JP4648187B2 - Toner, developer, toner manufacturing method, image forming apparatus, and image forming method - Google Patents

Description

  The present invention relates to a toner, a developer, a toner manufacturing method, an image forming apparatus, and an image forming method, and more particularly, to an image forming apparatus such as a copying machine, a facsimile, or a printer that forms an image by electrophotography (electrostatic copying process). The present invention relates to a toner, a developer, a method for producing the toner, an image forming apparatus using the toner, and an image forming method using the toner.

  As described in Patent Document 1, image formation by electrophotography or the like forms an electrostatic image on a photoconductor as an image carrier, develops the electrostatic latent image with a developer, and forms a toner image (visible). Then, the toner image is transferred to a recording medium such as recording paper and fixed to form a fixed image.

  As a developer used in such an image forming method, a one-component developer using a magnetic toner or a non-magnetic toner alone and a two-component developer composed of a toner and a carrier are known.

  As a fixing method in the electrophotographic method, a heating heat roller method in which a toner image is fixed by directly pressing a heating roller against a toner image on a recording medium is widely used because of its energy efficiency.

  However, in the case of the heating heat roller system, there is a problem that a large amount of electric power is required to heat the heating roller.

  From the viewpoint of solving this problem and saving energy, various studies have been made to reduce the power consumption of the heating roller. For example, the output of the heater for the heating roller is weakened when the image is not output, and the heater is output when the image is output. Generally, a method of increasing the output of the heating roller to increase the temperature of the heating roller is used.

  In the case of such a system, a standby time of about several tens of seconds is required to raise the temperature of the heating roller to a temperature necessary for fixing when the sleep mode is switched to the operation mode. In addition, when not outputting images, it is desirable to further reduce power consumption by turning off the heater completely. However, when starting up the operation mode from completely off, an equivalent standby time is required. It becomes. Since this waiting time is stressful for the user, shortening the waiting time as much as possible contributes to the convenience of the user.

  In order to shorten the standby time for heating the heating roller, it is considered essential to lower the fixing temperature of the toner itself and lower the toner fixing temperature when it can be used.

  As a technique for realizing low-temperature fixing of the toner, there is a method of controlling the thermal characteristics of the resin itself. For example, by adding a melt-miscible substance compatible with the resin into the toner, the glass transition temperature of the resin ( Techniques for reducing Tg) have been used. However, if the Tg is lowered too much, the heat resistant storage stability is deteriorated.

  In recent years, it has been a long-standing challenge to develop a toner that can achieve both a low-temperature fixability and a heat-resistant storage stability having a trade-off relationship as described above at a good level. The following has been proposed as an invention relating to a toner capable of achieving both such low-temperature fixability and heat-resistant storage stability at good levels.

  Patent Document 2 proposes a heat-fixable toner in which a Tg of a binder resin is lowered by using a plasticizer in the toner inner layer, and resin protrusions containing no plasticizer are present on the particle surface.

  In Patent Document 3, for example, an electron containing a wax and a binder that does not separate and precipitate in the wax when the wax having a melting point of 20 to 150 ° C. is dissolved in the wax as a solvent and further rapidly cooled. Photographic toners have been proposed.

  Patent Document 4 proposes an electrostatic charge image developing toner containing a polyfunctional ester compound that is compatible with a resin monomer.

Patent Document 5 proposes a polyester resin toner composition in which an aliphatic ester compound having a melting point of 60 to 100 ° C. is added to a polyester resin toner.
US Pat. No. 2,297,691 JP-A-6-258861 JP 2002-221825 A JP 2001-281909 A JP 2000-56505 A

  However, the above-described invention has the following problems.

  In the invention described in Patent Document 2, although the toner particles are configured to have protrusions, the interior of the toner is mainly composed of a low Tg resin, so that it has a good level of low-temperature fixability and heat-resistant storage stability. It is difficult to achieve both.

  In the invention described in Patent Document 3, although the wax exhibits a plastic effect on a resin having a melting point higher than the fixing temperature, low temperature fixing can be realized, but the wax is produced by a pulverization method including a melt-kneading step. For this reason, a plasticizing effect has already been manifested during production, and the heat resistant storage stability is not sufficient.

  Further, the invention described in Patent Document 4 merely uses a resin monomer having a melting point of about the same value as that of the polyfunctional ester compound, and the glass transition temperature (Tg) of the toner. Is already in a state in which the plastic effect by the polyfunctional ester compound is exhibited, so that it is impossible to sufficiently achieve both low-temperature fixability and heat-resistant storage stability.

  In addition, the invention described in Patent Document 5 has a description that it is excellent in low-temperature fixability by using a polyester as a resin, and that it is excellent in hot offset property by an aliphatic ester. Is considered to be due to its effect as a release agent, which is not a drastic improvement.

  Therefore, it achieves both excellent low-temperature fixability and heat-resistant storage stability, has excellent properties such as fluidity and fixability, and provides high-quality images even under low-temperature fixing conditions. At present, a toner capable of realizing power saving and shortening of standby time and a related technology using the toner have not been realized yet.

  The present invention has been made in consideration of the above-mentioned current situation, and has both excellent low-temperature fixability and heat-resistant storage stability, and has excellent properties such as fluidity and fixability, even under low-temperature fixing conditions. An object of the present invention is to provide a toner capable of obtaining a high-quality image and realizing power saving and shortening of standby time. It is another object of the present invention to provide a developer using the toner, a method for producing the toner, an image forming apparatus using the toner, and an image forming method.

  The invention described in claim 1 is a toner containing at least a polyester resin and a colorant, and the toner further contains a polyalkylene glycol ester compound represented by the following chemical formula 1, The polyalkylene glycol ester compound has a melting point in the range of 50 ° C. or higher and 100 ° C. or lower, and is incompatible with the polyester resin at 50 ° C. and is compatible with the polyester resin at 100 ° C. To do.

In the above chemical formula 1, R ¹ and R ² are linear or branched alkyl groups having 1 to 24 carbon atoms, and R _xm and R _ym are hydrogen or linear or branched alkyl groups having 1 to 6 carbon atoms. Represents an alkyl group. N represents an integer of 2 or more, and m represents an integer of 2 or more and 4 or less.

  According to a second aspect of the present invention, in the toner according to the first aspect, the polyalkylene glycol ester compound has a weight average molecular weight of 3000 to 20000.

  According to a third aspect of the present invention, in the toner according to the first or second aspect, the content of the polyalkylene glycol ester compound is 1 to 20 parts by weight with respect to 100 parts by weight of the polyester resin. .

  According to a fourth aspect of the present invention, in the toner according to any one of the first to third aspects, the melting point of the polyalkylene glycol ester compound obtained by DSC measurement at the first temperature increase is 50 ° C. or higher. It is characterized by.

