion of resin particles. As a result of partial sampling and measurement by gas chromatography using an internal standard method, it was confirmed that the polymerization rate exceeded 90%. Further, when the particle size distribution was measured with a Coulter Multisizer (100 μm aperture tube), the weight average particle size Dw was 6.9 μm and the number average particle size Dn was 6.1 μm.

Next, 30 parts of solvent black was dissolved in 20 parts of ethanol by heating, and after removing undissolved parts with a 1 μm filter, 20 parts of ethanol particles, 100 parts of ethanol, and 100 parts of resin particles were placed in a container and stirred at 50 ° C. for 1 hour. The resin particles were dyed. Thereafter, the dyeing solution was cooled to room temperature, centrifuged, and the supernatant was removed, followed by redispersion in ethanol three times, followed by filtration to obtain a toner.
(Development of developer)
The external additive treatment was performed by mixing 100 parts of toner with 0.7 part of hydrophobic silica and 0.3 part of hydrophobic titanium oxide using a Henschel mixer. Next, a developer comprising 5% by weight of the toner subjected to external additive treatment and 95% by weight of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin was prepared.

The resulting developer was measured for image density, fusion to the photoreceptor, and charge amount as follows.
(Image density)
Using a tandem color electrophotographic apparatus imagio Neo450 (manufactured by Ricoh), a solid image with a developer adhesion amount of 1.00 ± 0.05 mg / cm ² is formed on a copy paper TYPE6000 <70W> (manufactured by Ricoh). did. The solid image was formed repeatedly on 8000 copy sheets. The image density was evaluated by visually observing a solid image at the initial stage and after the endurance of 8000 sheets. At this time, the image density did not change at the initial stage and after the end of 8000 sheets, and a high image quality was obtained, and after the end of 8000 sheets, the image density was slightly decreased and the image quality was decreased, Δ, 8000 After the endurance of the sheet, the image density significantly decreased and the image quality greatly decreased was determined as x.
(Fusion to photoconductor)
The fusion to the photoreceptor is evaluated by visually observing the fusion of the toner to the organic photoreceptor (OPC) after the solid image is formed, and the fusion of the toner to the photoreceptor is not recognized. As a result, the case where the toner was fused to the photosensitive member was evaluated as x.
(Charge amount)
6 g of developer was weighed, charged into a metal cylinder that could be sealed, and blown to determine the charge amount. At this time, the toner concentration was adjusted to 4.5 to 5.5% by weight.
(Evaluation results)
Table 3 shows the evaluation results.

これより、参考例１〜９、実施例１０のトナーを用いて得られる現像剤は、比較例１のトナーを用いて得られる現像剤に比べ、帯電性能に優れ、高画像濃度が得られることが確認された。なお、比較例１のトナーは、染料による着色性が低いことによって画像濃度も低いが、参考例１〜９、実施例１０のトナーは、染料が樹脂微粒子の内部にまで進入するため、十分な染着と画像濃度となることも判った。

As a result, the developer obtained using the toners of Reference Examples 1 to 9 and Example 10 is superior to the developer obtained using the toner of Comparative Example 1 and has a high image density. Was confirmed. The toner of Comparative Example 1 has a low image density due to the low colorability of the dye. However, the toners of Reference Examples 1 to 9 and Example 10 are sufficient because the dye enters the resin fine particles. It was also found that dyeing and image density were achieved.

  Further, in the toner manufacturing method of the embodiment, almost no waste liquid is generated, and a dry toner can be obtained simply by returning to normal pressure. Therefore, the conventional method is low cost, low environmental load, energy saving, and resource saving. It was found that this is an epoch-making toner production method compared with the other toner production methods.

1 is a schematic diagram illustrating an example of an image forming apparatus of the present invention. It is the schematic which shows the other example of the image forming apparatus of this invention. It is the schematic which shows the other example of the image forming apparatus of this invention. FIG. 4 is a schematic diagram illustrating a part of the image forming apparatus illustrated in FIG. 3.

