JP2009210907A - Toner, and image forming apparatus and image forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner etc. which has good hopping property even in a low-temperature and low-humidity environment and in a high-temperature and high-humidity environment, excels in sharpness of an image, and is used in a developing device with a hopping system having remarkably improved followup ability to a pulse electric field. <P>SOLUTION: The toner includes a first toner having a number average molecular weight of Dn1 and a second toner having a number average molecular weight of Dn2 which is 2-4 times the Dn1, and the toner is used in a developing device equipped with a surface-movable toner bearing member with an electrode pattern comprising a plurality of electrodes arranged in an insulated state from each other in a predetermined direction, wherein a potential difference is generated between an odd-numbered electrode group which is an assembly of odd-numbered electrodes based on a predetermined electrode among the plurality of electrodes, and an even-numbered electrode group which is an assembly of even-numbered electrodes, and according to the potential difference, toner on the surface of the toner bearing member is conveyed to a position opposite to an electrostatic latent image bearing member by surface movement of the toner beating member, while being moved between the electrodes, and the toner is deposited on a latent image on the electrostatic latent image bearing member to develop the latent image. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a toner, and an image forming apparatus and an image forming method such as a copying machine, a printer, and a facsimile that form an image using the toner.

  2. Description of the Related Art Conventionally, as a developing device, a toner that is hopped on the surface of a toner carrier such as a toner transport substrate is used for development, instead of using toner adsorbed on a developing roller or a magnetic carrier for development. Yes.

  For example, the developing device described in Patent Document 1 includes a cylindrical toner carrier including a plurality of electrodes arranged at a predetermined pitch in the circumferential direction. These electrodes are formed by repeatedly arranging electrode pairs composed of two adjacent electrodes. An alternating electric field is formed between the two electrodes in each electrode pair. Then, the toner located on one electrode in the electrode pair floats and landes on the other electrode, or floats on the other electrode and landes on one electrode. Then, while repeating the hopping in this way, the cylindrical toner carrier is transported to the developing region by the surface movement accompanying the rotational driving. In the developing region, the toner that has floated to the vicinity of the latent image on the latent image carrier is attracted to the electric field by the latent image and does not descend toward the electrode of the toner carrier, and adheres to the latent image. In such a configuration, not the toner adsorbed on the developing roller or the magnetic carrier but the toner that does not exhibit the adsorbing force by hopping is used for the development. As a result, it is possible to realize low potential development that could not be realized by the conventional one-component development method or two-component development method. For example, toner can be selectively attached to an electrostatic latent image having a potential difference of only a few tens [V] with respect to surrounding non-image portions.

  In such a developing device, the toner on the toner carrying member repeats the hopping phenomenon according to the electric field generated by the electrode in a good charge holding state. For example, if the apparatus is stopped and the hopping electric field is not applied, the developing toner is Then, it remains adhered on the toner carrier. If this state continues for a long time, the charge held by the developing toner is gradually attenuated and becomes lower than the held charge amount before suspension. When a drive pulse is applied again due to such a phenomenon, there is a possibility that the hopping phenomenon cannot occur linearly, and it may be severe under conditions where the toner particles easily lose charge, such as under high humidity. With respect to such a phenomenon, increasing the particle diameter of the toner makes it possible to increase the amount of retained charge in one particle. In other words, since the surface charge density on the toner surface is limited as long as the same material and external additive are used, it is a very effective means for the problem of maintaining the hopping property by holding charge attenuation. In order to form the toner, a toner having a small toner particle size is desired to be traded off, and the improvement is desired at present.

JP-A-3-21967

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, according to the present invention, by using a developing toner in which a second toner having a certain number average particle diameter different from that of the first toner is used, good hopping can be performed in a low temperature and low humidity environment or a high temperature and high humidity environment. Providing a toner used in a hopping developing device capable of significantly improving the followability to a pulsed electric field, and having an image sharpness, and an image forming apparatus and an image forming method using the toner The purpose is to do.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies, and as a result, the first toner is excellent in charge retention and has a number average particle diameter sufficiently larger than that of the first toner. By mixing a certain amount of toner, the flying property of the second toner with respect to the drive pulse is maintained even under the condition where the retained charge is attenuated, and the hopping behavior of the second toner is the first toner on the toner carrier. The impact on the particle group is such that the hopping property of the developing toner composed of the first toner and the second toner is improved from the initial stage, and the hopping property is not only in a normal normal temperature and normal humidity environment but also in a high temperature and high humidity environment. And it was found that it works effectively even in a low temperature and low humidity environment.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> An odd-numbered electrode including a surface-movable toner carrier including an electrode pattern having a plurality of electrodes arranged in a predetermined direction in a state of being insulated from each other, and starting from the predetermined electrode of the plurality of electrodes By generating a potential difference between an odd-numbered electrode group that is an aggregate of the above and an even-numbered electrode group that is an aggregate of even-numbered electrodes, the toner on the surface of the toner carrier is moved between the electrodes while moving the toner between the electrodes. A toner used in a developing device that transports a toner carrier to a position facing the electrostatic latent image carrier and moves the toner carrier to a position opposite to the electrostatic latent image carrier and attaches the toner to the latent image on the electrostatic latent image carrier. ,
A first toner having a number average particle diameter Dn1, and a second toner having a number average particle diameter Dn2 that is 2 to 4 times the number average particle diameter Dn1 of the first toner. Toner.
<2> The toner according to <1>, wherein the content of the second toner is 1% by mass to 10% by mass with respect to the first toner.
<3> The toner according to any one of <1> to <2>, wherein the second toner is any one of colorless particles and colored particles.
<4> The toner according to any one of <1> to <3>, wherein the second toner has the same charging polarity as the first toner.
<5> When the average charge amount per particle of the first toner is AvgQ1 and the average charge amount per particle of the second toner is AvgQ2, the absolute values satisfy AvgQ1 <AvgQ2 above <1> to <4 > The toner according to any one of the above.
<6> Any one of <1> to <5>, wherein the surface of the toner carrying member is coated with a material capable of giving a normal charge to the first toner by friction with the first toner. The toner described in 1.
<7> Any one of <1> to <6>, wherein the surface of the toner carrying member is coated with a material capable of giving a regular charge to the second toner by friction with the second toner. The toner described in 1.
<8> The toner according to any one of <1> to <7>, further including means for forming a charged toner layer on the surface of the toner carrier.
<9> An electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, and exposure means for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image Developing means for developing the electrostatic latent image with toner to form a visible image; transfer means for transferring the visible image to a recording medium; and fixing the transferred image transferred to the recording medium. An image forming apparatus having at least a fixing unit,
The developing means includes a surface-movable toner carrier having an electrode pattern having a plurality of electrodes arranged in a predetermined direction in a state of being insulated from each other, and the odd-numbered number starting from the predetermined electrode in the plurality of electrodes The toner on the surface of the toner carrier is moved between the electrodes by generating a potential difference between the odd-numbered electrode group that is an aggregate of the electrodes and the even-numbered electrode group that is the aggregate of the even-numbered electrodes. A developing device that transports the toner carrier to a position facing the electrostatic latent image carrier by moving the surface of the toner carrier and attaches the toner to the latent image on the electrostatic latent image carrier and develops the toner.
The toner is the toner according to any one of <1> to <8>.
<10> The image forming apparatus according to <9>, wherein an image is formed by superimposing two or more kinds of toners on the electrostatic latent image carrier.
<11> A charging step for charging the surface of the electrostatic latent image carrier, an exposure step for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the electrostatic latent image with toner. An image forming method comprising at least a developing step for developing a visible image by using the developing method, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium Because
The developing step includes a surface-movable toner carrier having an electrode pattern having a plurality of electrodes arranged in a predetermined direction in a state of being insulated from each other, and is an odd number starting from the predetermined electrode of the plurality of electrodes. The toner on the surface of the toner carrier is moved between the electrodes by generating a potential difference between the odd-numbered electrode group that is an aggregate of the electrodes and the even-numbered electrode group that is the aggregate of the even-numbered electrodes. While the surface of the toner carrying member is moved to a position opposite to the electrostatic latent image carrying member, and the developing device for developing the toner by attaching the toner to the latent image on the electrostatic latent image carrying member,
The toner is the toner according to any one of <1> to <8>.
<12> The image forming method according to <11>, wherein an image is formed by superposing two or more kinds of toners on the electrostatic latent image carrier.

  According to the present invention, the conventional problems can be solved, and by using a developing toner in which a second toner having a certain number of different number average particle diameters is added to the first toner, a low temperature and low humidity environment or Toner used in a hopping developing device that has good hopping properties in a high-temperature and high-humidity environment, has excellent image sharpness, and can significantly improve followability to a pulsed electric field, and the toner An image forming apparatus and an image forming method can be provided.

(toner)
The toner of the present invention includes a first toner having a number average particle diameter Dn1, and a second toner having a number average particle diameter Dn2 that is 2 to 4 times the number average particle diameter Dn1 of the first toner. It is included and used in the following developing device.

<Developing device>
A developing device using the toner of the present invention comprises a surface-movable toner carrier having an electrode pattern having a plurality of electrodes arranged in a predetermined direction in a state of being insulated from each other, and the predetermined electrodes in the plurality of electrodes The toner on the surface of the toner carrier is generated by generating a potential difference between an odd-numbered electrode group that is an aggregate of odd-numbered electrodes starting from the point and an even-numbered electrode group that is an aggregate of even-numbered electrodes. Development that moves the surface of the toner carrying member to a position facing the electrostatic latent image carrying member while moving the toner between the electrodes, and attaches the toner to the latent image on the electrostatic latent image carrying member and develops it. Device.
The developing device has a cylindrical toner carrier having a plurality of electrodes arranged at a predetermined pitch in the circumferential direction. These electrodes are formed by repeatedly arranging electrode pairs composed of two adjacent electrodes. An alternating electric field is formed between the two electrodes in each electrode pair. Then, the toner located on one electrode in the electrode pair floats and landes on the other electrode, or floats on the other electrode and landes on one electrode. Then, while repeating the hopping in this way, the cylindrical toner carrier is transported to the developing region by the surface movement accompanying the rotational driving. In the developing area, the toner that has floated to the vicinity of the latent image on the electrostatic latent image carrier is attracted to the electric field by the latent image and attached to the latent image without descending toward the electrode of the toner carrier. In such a configuration, not the toner adsorbed on the developing roller or the magnetic carrier but the toner that does not exhibit the adsorbing force by hopping is used for the development. As a result, it is possible to realize low potential development that could not be realized by the conventional one-component development method or two-component development method. For example, toner can be selectively attached to an electrostatic latent image having a potential difference of only a few tens [V] with respect to surrounding non-image portions.