  According to a fifth aspect of the present invention, in the toner according to any one of the first to fourth aspects, the polyalkylene glycol ester compound has a hydroxyl value of 20 mgKOH / g or more.

  According to a sixth aspect of the present invention, in the toner according to any one of the first to fifth aspects, the polyalkylene glycol ester compound is a polyethylene glycol diester compound.

  A seventh aspect of the present invention is a developer using the toner according to any one of the first to sixth aspects.

  The invention according to claim 8 is obtained by emulsifying or dispersing 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 in an aqueous medium. A method for producing a toner comprising preparing an emulsified or dispersed liquid and granulating the toner after the preparation.

  According to a ninth aspect of the present invention, in the toner manufacturing method according to the eighth aspect, the toner is granulated by reacting the active hydrogen group-containing compound and the polymer to produce an adhesive substrate. It is performed by obtaining particles containing at least the adhesive substrate.

  According to a tenth aspect of the present invention, in the toner production method according to the eighth or ninth aspect, the polymer includes a polyalkylene glycol ester compound represented by the following chemical formula 2.

In the above chemical formula 2, R ¹ and R ² are linear or branched alkyl groups having 1 to 24 carbon atoms, and R _xm and R _ym are hydrogen or linear or branched alkyl groups having 1 to 6 carbon atoms. Represents an alkyl group. N represents an integer of 2 or more, and m represents an integer of 2 or more and 4 or less.

  According to an eleventh aspect of the present invention, there is provided an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and a developer. Developing means for developing the electrostatic latent image formed on the carrier to form a visible image; transfer means for transferring the visible image formed on the electrostatic latent image carrier to a recording medium; An image forming apparatus comprising at least a fixing unit that fixes the transferred image transferred onto the recording medium, wherein the developer is the developer according to claim 7. To do.

  According to a twelfth aspect of the present invention, an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier and developing the electrostatic latent image using a developer to form a visible image An image forming method for forming an image by performing at least a development step, a transfer 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 developer is the developer according to claim 7.

  The toner of the present invention comprises at least a polyester resin and a polyalkylene glycol ester compound having a melting point of 50 ° C. to 100 ° C., and the polyester resin and the polyalkylene glycol ester compound are present in the toner independently in an incompatible state during storage. In addition, since the polyester resin and the polyalkylene glycol ester compound are compatibilized by heating at the time of fixing, they exhibit excellent heat-resistant storage stability during storage and excellent low-temperature fixing properties during fixing. Therefore, the toner of the present invention is excellent in various properties as a toner such as fluidity and fixability, and can achieve both excellent low-temperature fixability and heat-resistant storage stability.

  Hereinafter, a toner, a toner, a developer, a method for producing the toner, an image forming apparatus using the toner, and an image forming method using the toner according to the present invention will be described in detail according to the embodiments.

<Toner>
The toner according to the exemplary embodiment includes at least a polyester resin and a polyalkylene glycol ester compound having a melting point of 50 ° C. or higher and lower than 100 ° C., and further, as necessary, a colorant, a release agent, and a charge control agent. It contains other components such as.

  The polyester resin and the polyalkylene glycol ester compound are incompatible with each other at 50 ° C. or lower, and are compatible at 100 ° C. or higher.

<Polyester resin>
The polyester resin is not particularly limited as long as it contains at least one polyester resin and can be appropriately selected and used according to the purpose. For example, a known binder resin can be used.

  The polyester resin used in this embodiment is a dehydration-condensation of one or more polyols represented by the following chemical formula 3 and one or more polycarboxylic acids represented by the following chemical formula 4. Alternatively, it is dealcoholized and polyesterified.

  In the above chemical formula 3, A represents an alkylene group having 1 to 20 carbon atoms, an alkyne group, an aromatic group that may have a substituent or a heterocyclic aromatic group, and m represents an integer of 2 to 4. , R represents an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. When m is plural, the OR groups may be the same or different.

  In the above chemical formula 4, B represents an alkylene group having 1 to 20 carbon atoms, an alkyne group, an aromatic group that may have a substituent or a heterocyclic aromatic group, and n represents an integer of 2 to 4. To express.

  Among the compounds represented by Chemical Formula 3, as the polyol, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1 , 4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3 , 6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, -Methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A oxidation Examples include propylene adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, and the like. An example of an ether compound represented by Formula 3 in which at least one hydrogen group (hydrogen atom) of the OH group of the above-described compound is substituted with an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group) Become.

  Examples of the polycarboxylic acid represented by Chemical Formula 4 include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, Malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, , 2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, butanetetra Examples thereof include carboxylic acid, diphenylsulfone tetracarboxylic acid, ethylene glycol bis (trimellitic acid) and the like.

  The amount of the polyester resin used is preferably 50 to 95% by weight, more preferably 70 to 85% by weight, based on the toner composition.

  The resin preferably has a hydroxyl value of 20 mgKOH / g or more. This is because when the hydroxyl value is 20 mgKOH / g, the hot offset property is excellent. It is considered that such a characteristic appears because the hydroxyl value is three-dimensionally composed of a site that easily reacts to a crosslinking structure with a crosslinking agent described later and a weak crosslinking.

<Polyalkylene glycol ester compound>
The polyalkylene glycol ester compound is a compound obtained by esterifying one or more carboxylic acids represented by the following chemical formula 5 and a polyalkylene glycol represented by the following chemical formula 6.

In the above chemical formula 5, X represents an aliphatic saturated alkyl group or alkylene group having 1 to 24 carbon atoms. Moreover, in said Chemical formula 6, n represents an integer greater than or equal to 2, m represents an integer greater than or equal to 2 and less than or equal to 4, _Rxm and _Rym are H or a linear or branched chain shape having 1 to 6 carbon atoms. Represents an alkyl group.

  A polyalkylene glycol ester compound composed of a carboxylic acid represented by Chemical Formula 5 and a polyalkylene glycol represented by Chemical Formula 6 uses a conventionally known acid catalyst or alkali catalyst in the presence or absence of a solvent. It can be obtained by dehydration condensation.

  Examples of the carboxylic acid represented by Chemical Formula 5 include linear, branched or cyclic aliphatic saturated carboxylic acids. Specific examples include propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid.

  The polyalkylene glycol ester compound is preferably a polyethylene glycol diester compound. This is because when the polyalkylene glycol ester compound is a polyethylene glycol diester compound, it is incompatible with the polyester resin at 50 ° C. or lower, and is easily compatible with the polyester resin at 100 ° C. or higher.