Explanation of symbols

10, 10K, 10Y, 10M, 10C Photoconductor (Photoconductor drum)
14, 15, 16 Support roller 17 Cleaning device 18 Image forming unit 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K, 42Y, 42M, 42C Developer container 43K, 43Y, 43M, 43C Developer supply roller 44K, 44Y , 44M, 44C Developing roller 45K, 45Y, 45M, 45C Developer 48 Feed roller 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Rona charger 59 charger 60 cleaning device 61 developing device 62 transfer charger 63 cleaning device 64 discharger 70 discharger lamp 80 transfer roller 90 cleaning device 95 transfer paper 100A, 100B, 100C image forming device 110 belt type fixing device 120 tandem type Image forming unit 130 Document base 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Claims (17)

A step of synthesizing the surfactant by polymerizing the fluorinated vinyl monomer in the pressure vessel ;
A surfactant in said pressure vessel, by polymerizing a radical polymerizable monomer in a fluid containing a coloring agent and / or mold release agent, a step of synthesizing a polymer which is insoluble in the fluid Yes, and
The fluorine-based vinyl monomer has a general formula

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a methylene group, an ethylene group or a 2-hydroxypropylene group, and R _f is a perfluoroalkyl having 4 to 10 carbon atoms. Represents a group.)
A compound represented by
The surfactant has a weight average molecular weight of 4.0 × 10 ³ or more and 2.1 × 10 ⁶ or less,
The method for producing a toner, wherein the fluid is supercritical carbon dioxide or subcritical carbon dioxide . The toner production method according to claim 1, wherein the radical polymerizable monomer is soluble in the fluid . The surfactant has the general formula

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a methylene group, an ethylene group or a 2-hydroxypropylene group, and R _f is a perfluoroalkyl having 4 to 10 carbon atoms. Group.)
Method for producing a toner according to claim 1 or 2, characterized in that a structural unit in represented. The method for producing a toner according to claim 3 , wherein the surfactant has a composition ratio of the structural unit represented by the general formula of 20 mol% to 100 mol%. Method for producing a toner according to any one of claims 1 to 4, characterized in that the polymerization of the fluorine-based vinyl monomers in supercritical carbon dioxide. Method for producing a toner according to any one of claims 1 to 4, characterized in that bulk polymerization of the fluorine-based vinyl monomer. Method for producing a toner according to any one of claims 1 to 6, characterized in that the weight ratio of the radical polymerizable monomer to the surfactant is 10 or more 1.0 × 10 ⁴ or less. Toner characterized in that it is manufactured using the method for producing a toner according to any one of claims 1 to 7. The toner according to claim 8 , further comprising a charge control agent. Developing agent characterized by containing the toner according to claim 8 or 9. The developer according to claim 10 , further comprising a carrier. A developer-containing container, wherein the developer according to claim 10 or 11 is contained in a container. Forming a toner image by developing with a developer according to an electrostatic latent image formed on an image bearing member to claim 10 or 11,
A step of transferring a toner image formed on the image bearing member to a transfer target ;
Image forming method characterized in that the fixing member該被transfer member roller shape the transferred toner image on or belt form, to have a heating pressure fixing to process. The image forming method according to claim 13 , wherein an alternating electric field is applied when developing the electrostatic latent image formed on the image carrier. An image bearing member for bearing an electrostatic latent image,
A charging unit that Ru charges the image carrier,
Exposed to the charged and image bearing member, an exposure means for forming an electrostatic latent image,
A developing means for forming a preparative toner image is developed with a developer according to an electrostatic latent image formed on the image bearing member to claim 10 or 11,
Transfer means for transferring a toner image formed on the image carrier to a transfer target ;
An image forming apparatus comprising: a cleaning unit that cleans an image carrier on which the toner image is transferred to a transfer target . A heating member having a heating element, a film in contact with the heating body has a pressure member for the heating element and the pressure through the film, the transferred object to the toner image has been transferred and the film The image forming apparatus according to claim 15 , further comprising a fixing unit configured to perform heat and pressure fixing between the pressure members. An image carrier and an electrostatic latent image formed on the image carrier are developed with the developer according to claim 10 or 11 to integrally support a developing unit for forming a toner image ,
A process cartridge, wherein the removable der Turkey in the main body of the image forming apparatus.

Images