The surface of the toner carrier is coated with a material that can give a normal charge to the first toner by friction with the first toner.
Examples of such materials include polyolefin resins such as polyethylene, polypropylene, chlorinated polyethylene and chlorosulfonated polyethylene; polyacrylates such as polystyrene and polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, and polychlorinated. Polyvinyl and polyvinylidene resins such as vinyl, polyvinyl carbazole, polyvinyl ether and polybiliketones; copolymers such as vinyl chloride-vinyl acetate copolymer and styrene-acrylic acid copolymer polytetrachloroethylene, polyvinyl fluoride, polyfluoride Fluorine resins such as vinylidene and polychlorotrifluoroethylene; polyamides; polyesters; polyurethanes; polycarbonates; urea-formaldehyde resins, etc. Amino resins, epoxy resins, silicone resins or modified resins comprising organosiloxane bonds (e.g. alkyd resins, polyester resins, epoxy resins, modified resin by polyurethane or the like), and the like.
The surface of the toner carrier is coated with a material that can give a normal charge to the second toner by friction with the second toner.
Examples of such materials include polyolefin resins such as polyethylene, polypropylene, chlorinated polyethylene and chlorosulfonated polyethylene; polyacrylates such as polystyrene and polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, and polychlorinated. Polyvinyl and polyvinylidene resins such as vinyl, polyvinyl carbazole, polyvinyl ether and polybiliketones; copolymers such as vinyl chloride-vinyl acetate copolymer and styrene-acrylic acid copolymer polytetrachloroethylene, polyvinyl fluoride, polyfluoride Fluorine resins such as vinylidene and polychlorotrifluoroethylene; polyamides; polyesters; polyurethanes; polycarbonates; urea-formaldehyde resins, etc. Amino resins, epoxy resins, silicone resins or modified resins comprising organosiloxane bonds (e.g. alkyd resins, polyester resins, epoxy resins, modified resin by polyurethane or the like), and the like.
Further, it is preferable to have means for forming a charged toner layer on the surface of the toner carrier. Examples of such means include a simultaneous supply and recovery mechanism using a porous roller, regulation using a blade, and a toner supply system using a two-component supply unit.

Here, the developing device used in the present invention will be described with reference to the drawings.
As shown in FIG. 1, an electrode comprising a plurality of electrodes 1, 2, 3, 4, 5,... Arranged in the moving direction at a pitch of W [μm] by depositing aluminum on a glass substrate 11. A substrate is formed as a toner carrier by forming a pattern and forming a resin coating having a thickness of 5 μm and a volume resistivity of about 1 × 10 ¹⁰ Ω · cm as the resin protective layer 10 on the pattern. On the top, a charged toner layer is formed.
For the toner layer in this state, an AC voltage is applied from an AC power source to an odd-numbered electrode group, which is an assembly of odd-numbered electrodes 1, 3,. When an alternating voltage having a phase opposite to that of the alternating voltage is applied to the even-numbered electrode group which is an aggregate, the toner layer has an odd-numbered electrode group position 1, 3... And an even-numbered electrode group position 2, 4. Perform a hopping motion that reciprocates. Then, while repeating the hopping in this way, the cylindrical toner carrier is transported to the developing region by the surface movement accompanying the rotational driving, and the development is performed there.

The toner of the present invention includes a first toner having a number average particle diameter Dn1, and a number 2 to 4 times (preferably 2.5 to 3.5 times) the number average particle diameter Dn1 of the first toner. And a second toner having an average particle diameter Dn2. When the number average particle diameter Dn2 of the second toner is less than twice the number average particle diameter Dn1 of the first toner, no difference is observed in the value of the retained charge, and expectation as a trigger particle for the hopping phenomenon If it exceeds 4 times, it causes an asymmetric friction phenomenon due to the difference in particle size, causing aggregation of toner particles, a decrease in fluidity, and an image quality (edge) that is easily recognized as coarse particles. The sharpness of the image and the resolution) may easily be caused.
The number average particle diameter Dn1 of the first toner is preferably 4 μm to 8 μm. The number average particle diameter Dn2 of the second toner is preferably 10 μm to 20 μm.
The toner number average particle diameter is measured with an aperture diameter of 100 μm using, for example, a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) and analyzed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). Can be measured.

  The content of the second toner is preferably 1% by mass to 10% by mass and more preferably 2.0% by mass to 8.0% by mass with respect to the first toner. When the content of the second toner is less than 1% by mass, the expected function as the expected starting point of the hopping operation does not function effectively, or the time until the hopping operation spreads over all particles. If it exceeds 10% by mass, it will be possible to visually recognize the presence of coarse particles in the output image. There is a problem related to image quality such as a reduction in sharpness of the edge of the toner, or agglomeration phenomenon of toner particles due to asymmetric chargeability.

The second toner may be either colorless particles or colored particles, but is preferably colored particles having the same color as the first toner.
The second toner has the same charging polarity as the first toner.
When the average charge amount per particle of the first toner is AvgQ1, and the average charge amount per particle of the second toner is AvgQ2, it is preferable that AvgQ1 <AvgQ2 is satisfied in absolute value. If this relationship is not satisfied, the expected function as hopping start particles in this developing device may not be achieved.

<First toner and second toner>
As the first toner and the second toner, those having the same composition and the same physical properties can be used except that the number average particle diameter is different as described above. The first toner and the second toner can be used. Each contains at least a binder resin, a colorant, and a release agent, and contains an external additive and, if necessary, other components.

-Binder resin-
The binder resin is not particularly limited and may be appropriately selected from known ones. For example, styrenes such as styrene and chlorostyrene; monoolefins such as ethylene, propylene, butylene and isoprene; vinyl acetate , Vinyl esters such as vinyl propionate, vinyl benzoate, vinyl butyrate; methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic acid esters such as butyl acid and dodecyl methacrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl butyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropenyl ketone Vinyl ketones such as down, homopolymers such as, or a copolymer, and the like.
Particularly representative binder resins include, for example, polystyrene resins, polyester resins, styrene-alkyl acrylate copolymers, styrene-alkyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene. -Maleic anhydride copolymer, polyethylene resin, polypropylene resin and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, polyester resins are preferable, urea-modified polyester resins are more preferable, and combinations of urea-modified polyester resins and unmodified polyester resins are most preferable.

-Colorant-
The colorant is not particularly limited and may 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 Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon. These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.
When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, 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 An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Among these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferable.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable. If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and if it exceeds 160 ° C., a cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  There is no restriction | limiting in particular as content in the toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable. When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

-Other ingredients-
The other components are not particularly limited and can be appropriately selected depending on the purpose. Can be mentioned.

The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. Examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, and molybdate chelate pigments. , Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine activators, salicylic acid metal salts And metal salts of salicylic acid derivatives. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include bontron 03 of a nigrosine dye, bontron P-51 of a quaternary ammonium salt, and bontron S-34 of a metal-containing azo dye. , Oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (both manufactured by Orient Chemical Industries); quaternary ammonium salt molybdenum complex TP- 302, TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.); quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, LR-, which is a boron complex 47 (manufactured by Japan Carlit Co., Ltd.); copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonate group, a carboxyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.

  The content of the charge control agent in the toner varies depending on the type of the resin, the presence or absence of an additive, a dispersion method, and the like, and cannot be generally defined. For example, with respect to 100 parts by mass of the binder resin, 0.1-10 mass parts is preferable and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

The inorganic fine particles can be used as an external additive for imparting fluidity, developability, chargeability and the like to toner particles.
The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The content of the inorganic fine particles in the toner is preferably 0.01% by mass to 5.0% by mass, and more preferably 0.01% by mass to 2.0% by mass.

The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

  The toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the toner can be produced by a pulverization method; a polymerization method such as a suspension polymerization method, an emulsion polymerization method, or a dissolution suspension method.

The pulverization method is, for example, a method of obtaining the toner base particles by melting or kneading the toner material, pulverizing, classifying or the like. In the case of the pulverization method, for the purpose of increasing the average circularity of the toner, the shape may be controlled by applying a mechanical impact force to the obtained toner base particles. In this case, the mechanical impact force can be applied to the toner base particles using a device such as a hybridizer or mechanofusion.
The above toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial continuous kneader, a biaxial continuous kneader, or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay Co., Ltd. Preferably used. This melt-kneading is preferably performed under appropriate conditions that do not cause the molecular chain of the binder resin to be broken. Specifically, the melt kneading temperature is performed with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed by removing the fine particle portion by, for example, a cyclone, a decanter, centrifugation, or the like.
After the pulverization and classification are completed, the pulverized product is classified in an air stream by centrifugal force or the like to produce a toner having a predetermined particle size.

The polymerization method can be obtained, for example, by emulsifying or dispersing a toner material dissolved or dispersed in an aqueous medium to prepare an emulsion or dispersion, and then granulating the toner.
As a preferred embodiment of the toner of the present invention, a solution or dispersion of a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is emulsified or dispersed in an aqueous medium. And a toner obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium to produce particles containing at least an adhesive substrate. .

Hereinafter, the toner according to a preferred embodiment of the present invention will be described.
-Dissolution or dispersion of toner material-
The solution or dispersion of the toner material is obtained by dissolving or dispersing the toner material in a solvent. The toner material is not particularly limited as long as the toner can be formed, and can be appropriately selected according to the purpose. For example, an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound (Prepolymer) at least, including the fixing aid, the colorant, preferably the wax, and, if necessary, the above-mentioned other such as an unmodified polyester resin, a release agent, a charge control agent, etc. Comprising the ingredients of:

The solution or dispersion of the toner material is preferably prepared by dissolving or dispersing the toner material in the organic solvent. The organic solvent is preferably removed during or after the toner granulation.
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, methyl isobutyl ketone, and the like, and ester solvents are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.
In the toner production method of the preferred embodiment of the present invention, the toner material can be dissolved or dispersed in the organic solvent so that it can react with the active hydrogen group-containing compound and the active hydrogen group-containing compound. A toner material such as a polymer, the fixing aid, the unmodified polyester resin, the wax, the colorant, and the charge control agent can be dissolved or dispersed in the toner material. Components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound may be added and mixed in the aqueous medium in the preparation of the aqueous medium described later, or the toner material may be dissolved or dissolved. When the dispersion is added to the aqueous medium, it may be added to the aqueous medium together with the dissolved or dispersed liquid.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) are preferred in that they can be increased in molecular weight by reactions such as elongation reaction and crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). is there.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, alcoholic hydroxyl groups are particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) or those blocked (ketimine compounds).