  In addition, the polyalkylene glycol ester compound preferably has a weight average molecular weight of 3000 to 20000. This is because if the molecular weight is less than 3000, the melting point of the polyalkylene glycol ester compound tends to be 50 ° C. or less, resulting in poor heat-resistant storage stability, and if the molecular weight exceeds 20000, the hydrophilicity of the polyalkylene glycol ester compound increases. This is because there is a possibility that the charging characteristics of the battery deteriorate.

  The content of the polyalkylene glycol ester compound in the toner is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the polyester resin. This is because if the amount is less than 1 part by weight, the amount of the polyalkylene glycol ester compound that is compatible with the polyester during fixing is small, so the low-temperature fixability may be inferior, and if it exceeds 20 parts by weight, the hot offset property may be inferior. Because there is.

<Measurement of compatible state>
There is no restriction | limiting in particular as a measuring method of the compatibility state of the polyester resin and polyalkylene glycol ester compound at the time of a preservation | save, According to the objective, it can select suitably. For example, the toner is embedded in an epoxy resin, cut into ultra-thin sections of about 100 μm, stained with ruthenium tetroxide, and then observed with a transmission electron microscope (TEM) at a magnification of 10,000 times for photography. Then, by evaluating the image of this photograph, it can be determined that the polyester-polyalkylene glycol ester compound is incompatible with each other during storage.

  There is no restriction | limiting in particular as a measuring method of the compatibility state of the polyester resin and polyalkylene glycol ester compound at the time of a heating, According to the objective, it can select suitably. For example, it can be judged by whether the toner is heated and melted to 100 ° C. or higher and the polyester resin and the polyalkylene glycol ester compound are separated from each other to form an interface. When no interface is formed in this method, it can be determined that the polyester resin and the polyalkylene glycol ester compound are compatible with each other when heated.

  The glass transition temperature and melting point of the resin, toner, and polyalkylene glycol ester compound are measured by the following method using, for example, a DSC system (differential scanning calorimeter “DSC-60”; manufactured by Shimadzu Corporation). be able to.

  The Tg (glass transition temperature) of the resin and toner at the first temperature increase is as follows. First, about 5.0 mg of resin or toner (sample) is placed in an aluminum sample container, and the sample container is placed on a holder unit. Then, in a nitrogen atmosphere, the sample is heated from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./min, and a DSC curve is measured with a differential scanning calorimeter “DSC-60”. From the obtained DSC curve, for example, using an analysis program in the DSC-60 system, calculation is performed from the intersection of the tangent line between the curve before the inflection point of the resin (or toner) and the curve after the inflection point.

  At the same time, the melting point of the polyalkylene glycol ester compound can be determined from the peak value derived from the polyalkylene glycol ester compound.

  When the melting point of the polyalkylene glycol ester compound overlaps with the peak of other substances (resin, wax, etc.) in the toner, the polyalkylene glycol ester compound is obtained by performing DSC measurement on the polyalkylene glycol ester compound alone. The melting point of can be determined.

  The obtained toner preferably has a first Tg of 50 ° C. or higher. This is because if the Tg is less than 50 ° C., the heat resistant storage stability of the toner may be inferior.

<Other ingredients>
Examples of other components other than the binder resin used in manufacturing the toner include a colorant, a release agent, a charge control agent, inorganic fine particles, a fluidity improver, a cleaning property improver, a magnetic material, and a metal. Soap and the like. These are not particularly limited and can be appropriately selected and used according to the purpose.

(Coloring agent)
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, Parare , Phi Sae 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, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue , Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid Lean lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon, etc. can be used. 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. This is because when the content of the colorant is less than 1% by mass, the coloring power of the toner is lowered, and when the content exceeds 15% by mass, the pigment is poorly dispersed in the toner, and the coloring power is lowered. This is because the electrical 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 resins, aromatic petroleum resins, chlorinated paraffin, paraffin wax, and the like can be used. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the styrene or substituted polymer thereof include polyester resin, polystyrene, poly p-chlorostyrene, and polyvinyl toluene. Examples of the styrene copolymer include styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer. Copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methacrylic copolymer Acid butyl copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene- Acrylonitrile-indene copolymer, steel Down - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch is produced by mixing or kneading a masterbatch resin and a colorant with a high shear force. 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 mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is used.

(Release agent)
There is no restriction | limiting in particular as a mold release agent, According to the objective, it can select suitably and can be used.

  As the release agent, for example, waxes, waxes and the like are used. Specifically, plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; petroleum oils such as paraffin, microcrystalline, and petrolatum And natural waxes such as waxes. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Also, fatty acid amides such as 12-hydroxystearic amide, stearic amide, phthalic anhydride imide, chlorinated hydrocarbons; low molecular weight crystalline polymer resins, poly-n-stearyl methacrylate, poly-n-lauryl A homopolymer or copolymer of polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, and the like can also be used. These may be used alone or in combination of two or more.

  The melting point of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 to 120 ° C, more preferably 60 to 90 ° C. This is because if the melting point is less than 50 ° C., the release agent may adversely affect the heat resistant storage stability, and if it exceeds 120 ° C., a cold offset tends to occur during fixing at a low temperature. In this regard, if a low melting point release agent having a melting point of 50 to 120 ° C. is used, it is dispersed with the resin, so that it effectively acts as a release agent between the fixing roller and the toner interface. Even when a release agent such as oil is not applied to the fixing roller, a good hot offset property can be realized.

  The melt viscosity of the release agent is preferably 5 to 1000 cps (5 to 1000 mPa · S), more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. This is because if the melt viscosity is less than 5 cps (5 mPa · S), the releasability may be lowered, and if it exceeds 1,000 cps, the improvement effect on hot offset resistance and low-temperature fixability may not be obtained. Because there is.

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

(Charge control agent)
The charge control agent is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate Pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine activators, salicylic acid metals A salt, a metal salt of a salicylic acid derivative, or the like can be used. These may be used individually by 1 type and may use 2 or more types together.

  A commercially available charge control agent may be used. Examples of the commercially available products include bontron 03, a nigrosine dye, bontron P-51, a quaternary ammonium salt, bontron S-34, a metal-containing azo dye, E-82, an oxynaphthoic acid metal complex, and a salicylic acid metal. E-84 of the complex, E-89 of the phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of the quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, boron complex LR-147 (Nippon Carlit), copper phthalocyanine, peri Examples include lenic, quinacridone, azo pigments, and other high molecular compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  The content of the charge control agent in the toner varies depending on the type of resin, the presence / absence of an additive, a dispersion method, and the like, and thus cannot be defined unconditionally. A mass part is preferable and 0.2-5 mass parts is more preferable. This is because if the content is less than 0.1 parts by mass, the charge controllability may not be obtained. If 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. This is because the electrostatic attraction force with the developing roller is increased and the fluidity of the developer and the image density are lowered.

(Inorganic fine particles)
The inorganic fine particles are used as an external additive for imparting fluidity, developability, chargeability and the like to the toner particles. The inorganic fine particles are not particularly limited and can be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanium Strontium acid, 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, Silicon carbide, silicon nitride, or the like can be used. 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. Further, the content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass.

(Fluidity improver)
A fluidity improver is 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, Silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like.

  Silica and titanium oxide are particularly preferably subjected to surface treatment with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

(Cleaning improver)
The cleaning property 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 or the like. And polymer fine particles produced by soap-free emulsion polymerization such as polymethyl 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 to 1 μm are suitable.

(Magnetic material)
There is no restriction | limiting in particular as a magnetic material, According to the objective, it can select and use suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. can be used. Note that. Among these, white is particularly preferable in terms of color tone.

<Manufacture of toner>
The toner described above can be obtained (manufactured) using a known method such as a suspension polymerization method, an emulsion polymerization method, or a dissolution suspension method. For example, the toner material is dissolved or dispersed in an aqueous medium. It can be obtained by granulating a toner after preparing an emulsified or dispersed liquid by emulsifying or dispersing.

  As a preferred embodiment, 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. It is obtained by reacting an active hydrogen group-containing compound with a polymer capable of reacting with the active hydrogen group-containing compound to produce particles containing at least an adhesive substrate.

(Dissolution or dispersion of toner material)
The dissolved or dispersed liquid of the toner material is obtained by dissolving or dispersing the toner material in a solvent or a dispersion medium.

  The toner material is not particularly limited as long as the toner can be formed, and can be appropriately selected and used according to the purpose. For example, a compound comprising at least one of an active hydrogen group-containing compound and a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound, preferably further comprising a plasticizer, and further if necessary In addition, those containing the above-mentioned other components such as an unmodified polyester resin, a release agent, a colorant, and a charge control agent can be used.

  The solution or dispersion of the toner material is prepared by dissolving or dispersing the toner material in an organic solvent. The organic solvent is preferably removed during or after the toner granulation.

  The organic solvent or dispersant 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, and in particular, has a boiling point in terms of ease of removal. Volatile ones below 150 ° C are preferred. Examples include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Examples thereof include methyl isobutyl ketone, but a steal solvent is preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.

  The amount of the organic solvent used is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 40 to 300 parts by weight, more preferably 60 to 140 parts by weight, based on 100 parts by weight of the toner material. -120 mass parts is still more preferable.

  In the toner production, the toner material is dissolved or dispersed in an organic solvent in an active hydrogen group-containing compound, a polymer that can react with the active hydrogen group-containing compound, an unmodified polyester resin, a release agent, It can be carried out by dissolving or dispersing a toner material such as a colorant and a charge control agent. 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. When the solution or dispersion is added to the aqueous medium, it may be added to the aqueous medium together with the solution or dispersion.

(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 an 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 according to the purpose. For example, when the polymer capable of reacting with the active hydrogen group-containing compound is an isocyanate group-containing polyester prepolymer (A), the polymer is highly reactive with the isocyanate group-containing polyester prepolymer (A) by a reaction such as an extension reaction or a crosslinking reaction. The amines (B) are preferable from the viewpoint of molecular weight.

  There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably. Examples of the active hydrogen group include a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), amino group, carboxyl group, mercapto group, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, alcoholic hydroxyl groups are particularly preferable.

  There is no restriction | limiting in particular as amines (B), According to the objective, it can select suitably and can be used, for example, diamine (B1), trivalent or more polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), amino acid block of B1 to B5 (B6), and the like can be used. 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 amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan, aminopropyl mercaptan, and the like. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.

  In addition, as the block (B6) in which the amino group of B1 to B5 is blocked, 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 is used to stop the elongation reaction, the crosslinking reaction, and the like between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of a reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. As the reaction terminator, monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), or those obtained by blocking them (ketimine compounds) can be used.

  As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), an isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and an amino group in the amines (B) [ The mixing equivalent ratio of NHx] ([NCO] / [NHx]) is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, and 1 / 1.5 to Particularly preferred is 1.5 / 1. This is because if the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be lowered, and if it exceeds 3/1, the molecular weight of the urea-modified polyester resin is lowered, and It is because hot offset property may deteriorate.

(Polymer capable of reacting with active hydrogen group-containing compound)
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter 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. It can be used by appropriately selecting from the above. Examples of the prepolymer include polyol resin, polyacrylic resin, polyester resin, epoxy resin, 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 can be appropriately selected from known substituents, for example, an isocyanate group, an epoxy group, a carboxylic acid, and an acid chloride group. , Etc. These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

  Among prepolymers, it is easy to adjust the molecular weight of the polymer component, ensuring oil-free low-temperature fixing characteristics for dry toners, especially good release and fixing properties even without a release oil coating mechanism for the heating medium for fixing. In view of the capability, a urea bond-forming group-containing polyester resin (RMPE) is particularly preferable.

  As a urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond generating group in the urea bond generating group-containing polyester resin (RMPE) is an isocyanate group, the polyester resin (RMPE) is particularly preferably an isocyanate group-containing polyester prepolymer (A).

  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 is active. Examples include those obtained by reacting a hydrogen group-containing polyester resin with polyisocyanate (PIC).

  There is no restriction | limiting in particular as a 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 ( TO) and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, diol (DIO) alone or a mixture of diol (DIO) and a small amount of 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, polytetramethylene ether glycol, and the like. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to alicyclic diol. Examples of bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of bisphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to bisphenols.

  Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

  The trivalent or higher polyol (TO) is preferably 3 to 8 or higher. For example, trihydric or higher polyhydric aliphatic alcohols, trihydric or higher polyphenols, trihydric or higher polyphenols alkylene oxide adducts, and the like.

  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 alkylene oxide adduct of trihydric or higher polyphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to trihydric 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 to 10 is preferable, and 100: 0.01-1 is more preferable.

  There is no restriction | limiting in particular as polycarboxylic acid (PC), According to the objective, it can select suitably, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) and A mixture with a polycarboxylic acid having a valence of 3 or more can be used. 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 (DIC) 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. Moreover, as alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As the aromatic dicarboxylic acid, those having 8 to 20 carbon atoms are preferable, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid and the like.

  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 the aromatic polycarboxylic acid, those having 9 to 20 carbon atoms are preferable, and examples thereof include trimellitic acid and pyromellitic acid.