As a mixing ratio of the amine (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amine group (B) The mixing equivalent ratio of amino group [NHx] ([NCO] / [NHx]) is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, and 1/1. It is particularly preferably 5 to 1.5 / 1.
When the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be lowered. When the mixing equivalent ratio exceeds 3/1, the molecular weight of the urea-modified polyester resin becomes low. The hot offset resistance may be deteriorated.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. However, it can be appropriately selected from known resins, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a heating medium for fixing. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And what made the said active hydrogen group containing polyester resin react with polyisocyanate (PIC), etc. are mentioned.

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol A mixture with (TO), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and the like are preferable. Mixtures are particularly preferred.

As the trivalent or higher polyol (TO), those having 3 to 8 or higher valences are preferable. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.
Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the trivalent or higher polyphenols alkylene oxide adducts include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trivalent or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tricarboxylic or higher polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, sebacic acid, and the like. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
As said aromatic polycarboxylic acid, a C9-C20 thing is preferable, For example, trimellitic acid, pyromellitic acid, etc. are mentioned.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5 mass%-40 mass% Is preferable, 1% by mass to 30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurates And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate. These can be used alone or in combination of two or more.

As a mixing ratio when reacting the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin), the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and 4/1 to 1.2 / 1. Is more preferable, and 3/1 to 1.5 / 1 is particularly preferable.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5 mass%-40 mass % Is preferable, 1% by mass to 30% by mass is more preferable, and 2% by mass to 20% by mass is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

The average number of isocyanate groups contained in one molecule of the isocyanate group-containing polyester prepolymer (A) is preferably 1 or more, more preferably 1.2 to 5, and still more preferably 1.5 to 4.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  The mass average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 3,000 to 40,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 4,000 to 30,000 is more preferable. When the mass average molecular weight (Mw) is less than 3,000, the heat resistant storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.

The measurement of the molecular weight distribution by the gel permeation chromatography (GPC) can be performed, for example, as follows.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Alternatively, the molecular weight of Toyo Soda Industry Co., Ltd. is 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8. It is preferable to use 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

-Aqueous medium-
The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.

  The aqueous medium can be prepared, for example, by dispersing resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5 mass%-10 mass% are preferable.

The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. , Etc.
These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins is preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used. The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). “Sanyo Chemical Industries, Ltd.”, divinylbenzene, 1,6-hexanediol acrylate, and the like.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

-Emulsification or dispersion-
In the emulsification or dispersion of the toner material in the aqueous medium, it is preferable to disperse the toner material in the aqueous medium with stirring. The dispersion method is not particularly limited and can be appropriately selected depending on the purpose. For example, the dispersion method can be performed using a known disperser, and the disperser includes the low-speed shear disperser. And the high-speed shearing disperser.

  In the method for producing a toner according to the preferable aspect of the present invention, when the emulsification or dispersion is performed, the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction. An adhesive substrate (the resin) is generated.

-Adhesive substrate-
The adhesive base material exhibits adhesiveness to a recording medium such as paper, and is formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It may contain at least a polymer and may further contain a binder resin appropriately selected from known binder resins.

There is no restriction | limiting in particular as a mass mean molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 3,000 or more are preferable and 5,000-1,000,000 are more preferable. 7,000 to 500,000 are particularly preferred.
When the mass average molecular weight is less than 3,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said adhesive base material, Although it can select suitably according to the objective, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable. In the toner, since a polyester resin subjected to a crosslinking reaction and an extension reaction coexists, the toner exhibits good storage stability even when the glass transition temperature is lower than that of a conventional polyester toner.
When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.

  The glass transition temperature can be measured by, for example, the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of a sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. can do.

Specific examples of the adhesive substrate are not particularly limited and may be appropriately selected depending on the intended purpose. Particularly preferred are polyester resins.
There is no restriction | limiting in particular as said polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are mentioned especially suitably.
The urea-modified polyester-based resin includes an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable. When the urea bond is less than 10, the hot offset resistance may be deteriorated.

  Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophoronediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol Polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate with isophorone diisocyanate and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene Mixture of oxide 2 mol adduct and terephthalic acid polycondensate, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A Polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and ureaated with hexamethylenediamine, a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate with urea and hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, (9) bisphenol A ethylene Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer urea-modified with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and isophthalic acid with toluene diisocyanate with urea methylenediamine, a 2-mole adduct of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

---- Binder resin ---
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, although a polyester resin etc. are mentioned, Undenatured polyester resin (unmodified polyester resin) is especially preferable.
When the unmodified polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of a polyol (PO) and a polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure that is compatible with each other. It is preferable in terms of hot offset resistance.

The mass average molecular weight (Mw) of the unmodified polyester resin is preferably 1,000 to 30,000, preferably 1,500 to 15, in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). 1,000 is more preferable. When the mass average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Is preferably 8 to 28% by mass. On the other hand, when the mass average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the unmodified polyester resin is preferably 35 ° C to 70 ° C. When the glass transition temperature is less than 35 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g or more, more preferably 10 to 120 mgKOH / g, still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 30.0 mgKOH / g, more preferably 5.0 to 20.0 mgKOH / g. Generally, it becomes easy to be negatively charged by giving the toner an acid value.
When the unmodified polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the unmodified polyester resin (PE) is 5/95. -25/75 is preferable, and 10 / 90-25 / 75 is more preferable.
When the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance may be deteriorated. .

  As content of the said unmodified polyester resin in the said binder resin, 50-100 mass% is preferable, for example, and 55-95 mass% is more preferable. When the content is less than 50% by mass, low-temperature fixability, fixed image strength, glossiness, and the like may be deteriorated.

  The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). A solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium together with the active hydrogen group-containing compound (for example, the amines (B)) to form the oil droplets, and both in the aqueous medium. (2) A solution or dispersion of the toner material may be emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance. It may be formed by forming droplets and subjecting both to extension reaction or crosslinking reaction in the aqueous medium, or (3) dissolving or dispersing the toner material in the aqueous medium After the addition and mixing in the system medium, the active hydrogen group-containing compound is added, the oil droplets are formed, and they are produced by subjecting both to an extension reaction or a crosslinking reaction from the particle interface in the aqueous medium. Good. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive base material by the emulsification or dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours.

  Examples of a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)) in the aqueous medium include, for example, the aqueous system. In a medium, a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, the release agent, the charge control agent, and the unmodified polyester resin And the like. A method in which a solution or dispersion of the toner material prepared by dissolving or dispersing the toner material in the organic solvent is added and dispersed by shearing force.

  In the emulsification or dispersion, the amount of the aqueous medium used is preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner material. When the amount used is less than 50 parts by mass, the toner material is in a poorly dispersed state, and toner particles having a predetermined particle size may not be obtained. When the amount exceeds 2,000 parts by mass, the production cost increases. Sometimes.

In the emulsification or dispersion, if necessary, it is preferable to use a dispersant from the viewpoint of stabilizing the oil droplets and sharpening the particle size distribution while obtaining a desired shape.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a sparingly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and the like. Among these, those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nippon Ink Chemical Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Neos)).

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass); Florard FC-135 (manufactured by Sumitomo 3M); F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products);

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, amides Examples thereof include homopolymers or copolymers of compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, celluloses, and the like.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In preparing the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include those that are soluble in acids and alkalis such as calcium phosphate. When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

The organic solvent is removed from the emulsified slurry obtained by the emulsification or dispersion.
The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed into a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.

The obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, mechanical impact force is applied to remove the release agent, etc. from the surface of the toner particles. It is possible to prevent the particles from being detached.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board, etc. are mentioned. As an apparatus used in this method, for example, an ong mill (manufactured by Hosokawa Micron Co.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure are lowered, and a hybridization system (manufactured by Nara Machinery Co., Ltd.) ), Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

The toner produced by the suspension polymerization method will be described below.
As described above, the toner produced by the suspension polymerization method is prepared by emulsifying or dispersing (suspending) a toner material in an aqueous medium after preparing the emulsion or dispersion (suspension). It can be obtained by granulating the toner.

-Dissolution or dispersion of toner material-
In the suspension polymerization method, the toner material is dissolved or dispersed in a polymerizable monomer, an oil-soluble polymerization initiator, the fixing aid, the colorant, and, if necessary, the wax, Components such as the charge control agent and the crosslinking agent are dissolved or dispersed. In addition, for example, in order to reduce the viscosity of the polymer produced by the polymerization reaction described later, an organic solvent, a high molecular polymer, a dispersant and the like may be added as appropriate.

--Polymerizable monomer--
Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like; acrylamide, methacrylamide , Diacetone acrylamide, or these methylol compounds; vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate and other acrylates or methacrylates that have amino groups, Functional groups can be introduced. In addition, by appropriately selecting a dispersant having an acid group or a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the surface of the toner particles to introduce a functional group.
Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; methyl acrylate, acrylic acid Acrylics such as ethyl, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. Acid esters; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methacrylic acid Eniru, dimethylaminoethyl methacrylate, methacrylic acid esters such as diethylaminoethyl methacrylate; and other acrylonitrile, methacrylonitrile, acrylamide, and the like.

  In addition to the polymerizable monomer, a resin may be used. For example, since the polymerizable monomer is soluble in water and cannot be emulsified by dissolution in an aqueous suspension, an amino group, a carboxylic acid group, a hydroxyl group, a sulfone group, a glycidyl group, a nitrile When a hydrophilic functional group-containing polymerizable monomer such as a group is to be introduced into the toner, a random copolymer of these with a vinyl compound such as styrene or ethylene, a block copolymer, a graft copolymer, etc. A resin in the form of a copolymer, a polycondensate such as polyester or polyamide, or a polyaddition polymer such as polyether or polyimine can be used.