  The polycarboxylic acid (PC) is any one selected from dicarboxylic acid (DIC), trivalent or higher polycarboxylic acid (TC), and a mixture of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid. These acid anhydrides or lower alkyl ester compounds can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  As a mixing mass ratio (DIC: TC) of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC) in a mixture of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), There is no restriction | limiting, 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, the hydroxyl group in the polyol (PO) [ OH] and the equivalent ratio ([OH] / [COOH]) of the carboxyl group [COOH] in the polycarboxylic acid (PC) are usually preferably 2/1 to 1/1, and 1.5 / The ratio is more preferably 1-1 / 1, and particularly preferably 1.3 / 1-1.02 / 1.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer (A) of a polyol (PO), Although it can select suitably according to the objective, 0.5-40 mass% is preferable, for example. -30 mass% is more preferable, and 2-20 mass% is especially preferable. This is because if 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. This is because the low-temperature fixability may deteriorate.

  There is no restriction | limiting in particular as polyisocyanate (PIC), According to the objective, it can select suitably, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurates, 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, tetra And methyl hexane 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 -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 isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate. These may be used alone or in combination of two or more.

  As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing polyester resin are used. In general, the mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1. 3/1 to 1.5 / 1 is particularly preferred. This is because if the isocyanate group [NCO] exceeds 5, the low-temperature fixability may deteriorate, and if it is less than 1, the offset resistance may deteriorate.

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

  As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable. This is because if the average number of isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with urea bond-forming groups is lowered, and the hot offset resistance may be deteriorated.

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

  In addition, the measurement of molecular weight distribution by gel permeation chromatography (GPC) is performed as follows, for example.

  First, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent was allowed to flow at a flow rate of 1 ml (1 ml) per minute, and 50 to 200 μl (microliter) of a tetrahydrofuran sample solution of a resin whose sample concentration was adjusted to 0.05 to 0.6% by mass. ) Inject and measure.

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 number of counts. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Alternatively, the molecular weights of Toyo Soda Kogyo Co., Ltd. are 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6. It is preferable to use those of × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

(Aqueous medium)
There is no restriction | limiting in particular as an aqueous medium, It can select suitably from well-known things and can use it, for example, water, the solvent miscible with this water, a mixture thereof, etc. can be used. Among these, water is particularly preferable.

  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, and ethylene glycol. Examples of 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, Although it can select suitably according to the objective, 0.5-10 mass% is especially preferable.

  The resin fine particles are not particularly limited as long as they can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose. The resin fine particles may be a thermoplastic resin or a thermosetting resin.

  Examples of the resin fine particles include 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, and the like. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, what is formed with at least 1 sort (s) selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin is preferable at the point from which the aqueous dispersion of a fine spherical resin particle is easy to be obtained.

  The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic ester polymer, Examples thereof include a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer.

  As the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can also be used. The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the purpose. For example, a sodium salt of methacrylic acid ethylene oxide adduct sulfate (“Eleminol RS-30”) ; Sanyo Chemical Industries), 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 it is particularly preferable to obtain the resin fine particles as an aqueous dispersion. As a method for preparing the aqueous dispersion of the resin fine particles, the following method is suitable.

(1) In the case of a vinyl resin, an aqueous dispersion of resin fine particles directly by a polymerization reaction selected from a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method using a vinyl monomer as a starting material (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, and epoxy resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof in an aqueous medium in the presence of an appropriate dispersant. (3) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc. , A suitable emulsifier is dissolved in a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably a liquid. It may be liquefied by heating). (4) Resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) Is obtained by pulverizing using a mechanical rotating type or jet type fine pulverizer and then classifying the resin fine particles to disperse them in water in the presence of an appropriate dispersant. (5) Polymerization reaction ( (Any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc. may be used.) A resin solution in which a resin prepared by dissolving in a solvent is sprayed in a mist to obtain resin fine particles. (6) Polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) Resin prepared by After adding a poor solvent to the resin solution dissolved in the solvent or by cooling the resin solution previously heated and dissolved in the solvent to precipitate resin fine particles, the solvent is removed to obtain resin particles, Method of dispersing resin particles in water in the presence of an appropriate dispersant (7) In advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) A method in which a resin solution in which a prepared resin is dissolved in a solvent is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then the solvent is removed by heating or decompression. (8) Polymerization reaction (addition polymerization, ring opening) (Either polymerization, polyaddition, addition condensation, condensation polymerization, etc. may be used) Any suitable emulsifier is dissolved in a resin solution prepared by dissolving a resin prepared in a solvent, and water is added to perform phase inversion. How to emulsify

(Emulsification or dispersion)
In the dissolution or dispersion of the toner material in the aqueous medium, the dissolution or dispersion of the toner material is dispersed in the aqueous medium while stirring. There is no restriction | limiting in particular as this dispersion | distribution method, According to the objective, it can select suitably, For example, it can carry out using a well-known disperser etc. Examples of the disperser include a low speed shear disperser and a high speed shear disperser.

  In the toner production method of the present embodiment, during emulsification or dispersion, an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a cross-linking reaction to produce an adhesive substrate. .

(Adhesive substrate)
The adhesive base material has an adhesive property to a recording medium such as paper, and includes at least an adhesive polymer obtained by reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium. Comprising. Further, a binder resin appropriately selected from known binder resins may be included.

  There is no restriction | limiting in particular as a weight average molecular weight of an adhesive base material, Although it can select suitably according to the objective, For example, 3,000 or more are preferable, 5,000-1,000,000 are more preferable, 7,000 to 500,000 are particularly preferred. This is because when the weight 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 an 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. This is because the toner of this embodiment exhibits good storage stability even when the glass transition temperature is lower than that of a conventional polyester-based toner due to the coexistence of a cross-linking and elongation-reacting polyester resin. However, if the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and if it exceeds 70 ° C., the low-temperature fixability may not be sufficient.

  The glass transition temperature is measured using, for example, a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). Specifically, first, about 10 mg of toner is put 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. To do.

  There is no restriction | limiting in particular as an adhesive base material, Although it can select suitably according to the objective, A polyester-type resin etc. are mentioned especially suitably.

  There is no restriction | limiting in particular as a polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are especially suitable. The urea-modified polyester resin comprises an amine (B) as an 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 in an aqueous medium. It can be obtained by reacting.

  The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the content molar ratio of the urea bond and the urethane bond (urea bond / urethane bond) is not particularly limited and may be appropriately selected depending on the intended purpose, but is 100/0 to 10/90. Preferably, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable. This is because if the urea bond is less than 10, the hot offset resistance may be deteriorated.

  As the urea-modified polyester resin, the following substances (1) to (10) are suitable.