Examples of the alcohol component and the acid component that form the polyester resin include the following.
Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, Examples include 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, and the like. Polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of novolac type phenol resins may be used.
Examples of the acid component include divalent carboxylic acids such as benzene dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; succinic acid, adipic acid, sebacic acid, azelaic acid, and the like. Alkyl dicarboxylic acid or anhydride thereof; succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or anhydride thereof Thing; etc. are mentioned. Further, polycarboxylic acids such as trimellitic acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid, benzophenonetetracarboxylic acid, and anhydrides thereof may be used.
As content of the said alcohol component and the said acid component in the said polyester resin, it is preferable that the said alcohol component is 45-55 mol%, and the said acid component is 55-45 mol%.

Two or more polyester resins may be used in combination as long as the physical properties of the obtained toner particles are not adversely affected. Moreover, physical properties can be adjusted, such as modification with silicone or a fluoroalkyl group-containing compound.
Here, when using a polymer having such a polar functional group, the average molecular weight of the polymer is preferably 5,000 or more.

Furthermore, in addition to the polymerizable monomer, the following resins can be used. Examples of the resin include homopolymers of styrene such as polystyrene and polyvinyltoluene, and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid. Methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer Polymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer Coalescence, styrene-vinylmethylke Copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc .; polymethyl methacrylate, polybutyl methacrylate , Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, Aromatic petroleum resin, and the like. These may be used individually by 1 type and may use 2 or more types together.
The addition amount of the resin is preferably 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the addition amount is less than 1 part by mass, the effect of adjusting the physical properties of the toner particles due to the addition may not be exhibited, and when it exceeds 20 parts by mass, the physical property design of the toner particles may be difficult. Further, a polymer having a molecular weight different from the molecular weight range of the toner obtained by polymerizing the polymerizable monomer can be dissolved in the polymerizable monomer and polymerized.

--Oil-soluble polymerization initiator--
The oil-soluble polymerization initiator has a half-life of 0.5 to 30 hours during the polymerization reaction and is added in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the polymerization reaction is performed, a polymer having a maximum between 10,000 and 100,000 in molecular weight can be obtained, and desirable strength and appropriate dissolution characteristics can be imparted to the toner.
The oil-soluble polymerization initiator is not particularly limited as long as it is oil-soluble, and can be appropriately selected according to the purpose. For example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyr Azo- or diazo-based polymerization initiators such as nitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butyl peroxide 2 -Peroxide polymerization initiators such as ethylhexanoate;

The crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. However, a compound having two or more polymerizable double bonds can be preferably used. For example, divinyl Aromatic divinyl compounds such as benzene and divinylnaphthalene; carboxylate esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline, divinyl ether, divinyl sulfide And divinyl compounds such as divinyl sulfone; and compounds having three or more vinyl groups. These may be used individually by 1 type and may use 2 or more types together.
As addition amount of the said crosslinking agent, 0.001 mass part-15 mass parts are preferable with respect to 100 mass parts of said polymerizable monomers, for example.

-Aqueous medium-
There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water is mentioned.
The aqueous medium preferably contains a dispersion stabilizer.
As the dispersion stabilizer, for example, a known surfactant, organic dispersant, inorganic dispersant and the like can be used. Therefore, an inorganic dispersant is preferable in that it maintains a stable state even when the reaction temperature is changed, is easy to wash, and does not adversely affect the toner.
Examples of the inorganic dispersant include polyvalent metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; calcium metasuccinate, calcium sulfate and barium sulfate. And inorganic oxides such as inorganic salts, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite, and alumina.

The inorganic dispersant can be used as it is, but in order to obtain finer particles, the inorganic dispersant particles may be generated and used in the aqueous medium. For example, in the case of the calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed with high-speed stirring to produce water-insoluble calcium phosphate, which enables more uniform and fine dispersion. At this time, water-soluble sodium chloride salt is by-produced at the same time. However, when the water-soluble salt is present in the aqueous medium, dissolution of the polymerizable monomer in water is suppressed, and ultrafine toner by emulsion polymerization is used. Is preferable because it is difficult to generate. However, since it becomes an obstacle when the remaining polymerizable monomer is removed at the end of the polymerization reaction, it is preferable to replace the aqueous medium or desalinate with an ion exchange resin. The inorganic dispersant can be almost completely removed by dissolution with an acid or alkali after completion of the polymerization.
The inorganic dispersant is preferably used alone in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the inorganic dispersant is used, it is difficult to produce ultrafine particles, but it is difficult to obtain a toner having a small particle diameter. Therefore, it is preferable to use 0.001 to 0.1 parts by mass of a surfactant in combination.
Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

-Suspension-
The suspension is performed by emulsifying or dispersing a solution or dispersion of the toner material in which the toner material is uniformly dissolved or dispersed in the aqueous medium. At this time, if a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser is used to disperse the toner particles to a desired size at once, a toner having a sharp particle size distribution can be obtained.
The oil-soluble polymerization initiator may be added simultaneously with the addition of other additives to the polymerizable monomer, or the solution or dispersion of the toner material is suspended in the aqueous medium. You may mix just before making. Further, during the granulation of the toner, the oil-soluble polymerization initiator dissolved in the polymerizable monomer or solvent may be added immediately after the granulation of the toner and before the start of the polymerization reaction.

-Granulation-
The granulation is performed by polymerizing the polymerizable monomer.
As temperature in the said polymerization reaction, it is 40 degreeC or more, for example, and is generally 50-90 degreeC. When the polymerization is performed within the temperature range, the release agent, the wax, and the like that should be present inside the toner particles are precipitated by phase separation, and can be encapsulated. In order to consume the remaining polymerizable monomer, the reaction temperature may be set to 90 to 150 ° C. As described above, when heated above the melting point of the fixing aid, the resin and the fixing aid are used. Therefore, it is necessary to react at a temperature not higher than the melting point of the fixing aid, specifically, it is preferable to react at 100 ° C. or lower.
In the granulation, it is also possible to use a seed polymerization method in which the polymerized monomer is further adsorbed on the obtained polymer particles and then polymerized using the oil-soluble polymerization initiator. At this time, a polar compound can be dissolved or dispersed in the polymerizable monomer to be adsorbed.

After completion of the polymerization reaction, it is preferable to perform stirring using a normal stirrer at a stirring speed that maintains the particle state and prevents the particles from floating and settling.
The polymer particles after completion of the polymerization reaction are filtered and washed by a known method to remove excess surfactant, dried, and further mixed with inorganic fine powder to adhere to the particle surface. Thus, toner particles are obtained. At this time, it is preferable to remove coarse powder and fine powder by classification.

In the toner of the present invention, an inorganic fine powder having a number average primary particle size of 4 to 80 nm is preferably added as a fluidizing agent.
Examples of the inorganic fine powder include silica, alumina, titanium oxide and the like.
Examples of the silica include, for example, so-called dry silica produced by vapor phase oxidation of silicon halides or dry silica called fumed silica, so-called wet silica produced from water glass, etc. Is mentioned. Among these, dry silica is preferable because there are few silanol groups on the surface and inside the silica fine powder, and there are few production residues such as Na ₂ O and SO ₃ ^— . In dry silica, for example, by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds, composite fine powders of the silica and other metal oxides can be obtained. Composite fine powders can also be used.

Said inorganic fine powder in order to impart good fluidity to the toner, the specific surface area measured by the BET method by nitrogen adsorption, for example, preferably 20~350m ² / g, more preferably 25~300m ² / g .
The specific surface area can be calculated according to the BET method using a specific surface area measuring device ("Autosorb 1"; manufactured by Yuasa Ionics Co., Ltd.) by adsorbing nitrogen gas to the sample surface and using the BET multipoint method.

As content of the said inorganic fine powder, 0.1-3.0 mass% is preferable with respect to a toner base particle, for example. When the addition amount is less than 0.1% by mass, the fluidity may be insufficient, and when it exceeds 3.0% by mass, the fixability may be deteriorated.
The content of the inorganic fine powder can be quantified using, for example, a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

The inorganic fine powder is preferably hydrophobized in that it can maintain excellent characteristics even in a high temperature and high humidity environment.
Examples of the treatment agent in the hydrophobic treatment include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds. These may be used individually by 1 type and may use 2 or more types together.
As a method of the hydrophobization treatment, for example, a silylation reaction is performed as a first-stage reaction and silanol groups are eliminated by chemical bonds, and then a hydrophobic thin film is formed on the surface with silicone oil as a second-stage reaction. The method of hydrophobizing by the above.
As a viscosity at 25 degrees C of the said silicone oil, 10-200,000 mm < ² > / s is preferable, for example, and 3,000-80,000 mm < ² > / s is more preferable.
When the viscosity is less than 10 mm ² / s, the performance of powder the inorganic fine powder becomes unstable due to thermal and mechanical stresses, it may affect the image quality, when it exceeds 200,000 mm ² / s, uniform It may be difficult to perform a hydrophobic treatment.

Preferred examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil.
As a method of using the silicone oil, for example, silica treated with a silane compound and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or a method of spraying silicone oil on silica is used. Alternatively, a method may be used in which after dissolving or dispersing silicone oil in a suitable solvent, silica fine powder is added and mixed to remove the solvent. Among these, the method using a sprayer is preferable in that the formation of aggregates of the inorganic fine powder is relatively small.
The treatment amount of the silicone oil is, for example, preferably 1 part by mass to 40 parts by mass, and more preferably 3 parts by mass to 35 parts by mass with respect to 100 parts by mass of the silica.

  The toner used in the present invention is not particularly limited as to various physical properties such as shape and size, and can be appropriately selected according to the purpose. The following volume average particle diameter (Dv), It is preferable to have a volume average particle diameter (Dv) / number average particle diameter (Dn).

The volume average particle diameter (Dv) of the toner is preferably 3 μm to 8 μm, for example, and more preferably 4 μm to 6 μm.
When the volume average particle size is less than 3 μm, in the two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned, and if it exceeds 8 μm, the resolution is high and the resolution is high. It becomes difficult to obtain an image having an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is, for example, preferably 1.30 or less, and more preferably 1.00-1.30.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is less than 1.00, with the two-component developer, the toner is fused to the surface of the carrier during long-term stirring in the developing device, The chargeability of the carrier may be reduced, and the cleaning property may be deteriorated. In the case of a one-component developer, the filming of the toner on the developing roller and the thinning of the toner are performed. Toner fusion may occur easily, and if it exceeds 1.30, it will be difficult to obtain a high-resolution and high-quality image, and toner particles in the developer balance will be generated. Variation in diameter may be large.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.00 to 1.30, the storage stability, low-temperature fixability, and hot offset resistance are all excellent. In particular, when used in a full-color copying machine, the glossiness of the image is excellent. With two-component developers, there is little fluctuation in the toner particle diameter in the developer even if the toner balance for a long period of time is achieved, and good and stable developability can be obtained even with long-term stirring in the developing device. Even if the balance of the toner is carried out with the agent, fluctuations in the particle diameter of the toner are reduced, and there is no filming of the toner on the developing roller and no fusion of the toner to the member to the blade for thinning the toner. Even in the long-term use (stirring) of the developing device, good and stable developability can be obtained, so that a high-quality image can be obtained.

  The volume average particle diameter and the ratio (Dv / Dn) between the volume average particle diameter and the number average particle diameter are measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can do.

  The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant.

<Developer>
The developer used in the present invention contains at least the toner, and other components appropriately selected such as the carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, and a blade for thinning the toner The toner is not fused to a member such as the above, and good and stable developability and an image can be obtained even in the long-term use (stirring) of the developing device. Further, in the case of the two-component developer using the toner, even if the toner balance is performed over a long period of time, the toner particle diameter fluctuation in the developer is small, and good and stable even with long-term stirring in the developing device. Developability is obtained.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and high magnetization materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The core material has a volume average particle size of preferably 10 μm to 150 μm, more preferably 40 μm to 100 μm.
When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

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

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

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method to use, the method using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90% by mass to 98% % By mass is preferable, and 93% by mass to 97% by mass is more preferable.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, a charging unit, an exposure unit, a developing unit, a transfer unit, and a fixing unit, and a cleaning unit, and further if necessary. Other means appropriately selected, for example, static elimination means, recycling means, control means and the like are provided. The charging unit and the exposure unit may be collectively referred to as an electrostatic latent image forming unit.
The image forming method of the present invention includes at least a charging step, an exposure step, a development step, a transfer step, and a fixing step, and a cleaning step, and other steps appropriately selected as necessary, for example, It includes a static elimination process, a recycling process, a control process, and the like. The charging process and the exposure process may be collectively referred to as an electrostatic latent image forming process.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the charging step can be performed by the charging unit, the exposure step can be performed by the exposing unit, The developing step can be performed by the developing unit, the transferring step can be performed by the transferring unit, the fixing step can be performed by the fixing unit, and the cleaning step can be performed by the cleaning unit. The other steps can be performed by the other means.

-Electrostatic latent image carrier-
The electrostatic latent image carrier (hereinafter also referred to as “electrophotographic photosensitive member”, “photoreceptor”, “latent image carrier”), as to its material, shape, structure, size, etc. There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, a drum shape, a sheet | seat shape, an endless belt shape etc. are mentioned as said shape. The structure may be a single-layer structure or a laminated structure, and the size may be appropriately selected according to the size and specifications of the image forming apparatus. Examples of the material include inorganic photoreceptors such as amorphous silicon, selenium, CdS, and ZnO; organic photoreceptors (OPC) such as polysilane and phthalopolymethine, and the like.

  For example, the amorphous silicon photosensitive member is heated to 50 to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method, or the like is applied on the support. A photosensitive layer made of a-Si is formed by a film forming method. Among these, the plasma CVD method is particularly preferable, and specifically, a method in which the source gas is decomposed by direct current, high frequency, or microwave glow discharge to form a photosensitive layer made of a-Si on the support is preferable. .

The organic photoreceptor (OPC) has (1) optical characteristics such as a wide light absorption wavelength range and a large amount of light absorption, (2) electrical characteristics such as high sensitivity and stable charging characteristics, (3) In general, it is widely applied because of the wide selection range of materials, (4) ease of production, (5) low cost, and (6) non-toxicity. The layer structure of such an organic photoreceptor is roughly classified into a single layer structure and a laminated structure.
The single-layered photoreceptor has a support and a single-layer type photosensitive layer provided on the support, and further includes a protective layer, an intermediate layer, and other layers as necessary.
The laminated structure of the photoreceptor comprises a support, and a laminate type photosensitive layer having at least a charge generation layer and a charge transport layer in this order on the support, and further includes a protective layer and an intermediate layer as necessary. And other layers.

-Charging step and charging means-
The charging step is a step of charging the surface of the electrostatic latent image carrier, and is performed by the charging unit.
The charging means is not particularly limited as long as it can apply a voltage to the surface of the latent electrostatic image bearing member to be uniformly charged, and can be appropriately selected according to the purpose. A non-contact charging means for charging in a non-contact manner with the electrostatic latent image carrier is used.
The non-contact charging means includes, for example, a non-contact charger and a needle electrode device using a corona discharge, a solid discharge element; a conductive or semiconductive material disposed with a small gap with respect to the electrophotographic photosensitive member. And a charging roller. Among these, corona discharge is particularly preferable.

The corona discharge is a non-contact charging method that gives positive or negative ions generated by corona discharge in the air to the surface of the electrophotographic photosensitive member, and has a characteristic of giving a certain amount of charge to the electrophotographic photosensitive member. There are a charger and a scorotron charger having a characteristic of giving a constant potential.
The coroton charger is composed of a casing electrode that occupies a half space around the discharge wire, and a discharge wire placed almost at the center thereof.
The scorotron charger is obtained by adding a grid electrode to the corotron charger, and the grid electrode is provided at a position 1.0 mm to 2.0 mm away from the surface of the electrophotographic photosensitive member.

-Exposure process and exposure means-
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure unit.
The optical system in the exposure is roughly classified into an analog optical system and a digital optical system. The analog optical system is an optical system that projects an original directly onto an electrostatic latent image carrier by the optical system. The digital optical system receives image information as an electrical signal, converts it into an optical signal, An optical system that exposes and forms an electrostatic latent image carrier.
The exposure means is not particularly limited as long as the surface of the electrostatic latent image carrier charged by the charging means can be exposed like an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, a liquid crystal shutter optical system, and an LED optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back surface side of the electrostatic latent image carrier may be adopted.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or developer of the present invention to form a visible image. The developing device used in the developing step is the hopping type described above. The developing device is used. That is, a surface-movable toner carrier having an electrode pattern having a plurality of electrodes arranged in a predetermined direction in a state of being insulated from each other, and the odd-numbered electrode starting from the predetermined electrode in the plurality of electrodes. By generating a potential difference between an odd-numbered electrode group that is an aggregate and an even-numbered electrode group that is an aggregate of even-numbered electrodes, the toner on the surface of the toner carrying body is moved between the electrodes while moving the toner. The development is performed using a developing device that transports the surface of the carrier to a position facing the electrostatic latent image carrier and attaches the toner to the latent image on the electrostatic latent image carrier for development.
The details of the developing device are as described above.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the electrophotographic photosensitive member with the transfer charger using the visible image, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) includes at least a transfer unit that peels and charges the visible image formed on the electrophotographic photosensitive member toward the recording medium. preferable. There may be one transfer means or two or more transfer means. 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 recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

-Fixing Step and Fixing Unit The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium. Alternatively, it may be performed at the same time in a state in which the toner of each color is laminated.

The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. A fixing unit and a heat source for heating the fixing member are used.
Examples of the fixing member include a combination of an endless belt and a roller, a combination of a roller and a roller, and the like. A combination of an endless belt and a roller having a small heat capacity is preferable in terms of expansion of the fixable width.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrophotographic photosensitive member, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrophotographic photosensitive member. For example, a neutralization lamp is preferably used. Can be mentioned.

The cleaning step is a step of removing the toner remaining on the electrophotographic photosensitive member, and can be suitably performed by a cleaning unit. In addition, it is also possible to employ a method in which the charge of the residual toner is made uniform by the rubbing member and collected by the developing roller without using the cleaning means.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrophotographic photosensitive member, and can be appropriately selected from known cleaners. For example, a magnetic brush cleaner Suitable examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

  The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit. There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

Here, FIG. 2 is a schematic view showing an example of the image forming apparatus of the present invention. The image forming apparatus includes the developing device used in the present invention using a toner carrying roller 31.
The toner carrying roller 31 is in contact with the spikes of the two-component developer by a normal two-component developer 56. Specifically, a magnetic sleeve containing a permanent magnet of the two-component developer 56 with a two-component developer obtained by mixing 7 to 8% by mass of a magnetic carrier powder having a particle size of 50 μm and a polyester toner having a particle size of about 6 μm. The toner is conveyed to the toner carrying roller 31 by 57, and a part of the toner is transferred to the toner carrying roller 31 by a DC bias potential applied between the magnet sleeve 57 and the toner carrying roller 31. The toner transferred to the toner carrying roller 31 is conveyed to a portion facing the latent image carrier 58 when the toner carrier 31 is rotationally driven by a drive unit (not shown) while forming a flare on the toner carrier 31. The electrostatic latent image is developed by the difference between the average potential of the surface of the toner carrying roller 31 and the potential of the latent image carrying body 58, thereby developing the electrostatic latent image to form a toner image. . An AC voltage is applied as a bias potential from an AC power source 59 by an electrode brush or the like between the electrode shafts 40A and 40B, and between the odd-numbered electrode groups 41, 43... And the even-numbered electrode groups 42. A time-periodic potential difference is formed.

  Unnecessary toner that has not contributed to the development returns to the magnetic sleeve 57 from the developing portion again. Since the flare is formed, the adhesion force of the toner to the toner carrying roller 31 is very low, and the toner returned from the developing unit by the toner carrying roller 31 is the ear of the two-component developer following the rotation of the magnet sleeve 57. Is easily scraped or habituated. By repeating this, a substantially constant amount of toner flare is always formed on the toner carrying roller 31. The two-component developer 56 conveys and circulates the two-component developer 63 in the container 60 while stirring, and the magnet sleeve 57 conveys a part of the two-component developer to the toner carrying roller 31 and from the developing unit. Unnecessary toner that did not contribute to development is returned.