(1) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and isophthalic acid with isophorone diisocyanate and uread with isophorone diamine, bisphenol A ethylene oxide 2-mole adduct and isophthalic acid 2. Mixture with polycondensate (2) Polyester prepolymer obtained by reacting a 2-condensate of bisphenol A ethylene oxide adduct and a polycondensate of isophthalic acid with isophorone diisocyanate, and 2 moles of bisphenol A ethylene oxide Mixture with adduct and polycondensate of terephthalic acid (3) Bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate Mixture of polyester prepolymer reacted with holon diisocyanate and uread with isophoronediamine, bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct, and polycondensate of terephthalic acid (4) Bisphenol Polyester prepolymer obtained by reacting polycondensate of A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol and terephthalic acid with isophorone diisocyanate and 2 mol addition of bisphenol A propylene oxide 2 (5) Bisphenol A ethylene oxide 2-mole adduct and terephthalic acid polycondensate are reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with hexamethylenediamine and a polycondensate of bisphenol A ethylene oxide 2-mole adduct and terephthalic acid (6) A mixture of bisphenol A ethylene oxide 2-mole adduct and terephthalic acid A mixture of a polyester prepolymer obtained by reacting a condensate with isophorone diisocyanate with hexamethylenediamine and a polycondensate of bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid (7) A polyester prepolymer obtained by reacting a bicondensate of bisphenol A ethylene oxide 2 mol and a polycondensate of terephthalic acid with isophorone diisocyanate, urea-modified with ethylenediamine, (8) Polyester prepolymer obtained by reacting bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate with diphenylmethane diisocyanate is converted to hexamethylenediamine. (9) Bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid / dodecenyl succinate A polyester prepolymer obtained by reacting a polycondensate of acid anhydride with diphenylmethane diisocyanate and uread with hexamethylenediamine, and 2 mol of bisphenol A ethylene oxide. (10) Polyester prepolymer obtained by reacting bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate with toluene diisocyanate Preferable examples include a mixture of urea-methylenediamine, a bisphenol A ethylene oxide 2-mole adduct and a polycondensate of isophthalic acid.

(Binder resin)
There is no restriction | limiting in particular as binder resin, According to the objective, it can select and use suitably, For example, a polyester resin etc. can be used. In particular, an unmodified polyester resin (an unmodified polyester resin) is preferable. This is because when the unmodified polyester resin is contained in the toner, the 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 polyol (PO) and polycarboxylic acid (PC). A part of the unmodified polyester resin is compatible with a 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.

  The weight 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). 000 is more preferable. This is because when the weight average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may deteriorate, and when the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may deteriorate. Because. In addition, as above-mentioned, content of the component whose weight average molecular weight (Mw) is less than 1,000 needs to be 8-28 mass%.

  The glass transition temperature of the unmodified polyester resin is preferably 35 to 70 ° C. This is because if the glass transition temperature is less than 35 ° C., the heat-resistant storage stability of the toner may deteriorate, and if 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. This is because if the hydroxyl value is less than 5, 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 in the range of 1.0 to 30.0 mgKOH / g, particularly preferably 5.0 to 20.0 mgKOH / g. This is because the toner tends to be negatively charged by giving an acid value to the toner.

  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 to 25 / 75 is preferable, and 10/90 to 25/75 is more preferable. This is because when the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance may be deteriorated, and when it is less than 75, the low-temperature fixability and the glossiness of the image may be deteriorated. It is.

  The content of the unmodified polyester resin in the binder resin is preferably 50 to 100% by mass, and more preferably 55 to 95% by mass. This is because if the content is less than 50% by mass, the low-temperature fixability, fixed image strength, glossiness, and the like may deteriorate.

  The adhesive substrate (for example, a urea-modified polyester resin) is, for example, (1) a toner material containing a polymer (for example, an isocyanate group-containing polyester prepolymer (A)) that can react with an active hydrogen group-containing compound. The dispersion is emulsified or dispersed in an aqueous medium together with an active hydrogen group-containing compound (for example, amines (B)), oil droplets are formed, and both are subjected to an extension reaction or a crosslinking reaction in the aqueous medium. (2) A solution or dispersion of the toner material is emulsified or dispersed in an aqueous medium to which an active hydrogen group-containing compound has been added in advance to form oil droplets, and both are elongated in the aqueous medium. It may be produced by a reaction or a crosslinking reaction, or (3) an active hydrogen group containing after dissolving and dispersing the toner material in an aqueous medium. The compound was added to form oil droplets, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in aqueous medium.

  In the case of (3), a modified polyester resin is preferentially produced on the toner surface to be produced, so that it is possible to provide a concentration gradient in the toner particles.

  The reaction conditions for producing an adhesive substrate by emulsification or dispersion are not particularly limited, and are appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. be able to. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours.

  Examples of a method for stably forming a dispersion containing a polymer capable of reacting with an active hydrogen group-containing compound (for example, an isocyanate group-containing polyester prepolymer (A)) in an aqueous medium include, for example, an activity in an aqueous medium. Dissolve or disperse a toner material such as an isocyanate group-containing polyester prepolymer (A), a colorant, a release agent, a charge control agent, and an unmodified polyester resin in an organic solvent that can react with a hydrogen group-containing compound. For example, a method of adding a solution or dispersion of a toner material prepared in such a manner and dispersing the toner material by shearing force may be used.

  In 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. This is because when the amount used is less than 50 parts by mass, the toner material is not well dispersed, 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. Because there is.

(Dispersant)
In emulsification or dispersion, 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, if necessary. There is no restriction | limiting in particular as a dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly 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, and those having a fluoroalkyl group are particularly 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 (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 Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of amine salt type surfactants 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 Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); F-824 (manufactured by Dainippon Ink, Inc.); Xtop EF-132 (manufactured by Tochem Products);

  Examples of nonionic surfactants 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 hardly 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 a compound containing a carboxyl group, amide compounds Alternatively, homopolymers or copolymers such as those having methylol compounds, chlorides, nitrogen atoms or heterocyclic rings thereof, polyoxyethylenes, celluloses, and the like can be given.

  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, glycerin monoacrylate, Examples include glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like.

  Examples of esters of a compound containing vinyl alcohol and 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 chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of homopolymers or copolymers 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 type include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, Examples include polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of celluloses include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

  In preparing the dispersion, a dispersion stabilizer can be used as necessary. Examples of the dispersion stabilizer include acids that can be dissolved in acids and alkalis such as calcium phosphate salts. When a calcium phosphate salt is used as a dispersion stabilizer, the calcium phosphate salt can be removed from the fine particles by a method in which the calcium phosphate salt is dissolved with an acid such as hydrochloric acid and then washed with water or decomposed with an enzyme.