  The case where an organic photoreceptor (OPC) having a thickness of 13 μm is used as the electrostatic latent image carrier 58 and a latent image is formed using a 1200 dpi laser writing system will be described below. The photosensitive member 58 is rotationally driven by a driving unit (not shown), is uniformly charged by a charging device, and is exposed by a laser writing system as an exposure unit to form an electrostatic latent image. In this case, the electrostatic potential image is formed on the condition that the charging potential of the photosensitive member 58 is −300 V to −500 V and the writing potential at the solid portion is 0 V to −50 V.

  The electrostatic latent image is developed with toner that forms flare on the toner carrier 31 to become a toner image. At this time, using a toner having a charge amount of about −22 μC / g and a particle size of 6 μm, conditions are set so that there is no background stain, the solid portion is well filled, and one dot of 1200 dpi can be reproduced. The gap between the toner carrier 31 and the photoconductor 58 is about 500 μm, and the odd-numbered electrode group and the even-numbered electrode group of the toner carrier 31 have an average potential at each instantaneous moment having peaks of −400V and 0V, respectively. An AC bias of −200 V was realized by applying the AC bias from the AC power supply 59 at a frequency of 5 kHz (the phase of the AC bias was reversed between the odd-numbered electrode group and the even-numbered electrode group).

The toner image on the toner carrier 31 is transferred to a recording medium such as recording paper fed from a paper feeding device by a transfer means, and the toner image is fixed to the recording medium by a fixing device and discharged to the outside.
If excessive toner is placed on the toner carrying roller 31, the electric field curtain is shielded by the charge of the toner and flare cannot be formed, so the amount of toner on the toner carrying roller 31 per unit area is 0. A DC bias of about 200 V is applied from the power source between the magnet sleeve 57 and the toner carrying roller 31 so as to be ² mg / cm ² . Incidentally, since there is a toner diffusion effect due to flare, there is no problem even if there is some unevenness in toner transfer from the magnet sleeve 57 to the toner carrying roller 31, and there is no problem between the magnet sleeve 57 and the toner carrying roller 31. There is no particular need to devise superimposing the AC bias on the DC bias, and no special contrivance to make the spikes of the two-component developer strictly uniform.

On the other hand, since the amount of toner required as a solid image on the photoreceptor 58 is 0.4 mg / cm ² , the moving speed of the toner carrying roller 31 is set so that the toner carrying roller 31 does not run out of toner in the developing unit. The moving speed of the body 58 needs to be twice or more, and here, the moving speed of the photoconductor 58 is set to 2.5 times. The moving direction of the toner carrying roller 31 and the moving direction of the photosensitive member 58 may be the same as shown in FIG. The moving direction of the magnet sleeve 57 and the toner carrying roller 31 is preferably reversed as shown in FIG. 2 in order to obtain a return toner scraping effect.
With the above system, it was confirmed that high-quality development without smearing excellent in solid portion filling property and 1200 dpi dot reproducibility can be realized under the linear velocity of the photosensitive member 58 of 300 mm / s.

  In the image forming apparatus according to the present embodiment, toner having a normal charging polarity of negative polarity (negative polarity) is used as the toner. Then, both the uniformly charged portion (background portion) and the latent image portion of the latent image carrier 58 have the same polarity as the normal charging polarity of the toner (negative polarity in this example), and the potential is attenuated from the background portion. So-called reversal development in which toner is selectively attached to the latent image portion is performed.

As shown in FIG. 1, the cylindrical toner carrying roller 31 in FIG. 2 includes a glass substrate 11, a plurality of electrodes (1, 2, 3, 4, 5, 6...), And these electrodes. And a protective layer 10 which is a surface protective layer covering the surface. The protective layer 10 is made of a material that promotes frictional charging to the normal charging polarity side (minus side in this example) of the toner in accordance with the rubbing with the toner hopping on the surface of the toner carrying roller 31 as the toner carrying body. Is used. That is, the toner is positioned on the minus side in the triboelectric charging series than the protective layer 10. Examples of the material of the protective layer 10 that can realize such a relationship include organic materials such as silicone, nylon, melamine resin, acrylic resin, PVA, and urethane. Moreover, a quaternary ammonium salt, a nigusilon type dye, etc. may be sufficient. Moreover, metal materials, such as Ti, Sn, Fe, Cu, Cr, Ni, Zn, Mg, Al, may be used. _{Also, TiO 2, SnO 2, Fe} 2 O 3, Fe 3 O 4, CuO, Cr 2 O 3, NiO, ZnO, MgO, may be an inorganic material such as _Al 2 _{O 3.} Furthermore, the material which mixed 2 or more of the material illustrated so far may be used.

  In the image forming apparatus having such a protective layer 10, the protective layer 10 (surface protective layer) of the toner carrying roller 31 serving as a toner carrying member is rubbed with the toner to be hopped toward the normal charging polarity side of the toner. Promotes frictional charging. Then, frictional charging to the side opposite to the normal charging polarity of the toner due to rubbing with the protective layer 10 is avoided. Thereby, by suppressing the decrease in the toner charge amount (regular charge polarity) due to hopping, it is possible to suppress the development failure due to the toner hopping failure.

  As the toner, a toner whose normal charging polarity is positive polarity (positive polarity) may be used. In this case, the protective layer 10 may be made of a material that promotes frictional charging of the toner toward the positive polarity side as the toner rubs.

  The toner charging series means a charging series of the whole toner in which an external additive such as silica or titanium oxide is added to the toner base resin (particles). The order in the charging series can be examined as follows. That is, after the toner is rubbed against the surface protective layer for a predetermined time on the surface protective layer, the toner is sucked and collected. Then, the charge amount of the collected toner is measured with an electrometer. If this measurement result indicates an increase in the charge amount of the toner to the negative polarity, the toner becomes a negative charge series with respect to the surface protective layer. Further, if the measurement result indicates an increase in the charge amount of the toner to the positive polarity, the toner becomes a positive charge series with respect to the surface protective layer.

  FIG. 3 is a schematic view of an image forming apparatus according to another embodiment of the present invention. The image forming apparatus is configured to use the same developing device as the developing device including the two-component developing device 56 and the toner carrying roller 31 in the embodiment shown in FIG. 3 and forms the toner images of the respective colors on the photoreceptor. It is an example. In this embodiment, the belt-shaped organic photoconductor 69 as a photoconductor is wound around two rollers (not shown) and is rotationally driven by a drive unit (not shown).

  On the left side of the photoreceptor 69, image forming devices 70K, 70Y, 70C, and 70M are arranged as a plurality of image forming units that respectively form images of a plurality of colors, for example, black, yellow, cyan, and magenta. First, the photoreceptor 69 is uniformly charged by the charging device 71K in the image forming device 70K, and is exposed by the light beam 72K modulated by the black image data by a writing device as an exposure unit (not shown). An electrostatic latent image is formed, and this electrostatic latent image is developed by a developing device 73K having the same configuration as the developing device comprising the two-component developing device 56 and the toner carrying roller 31 in the embodiment shown in FIG. It becomes a toner image. Thereafter, the photoreceptor 69 is neutralized by the static eliminator 74K to prepare for the next image formation.

  Next, the photosensitive member 69 is uniformly charged by the charging device 71Y in the image forming device 70Y, and exposed by a light beam 72Y modulated by yellow image data by a writing device as an exposure unit (not shown). The electrostatic latent image is formed by the developing device 73Y having the same configuration as the developing device including the two-component developing device 56 and the toner carrying roller 31 in the embodiment shown in FIG. The yellow toner image overlaps with the toner image. Thereafter, the photoreceptor 69 is neutralized by the static eliminator 74Y to prepare for the next image formation.

  Next, the photoreceptor 69 is uniformly charged by the charging device 71C in the image forming device 70C, and exposed by a light beam 72C modulated by cyan image data by a writing device as an exposure unit (not shown). Thus, an electrostatic latent image is formed, and this electrostatic latent image is developed by the developing device 73C having the same configuration as the developing device including the two-component developing device 56 and the toner carrying roller 31 in the embodiment shown in FIG. A black toner image and a cyan toner image overlapping the yellow toner image are obtained. Thereafter, the photoreceptor 69 is neutralized by the static eliminator 74C to prepare for the next image formation.

  Next, the photosensitive member 69 is uniformly charged by the charging device 71M in the image forming device 70M, and exposed by a light beam 72M modulated by magenta image data by a writing device as an exposure unit (not shown). Thus, an electrostatic latent image is formed, and this electrostatic latent image is developed by the developing device 73M having the same configuration as the developing device including the two-component developing device 56 and the toner carrying roller 31 in the embodiment shown in FIG. A full-color image is formed by forming a black toner image, a yellow toner image, and a magenta toner image overlapping the cyan toner image.

  On the other hand, a recording medium such as recording paper is fed from a sheet feeding device (not shown), and a full color image on the photosensitive member 69 is transferred to the recording medium by a transfer roller 75 as a transfer unit to which a transfer bias is applied from a power source. . The recording medium on which the full color image is transferred is fixed by the fixing device 76 and discharged to the outside. Residual toner and the like are removed from the photoconductor 69 by a cleaner 77 as a cleaning unit after the transfer of a full-color image.

  In this embodiment, four colors are written on the same photoconductor 69, and therefore, in principle, there is almost no positional deviation compared to the normal quadruple tandem system, and colors can be superimposed on the photoconductor. Therefore, it is possible to obtain a high-quality full-color image with no positional deviation.

  In the image forming method and the image forming apparatus of the present invention, as described above, the hopping type developing device is used, and further, the toner including the first toner and the second toner suitable for the developing device is used. Therefore, the followability to the pulse electric field can be greatly improved, and an image excellent in environmental characteristics and sharpness can be obtained.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples, the number average particle diameter of the toner was measured as follows.

<Measurement of number average particle diameter of toner>
The number average particle diameter of the toner was measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm, and analyzed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). . Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml beaker made of glass, and 0.5 g of each toner is added. Next, 80 ml of ion-exchanged water was added.
The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important to adjust the concentration to 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size. After measuring the number of toners, the number distribution was calculated.
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; 13 channels of 32.00 μm or more and less than 40.30 μm were used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm were targeted.

(Production Example 1)
<Preparation of Toner A>
-Synthesis of organic fine particle emulsion-
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 83 parts by mass of styrene Part, 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). An aqueous dispersion of [fine particle dispersion 1] was prepared.
The obtained [Fine Particle Dispersion 1] was measured with a particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.), and the mass average particle diameter was 105 nm. Moreover, a part of [Fine Particle Dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 59 ° C., and the mass average molecular weight was 150,000.

-Preparation of aqueous phase-
990 parts by weight of water, 83 parts by weight of [Fine Particle Dispersion 1], 37 parts by weight of a 48.5% by weight aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.), and 90 parts by weight of ethyl acetate Were mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].

-Synthesis of low molecular weight polyester-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propylene oxide 3-mole adduct, 208 parts by mass of terephthalic acid, adipic acid 46 parts by mass and 2 parts by mass of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at 5 to 15 mm under reduced pressure, and then 44 parts by mass of trimellitic anhydride in the reaction vessel And reacted at 180 ° C. for 2 hours under normal pressure to synthesize [low molecular weight polyester 1].
The obtained [Low molecular weight polyester 1] had a number average molecular weight of 2,500, a weight average molecular weight of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25 mgKOH / g.

-Synthesis of intermediate polyester and prepolymer-
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, anhydrous 22 parts by mass of trimellitic acid and 2 parts by mass of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to synthesize [Intermediate Polyester 1]. .
The obtained [Intermediate polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g. .

  Next, 410 parts by mass of [Intermediate Polyester 1], 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The reaction was performed for a while to obtain [Prepolymer 1]. [Prepolymer 1] obtained had a free isocyanate mass% of 1.53%.

-Synthesis of ketimine-
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of the obtained [ketimine compound 1] was 418.

-Preparation of master batch-
35 parts by mass of water, 40 parts by mass of phthalocyanine pigment (manufactured by Toyo Ink Manufacturing Co., Ltd., FG7351), and 60 parts by mass of polyester resin (manufactured by Sanyo Chemical Industries, Ltd., RS801) are mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, cooled by rolling, and pulverized with a pulverizer to produce [Masterbatch 1].

-Preparation of oil phase-
In a container in which a stir bar and a thermometer are set, 378 parts by mass of [low molecular weight polyester 1], 110 parts by mass of carnauba wax, 22 parts by mass of a charge control agent (salicylic acid metal complex E-84, manufactured by Orient Chemical Industry Co., Ltd.) , And 947 parts by mass of ethyl acetate were added, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts by mass of [Masterbatch 1] and 500 parts by mass of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
1,324 parts by mass of the obtained [raw material solution 1] was transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / second, and 0.5 mm. Filled with 80% by volume of zirconia beads, the pigment and the wax were dispersed under conditions of 3 passes. Next, 1,324 parts by mass of a 65% by weight ethyl acetate solution of [low molecular weight polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1].
The [Pigment / Wax Dispersion 1] obtained had a solid content concentration (130 ° C., 30 minutes) of 50% by mass.

-Emulsification-
[Pigment / Wax Dispersion 1] 648 parts by mass, [Prepolymer 1] 154 parts by mass, and [Ketimine Compound 1] 6.6 parts by mass are put in a container and 5 are added using a TK homomixer (made by Tokushu Kika Co., Ltd.). After mixing at 3,000 rpm for 1 minute, 1,200 parts by mass of [Aqueous Phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 20 minutes to prepare [Emulsion Slurry 1].

-Shape control-
[Emulsion slurry 1] is mixed with an aqueous solution in which ion-exchanged water, an activator, and a thickener are put in a container at an appropriate ratio and stirred, and the mixture is mixed at 2,000 rpm with a TK homomixer (made by Tokushu Kika Co., Ltd.). The mixture was mixed for 1 hour to obtain [Shape Control Slurry 1].

-Solvent removal-
[Shape control slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

-Cleaning and drying-
[Dispersion Slurry 1] 100 parts by mass were filtered under reduced pressure, and then washed and dried as follows.
(1) 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2) 100 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3) 100 parts by mass of 10 mass% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4) Add 300 parts by mass of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [filter cake 1]. It was.
The obtained [Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, sieved with a mesh of 75 μm, and [Toner base particle A] having a number average particle diameter Dn1 of 5.3 μm was produced. .

  0.8 parts by mass of isobutyl-treated hydrophobic titanium oxide having an average particle diameter of 15 nm was added to 100 parts by mass of the obtained [toner base particle A], and the peripheral speed of the stirring blade was 20 m / s using a Henschel mixer. And then dispersed and adhered to the surface of the toner base. After these operations, 1.0 part by mass of hexamethyldisilazane-treated hydrophobic silica having an average particle size of 12 nm was added, and the stirring blade was mixed at a peripheral speed of 20 m / s with a Henschel mixer, and the opening was 38 μm. Coarse powder and agglomerates were removed using a mesh of [Toner A] as a first toner.

(Production Example 2)
-Preparation of auxiliary particles A-
In the production process of [toner base particle A] in Production Example 1, the conditions after the emulsification process were changed to produce auxiliary particle base A having a number average particle diameter Dn2 of 8.2 μm.
The obtained auxiliary base particle A was subjected to an external additive mixing step in the same manner as in the toner base particle A, thereby producing auxiliary particles A as a second toner coated with the external additive. However, the amount of the external additive to be added is determined so that the surface charge density is equal by carrying out with the addition amount converted based on the covering ratio in consideration of the difference in diameter between the toner base particles and the auxiliary particles. Carried out.

(Production Example 3)
-Preparation of auxiliary particles B-
In the production process of [toner base particle A] in Production Example 1, the conditions after the emulsification process were changed to produce auxiliary particle base B having a number average particle diameter Dn2 of 12.1 μm.
The obtained auxiliary base particle B was subjected to an external additive mixing step in the same manner as in the toner base particle A, thereby preparing auxiliary particles B as a second toner coated with the external additive. However, the amount of the external additive to be added is determined so that the surface charge density is equal by carrying out with the addition amount converted based on the covering ratio in consideration of the difference in diameter between the toner base particles and the auxiliary particles. Carried out.

(Production Example 4)
-Production of auxiliary particles C-
In the production process of [toner base particle A] in Production Example 1, the conditions after the emulsification process were changed to produce auxiliary particle base C having a number average particle diameter Dn2 of 17.4 μm.
The obtained auxiliary base particle C was subjected to an external additive mixing step in the same manner as in the toner base particle A, thereby producing auxiliary particles C as a second toner coated with the external additive. However, the amount of the external additive to be added is determined so that the surface charge density is equal by carrying out with the addition amount converted based on the covering ratio in consideration of the difference in diameter between the toner base particles and the auxiliary particles. Carried out.

(Production Example 5)
-Production of auxiliary particles D-
In the production process of [toner base particle A] in Production Example 1, the conditions after the emulsification process were changed to prepare auxiliary particle base D having a number average particle diameter Dn2 of 23.2 μm.
The obtained auxiliary base particle D was subjected to an external additive mixing step in the same manner as in the toner base particle A, thereby preparing auxiliary particles D as a second toner coated with the external additive. However, the amount of the external additive to be added is determined so that the surface charge density is equal by carrying out with the addition amount converted based on the covering ratio in consideration of the difference in diameter between the toner base particles and the auxiliary particles. Carried out.

(Comparative Example 1)
-Preparation of toner A and image formation-
A developing toner A was prepared by mixing toner A and auxiliary particles A so that the mass ratio (toner A: auxiliary particles A) was 100: 0.5.
Using this development toner A, image formation was performed as follows, and performance was evaluated. The results are shown in Table 1.

<Measurement of average charge amount of toner and auxiliary particles>
The average charge amount of the toner and auxiliary particles was evaluated using a blow-off charge amount measuring device manufactured by Toshiba Chemical Corporation. The carrier was weighed so that the toner concentration was 7 mass% by mixing toner with carrier N-01 for spherical negatively charged polarity toner surface-treated with a ferrite core distributed by the Imaging Society of Japan. Subsequently, an electrostatic charge image developer was prepared by stirring and mixing with a ball mill for 5 minutes, and measurement was performed with a blow-off device manufactured by Toshiba Chemical Co., Ltd. at 23 ° C. and an humidity of 85% RH.

<Evaluation of hopping performance>
As shown in FIG. 1, an electrode comprising a plurality of electrodes 1, 2, 3, 4, 5,... Arranged in a moving direction at a pitch of W [μm] by depositing aluminum on a glass substrate 11. A substrate is formed as a toner carrier by forming a pattern and forming a resin (alkyd melamine) coat having a thickness of 5 μm and a volume resistivity of about 1 × 10 ¹⁰ Ω · cm as a resin protective layer 10 on the pattern. The hopping performance was evaluated using a developing device in which a charged toner layer was formed on the substrate.
For the toner layer in this state, an AC voltage is applied from an AC power source to an odd-numbered electrode group that is an assembly of odd-numbered electrodes 1, 3,. When an alternating voltage having a phase opposite to that of the alternating voltage is applied to the even-numbered electrode group which is an aggregate, the toner layer has an odd-numbered electrode group position 1, 3... And an even-numbered electrode group position 2, 4. A hopping exercise was performed to reciprocate.
The flare activity at this time and the followability after pulse application were observed with a high-speed camera (manufactured by Shimadzu Corporation, Hyper Vision HPV-1), and the hopping performance was evaluated.
Here, the activity of the flare is obtained by observing the state of the toner stuck to the surface of the substrate and not moving, and the individual follow-up characteristics are also similarly applied to the followability. The difference until the particle group behavior shifted to the overall behavior was determined by the following four sensory evaluations. This evaluation was performed at low temperature and low humidity (8 ° C., 30% RH), normal temperature and normal humidity (23 ° C., 50% RH), and high temperature and high humidity (35 ° C., 85% RH).
〔Evaluation criteria〕
◎: Good hopping property 〇: No hopping property △: Slightly poor hopping property ×: Poor hopping property

<Evaluation of sharpness of image>
The image forming apparatus shown in FIG. 3 equipped with the developing device shown in FIG. 1 is used, and a photosensitive drum is installed in a form facing the developing device, and a development toner in which an electrostatic latent image pattern is written is hopped. The image was developed and the sharpness of the image at the edge was evaluated according to the following four criteria.
〔Evaluation criteria〕
◎: Good ○: No problem △: Somewhat bad ×: Bad