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

(Removal of organic solvent)
The organic solvent is removed from the emulsified slurry obtained by emulsification or dispersion. As a method for removing the organic solvent, (1) 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. 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 can be employed.

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

(Applying mechanical shock)
Thus, the obtained toner particles are mixed with particles of a colorant, a release agent, a charge control agent and the like, and further, a mechanical impact force is applied to the particles of the release agent from the surface of the toner particles. Can be prevented from desorbing.

  As a method of applying a mechanical impact force, for example, a method of applying an impact force to a mixture with a blade rotating at high speed, a mixture of particles in a high-speed air stream and acceleration to mix particles or a composite particle is a suitable collision plate. It is possible to adopt a method of causing the collision to occur. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

<Toner physical properties>
Various physical properties such as the shape and size of the toner according to the exemplary embodiment are not particularly limited and may be appropriately selected depending on the intended purpose. However, the following volume average particle diameter (Dv), volume average particle may be used. It is preferable to have diameter (Dv) / number average particle diameter (Dn), penetration, low-temperature fixability, offset non-occurrence temperature, and the like.

  The volume average particle diameter (Dv) of the toner is preferably 3 to 8 μm. This is because when the volume average particle size is less than 3 μm, the two-component developer may cause the toner to be fused to the surface of the carrier during long-term agitation in the developing device, thereby reducing the charging ability of the carrier. This is because the component developer tends to cause toner filming on the developing roller and toner fusion to a member such as a blade because the toner is thinned. On the other hand, when the thickness exceeds 8 μm, it is difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase. .

  Further, 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. This is because when the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is less than 1.00, the two-component developer fuses the toner to the surface of the carrier during long-term agitation in the developing device. However, the charging ability of the carrier may be reduced or 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 may cause a blade or the like. This is because toner fusion to the member may easily occur. On the other hand, if it exceeds 1.30, it will be difficult to obtain a high-resolution and high-quality image, and if the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase. It is.

  In this respect, when the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.00 to 1.30, any of storage stability, low-temperature fixability, and hot offset resistance can be obtained. Excellent, especially when used in a full-color copying machine. In addition, even with a two-component developer, even if the toner balance is maintained over a long period of time, there is little variation in the toner particle diameter in the developer, and good and stable developability can be obtained even with long-term agitation in the developing device. In the developer, even if the balance of the toner is performed, the fluctuation of the particle diameter of the toner is reduced, and the toner filming on the developing roller and the fusion of the toner to the member to the blade for thinning the toner are performed. In addition, even when the developing device is used for a long time (stirring), good and stable developability can be obtained, so that a high-quality image can be obtained.

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

  As the penetration, for example, the penetration measured by a penetration test (JIS K2235-1991) is preferably 15 mm or more, and more preferably 20 to 30 mm. This is because if the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated.

  The penetration can be measured according to JIS K2235-1991. Specifically, a 50 ml glass container is filled with toner and left in a constant temperature bath at 50 ° C. for 20 hours. The toner is cooled to room temperature, and the penetration is measured by performing a penetration test. In addition, it has shown that heat resistance preservability is excellent, so that the value of penetration is large.

  The low-temperature fixability is preferably as the lower limit fixing temperature is lowered and from the viewpoint of achieving both lowering of the fixing temperature and occurrence of no offset, and more preferably as the temperature at which no offset is generated. As a temperature range in which both a decrease in fixing temperature and the occurrence of no offset can be achieved, the lower limit fixing temperature is less than 150 ° C., and the temperature at which no offset occurs is 200 ° C. or more.

  The minimum fixing temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the obtained fixed image is rubbed with a pad. The roll temperature is the lower limit fixing temperature.

  For example, the offset non-occurrence temperature is set by using an image forming apparatus to set a transfer paper, and develop a solid image of each color of yellow, magenta, cyan, and black, and a solid image of red, blue, and green as each intermediate color. The temperature of the fixing belt can be adjusted to be variable, and the temperature at which no offset occurs can be determined.

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

<Effect>
The toner according to the exemplary embodiment includes at least a polyester resin and a polyalkylene glycol ester compound represented by the following chemical formula 7. The polyalkylene glycol compound has a melting point of 50 to 100 ° C., and 50 ° C. with respect to the polyester resin. Is incompatible, and is compatible at 100 ° C. Since they exist independently in a non-compatible state during storage, they exhibit excellent heat-resistant storage during storage, and the polyester resin and polyalkylene glycol ester compound become compatible and fix at low temperatures by heating during fixing. Sometimes shows excellent low-temperature fixability. Therefore, the toner according to the exemplary embodiment is excellent in various properties as a toner such as fluidity and fixability, and can achieve both excellent low-temperature fixability and heat-resistant storage stability.

In the chemical formula 7, R ¹ and R ² are linear or branched alkyl groups having 1 to 24 carbon atoms, and R _xm and R _ym are hydrogen or linear or branched alkyl groups having 1 to 6 carbon atoms. Represents an alkyl group. N represents an integer of 2 or more, and m represents an integer of 2 or more and 4 or less.

<Other embodiments>
The toner according to the exemplary embodiment described above has good characteristics such as fluidity and fixability, and achieves both excellent low-temperature fixability and heat-resistant storage stability. Therefore, the above-described toner can be suitably used in various fields, and can be particularly suitably used for image formation by electrophotography. Further, it can be particularly suitably used for a developer, a process cartridge, an image forming apparatus, and an image forming method described later.

  Hereinafter, the developer, the process cartridge, the image forming apparatus, and the image forming method will be described.

<Developer>
The developer of this embodiment contains at least the toner described above. Further, it contains other appropriately selected components such as a carrier. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like corresponding to the recent improvement in information processing speed, the service life is improved. In this respect, a two-component developer is preferable.

  In the case of the one-component developer using the above-described toner, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, and the filming of the toner on the developing roller, the blade for thinning the toner, etc. There is no fusion of toner to the member, and good and stable developability and images can be obtained even in long-term use (stirring) of the developing device.

  In addition, in the case of the two-component developer using the above-described toner, even when the toner balance for a long period of time is performed, there is little fluctuation in the toner particle diameter in the developer, and it is good and stable even with long-term stirring in the developing device. Developability can be realized.

  There is no restriction | limiting in particular as a 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 a 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 can be used. From the viewpoint of securing the image density, highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable. In addition, weak magnetization such as a copper-zinc (Cu-Zn) system (30 to 80 emu / g) is advantageous in that it can weaken the hitting of the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Material is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably a volume average particle diameter of 10 to 150 μm, and more preferably 40 to 100 μm. This is because if the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the number of fine powder systems increases in the distribution of carrier particles, and the magnetization per particle may be lowered to cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur, and the reproducibility of the solid portion may be deteriorated particularly in a full color having a large solid portion.