(Comparative Example 2)
-Preparation of toner B and image formation-
A developing toner B was prepared by mixing toner A and auxiliary particles A so that the mass ratio (toner A: auxiliary particles A) was 100: 1.
Using this development toner B, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Comparative Example 3)
-Preparation of toner C and image formation-
A developing toner C was prepared by mixing toner A and auxiliary particles A so that the mass ratio (toner A: auxiliary particles A) was 100: 4.
Using this development toner C, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Comparative Example 4)
-Preparation of toner D and image formation-
A developing toner D was prepared by mixing toner A and auxiliary particles A so that the mass ratio (toner A: auxiliary particles A) was 100: 8.
Using this development toner D, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Comparative Example 5)
-Preparation of toner E and image formation-
A developing toner E was prepared by mixing toner A and auxiliary particles A so that the mass ratio (toner A: auxiliary particles A) was 100: 11.
Using this developing toner E, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Comparative Example 6)
-Preparation of toner F and image formation-
A developing toner F was prepared by mixing toner A and auxiliary particles A so that the mass ratio (toner A: auxiliary particles A) was 100: 15.
Using this development toner F, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

Example 1
-Preparation of toner G and image formation-
A developing toner G was prepared by mixing toner A and auxiliary particles B so that the mass ratio (toner A: auxiliary particles B) was 100: 0.5.
Using this developing toner G, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Example 2)
-Preparation of toner H and image formation-
A developing toner H was prepared by mixing toner A and auxiliary particles B so that the mass ratio (toner A: auxiliary particles B) was 100: 1.
Using this developing toner H, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Example 3)
-Preparation of toner I and image formation-
A developing toner I was prepared by mixing toner A and auxiliary particles B so that the mass ratio (toner A: auxiliary particles B) was 100: 4.
Using this development toner I, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

Example 4
-Preparation of toner J and image formation-
Developing toner J was prepared by mixing toner A and auxiliary particles B so that the mass ratio (toner A: auxiliary particles B) was 100: 8.
Using this developed toner J, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Example 5)
-Preparation of toner K and image formation-
A developing toner K was prepared by mixing toner A and auxiliary particles B such that the mass ratio (toner A: auxiliary particles B) was 100: 11.
Using this developing toner K, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Example 6)
-Production of toner L and image formation-
A developing toner L was prepared by mixing toner A and auxiliary particles B so that the mass ratio (toner A: auxiliary particles B) was 100: 15.
Using this development toner L, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Example 7)
-Preparation of toner M and image formation-
A developing toner M was prepared by mixing toner A and auxiliary particles C so that the mass ratio (toner A: auxiliary particles C) was 100: 0.5.
Using this developing toner M, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Example 8)
-Preparation of toner N and image formation-
A developing toner N was prepared by mixing toner A and auxiliary particles C so that the mass ratio (toner A: auxiliary particles C) was 100: 1.
Using this developed toner N, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

Example 9
-Preparation and image formation of developing toner O-
A developing toner O was prepared by mixing toner A and auxiliary particles C so that the mass ratio (toner A: auxiliary particles C) was 100: 4.
Using this developed toner O, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Example 10)
-Preparation of toner P and image formation-
A developing toner P was prepared by mixing toner A and auxiliary particles C so that the mass ratio (toner A: auxiliary particles C) was 100: 8.
Using this development toner P, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Example 11)
-Preparation of toner Q and image formation-
A developing toner Q was prepared by mixing toner A and auxiliary particles C so that the mass ratio (toner A: auxiliary particles C) was 100: 11.
Using this development toner Q, an image was formed as follows, and the performance was evaluated. The results are shown in Table 1.

Example 12
-Preparation of toner R and image formation-
A developing toner R was prepared by mixing toner A and auxiliary particles C such that the mass ratio (toner A: auxiliary particles C) was 100: 15.
Using this developing toner R, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Comparative Example 7)
-Production of toner S and image formation-
A developing toner S was prepared by mixing toner A and auxiliary particles D so that the mass ratio (toner A: auxiliary particles D) was 100: 0.5.
Using this development toner S, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Comparative Example 8)
-Preparation of toner T and image formation-
A developing toner T was prepared by mixing toner A and auxiliary particles D such that the mass ratio (toner A: auxiliary particles D) was 100: 1.
Using this developed toner T, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Comparative Example 9)
-Preparation of toner U and image formation-
A developing toner U was prepared by mixing toner A and auxiliary particles D such that the mass ratio (toner A: auxiliary particles D) was 100: 4.
Using this developing toner U, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Comparative Example 10)
-Preparation of toner V and image formation-
A developing toner V was prepared by mixing toner A and auxiliary particles D so that the mass ratio (toner A: auxiliary particles D) was 100: 8.
Using this development toner V, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Comparative Example 11)
-Production of developer toner W and image formation-
A developing toner W was prepared by mixing toner A and auxiliary particles D such that the mass ratio (toner A: auxiliary particles D) was 100: 11.
Using this developing toner W, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

(Comparative Example 12)
-Preparation of toner X and image formation-
A developing toner X was prepared by mixing toner A and auxiliary particles D such that the mass ratio (toner A: auxiliary particles D) was 100: 15.
Using this developing toner X, an image was formed in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Tables 1 and 2.

  The toner of the present invention has a good hopping property in a low-temperature and low-humidity environment or a high-temperature and high-humidity environment, is excellent in sharpness of an image, and can significantly improve the followability to a pulse electric field. It is suitable for an apparatus, and is preferably used for an electrophotographic image forming apparatus such as a copying machine, a printer, and a facsimile machine that forms an image using the developing device.

FIG. 1 is a schematic view showing an example of a developing device used in the present invention. FIG. 2 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 3 is a schematic view showing another example of the image forming apparatus of the present invention.

Explanation of symbols

1, 2, 3, 4, 5, 6 Electrode 10 Resin protective layer 11 Glass substrate T Toner 31 Toner carrier 56 Two-component developer 57 Magnet sleeve 58 Electrostatic latent image carrier 59 AC power supply 60 Container 61, 62 Conveying roller 63 Two-component developer 69 Belt-shaped organic photoreceptor 70K, 70Y, 70C, 70M Image forming device 71K, 71Y, 71C, 71M Charging device 72K, 72Y, 72C, 72M Exposure by exposure device 73K, 73Y, 73C, 73M Development Device 74K, 74Y, 74C, 74M Static eliminator 75 Transfer roller 76 Fixing device 77 Cleaner

Claims (12)

An assembly of odd-numbered electrodes having a surface-movable toner carrier provided with an electrode pattern having a plurality of electrodes arranged in a predetermined direction in a state of being insulated from each other, starting from the predetermined electrodes of the plurality of electrodes The toner carrier while moving the toner on the surface of the toner carrier between the electrodes by generating a potential difference between the odd-numbered electrode group and the even-numbered electrode group which is an assembly of even-numbered electrodes. A toner used in a developing device that transports to a position facing the electrostatic latent image carrier by moving the surface of the toner and attaches the toner to the latent image on the electrostatic latent image carrier and develops the toner.
A first toner having a number average particle diameter Dn1, and a second toner having a number average particle diameter Dn2 that is 2 to 4 times the number average particle diameter Dn1 of the first toner. toner.   The toner according to claim 1, wherein the content of the second toner is 1% by mass to 10% by mass with respect to the first toner.   The toner according to claim 1, wherein the second toner is any one of colorless particles and colored particles.   The toner according to claim 1, wherein the second toner has the same charging polarity as the first toner.   5. The absolute value of AvgQ1 <AvgQ2 is satisfied, where AvgQ1 is an average charge amount per particle of the first toner and AvgQ2 is an average charge amount per particle of the second toner. Toner.   The toner according to claim 1, wherein the surface of the toner carrying member is coated with a material capable of giving a normal charge to the first toner by friction with the first toner.   The toner according to claim 1, wherein the surface of the toner carrying member is coated with a material capable of giving a regular charge to the second toner by friction with the second toner.   The toner according to claim 1, further comprising means for forming a charged toner layer on the surface of the toner carrier. An electrostatic latent image carrier, a charging unit for charging the surface of the electrostatic latent image carrier, an exposure unit for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the static Developing means for developing an electrostatic latent image with toner to form a visible image; Transfer means for transferring the visible image to a recording medium; Fixing means for fixing the transferred image transferred to the recording medium; An image forming apparatus having at least
The developing means includes a surface-movable toner carrier having an electrode pattern having a plurality of electrodes arranged in a predetermined direction in a state of being insulated from each other, and the odd-numbered number starting from the predetermined electrode in the plurality of electrodes The toner on the surface of the toner carrier is moved between the electrodes by generating a potential difference between the odd-numbered electrode group that is an aggregate of the electrodes and the even-numbered electrode group that is the aggregate of the even-numbered electrodes. A developing device that transports the toner carrier to a position facing the electrostatic latent image carrier by moving the surface of the toner carrier and attaches the toner to the latent image on the electrostatic latent image carrier and develops the toner.
An image forming apparatus, wherein the toner is the toner according to claim 1.   The image forming apparatus according to claim 9, wherein two or more types of toner are superimposed on the electrostatic latent image carrier to form an image. A charging process for charging the surface of the electrostatic latent image carrier, an exposure process for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and developing the electrostatic latent image using toner. An image forming method including at least a developing step for forming a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. ,
The developing step includes a surface-movable toner carrier having an electrode pattern having a plurality of electrodes arranged in a predetermined direction in a state of being insulated from each other, and is an odd number starting from the predetermined electrode of the plurality of electrodes. The toner on the surface of the toner carrier is moved between the electrodes by generating a potential difference between the odd-numbered electrode group that is an aggregate of the electrodes and the even-numbered electrode group that is the aggregate of the even-numbered electrodes. While the surface of the toner carrying member is moved to a position opposite to the electrostatic latent image carrying member, and the developing device for developing the toner by attaching the toner to the latent image on the electrostatic latent image carrying member,
The image forming method, wherein the toner is the toner according to claim 1.   The image forming method according to claim 11, wherein an image is formed by superposing two or more kinds of toners on the electrostatic latent image carrier.