  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, polyesters 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 with vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, a silicone resin, or the like can be used. 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, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. 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 as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. In addition, the average particle diameter of the conductive powder is preferably 1 μm or less. This is because if the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

  The resin layer is prepared by, for example, preparing a coating solution by dissolving a silicone resin or the like in a solvent, then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. Can be formed. Examples of the application method include an immersion method, a spray method, and a brush coating method.

  There is no restriction | limiting in particular as a solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. can be used.

  The baking method 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. Techniques such as a method to be used and a method to use a microwave can be employed.

  The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. This is because if the amount is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. If the amount exceeds 5.0% by mass, the resin layer becomes too thick and the carrier is too thick. This is because granulation of each other occurs and uniform carrier particles may not be obtained.

  When the developer is a 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 to 98% by mass is preferable. 93-97 mass% is more preferable.

  Since the developer of the present embodiment contains the above-described toner, the properties as a toner such as fluidity and fixability are good, and both excellent low-temperature fixability and heat-resistant storage stability are compatible. Can do.

<Toner container>
The container for storing the above-described electrophotographic toner (developer) is not particularly limited and can be appropriately selected from known ones, and includes a toner container main body and a cap. As an example.

  The size, shape, structure, material and the like of the toner container main body are not particularly limited and can be appropriately selected according to the purpose. The shape is preferably cylindrical or the like, and in particular, spiral irregularities are formed on the inner peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and one part of the spiral portion is formed. A part or all of which has a bellows function is particularly preferable.

  The material of the toner container main body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin material is preferable. Among them, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like are preferable.

  The toner container is easy to store and transport, has excellent handleability, can be detachably attached to a process cartridge, an image forming apparatus, and the like, which will be described later, and can be used for replenishing toner.

<Process cartridge>
The process cartridge according to the present embodiment is detachably molded in various image forming apparatuses, and an electrostatic latent image carrier that carries an electrostatic latent image and a developer on the electrostatic latent image carrier. And developing means for developing the carried electrostatic latent image to form a visible image. In addition, you may have the other means suitably selected as needed.

  The developing means includes a developer container that contains the above-described electrophotographic toner or the developer, and a developer carrier that carries and transports the toner or developer contained in the developer container. At least. Furthermore, a layer thickness regulating member for regulating the toner layer thickness to be carried may be provided.

<Image Forming Method and Image Forming Apparatus>
The image forming step (image forming method) includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, preferably includes a cleaning step, and further appropriately selected as necessary. Including, for example, a static elimination process, a recycling process, a control process, and the like.

  In addition, the image forming apparatus includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and preferably includes a cleaning unit. Other means appropriately selected according to the above, for example, static elimination means, recycling means, control means, and the like are provided.

  The above-described image forming method can be preferably carried out by the above-described image forming apparatus. The electrostatic latent image forming step is performed by the electrostatic latent image forming unit, the developing step is performed by the developing unit, and the transfer step is performed by the transferring unit. The fixing process is performed by fixing means, and the other processes are performed by other means.

(Electrostatic latent image forming step / electrostatic latent image forming means)
The electrostatic latent image forming step is a step of forming an electrostatic latent image on an electrostatic latent image carrier such as a photoconductor.

  There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (“photoconductive insulator”, “photoconductor”), and it can be appropriately selected from known ones. The shape is preferably a drum shape, and the material is an inorganic photoreceptor such as amorphous silicon or selenium, or an organic photoreceptor such as polysilane or phthalopolymethine. Among these, amorphous silicon or the like is preferable in terms of long life.

  The formation of the electrostatic latent image is performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure. This electrostatic latent image is formed by electrostatic latent image forming means.

  The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Configured.

  Charging is performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using a charger. The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roll, brush, film, rubber blade, etc. A non-contact charger using corona discharge such as corotron and scorotron can be used.

  The exposure is performed, for example, by exposing the surface of the electrostatic latent image carrier imagewise using an exposure device. The exposure device is not particularly limited as long as exposure can be performed in an image-like manner to be formed on the surface of the electrostatic latent image carrier charged by the charger, and can be appropriately selected according to the purpose. Various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.

  In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of an electrostatic latent image carrier.

(Development process / Development means)
The development step is a step of developing a latent image by using the above-described electrophotographic toner or the above-described electrophotographic developer to form a visible image. The visible image is formed by a developing unit.

  The developing means is not particularly limited as long as it can be developed using, for example, the above-described electrophotographic toner or the above-described electrophotographic developer, and can be appropriately selected from known ones. For example, it is preferable to contain the above-described electrophotographic toner or electrophotographic developer and have at least a developing device capable of contacting or non-contacting the toner / the developer with an electrostatic latent image. A developing device including the above-described toner container is more preferable.

  The developing device may be of a dry development type, may be of a wet development type, may be a single color developer, or may be a multicolor developer. . For example, a preferable example includes a stirrer that frictionally stirs and charges the above-described electrophotographic toner or electrophotographic urine developer, and a rotatable magnet roller.

  In the developing device, the electrophotographic toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. The magnet roller is disposed in the vicinity of the electrostatic latent image carrier, and a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is supported by the electrostatic latent image by an electric attraction force. Move to the surface of the body. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the above-described electrophotographic toner. However, the developer may be a one-component developer or a two-component developer.

(Transfer process / Transfer means)
The transfer process is a process of transferring a visible image to a recording medium. A mode in which an intermediate transfer member is used, a visible image is primarily transferred onto the intermediate transfer member, and then the visible image is secondarily transferred onto a recording medium is preferable. In addition, a primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer member using two or more colors, preferably full color toner, as a toner, and transferring the composite transfer image onto a recording medium A mode including a secondary transfer step is more preferable.

  Transfer is performed by transfer means. The transfer unit includes a primary transfer unit that transfers a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer unit that transfers the composite transfer image onto a recording medium. Is preferred.

  The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, an endless transfer belt can be preferably used.

  The transfer means (primary transfer means, secondary transfer means) preferably has at least a transfer unit that peels and charges the visible image formed on the electrostatic latent image carrier to the recording medium side. 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.

  In addition, there is no restriction | limiting in particular as a recording medium, It can select suitably from well-known recording media (recording paper).

(Fixing process / fixing means)
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit. It may be performed each time the toner of each color is transferred to the recording medium, or may be performed simultaneously at a time in a state where the toner of each color is laminated.

  The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. However, a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.

  The heating temperature in the heating and pressing means is usually preferably 80 ° C to 200 ° C.

  Depending on the purpose, for example, a known optical fixing device may be used together with or instead of the above-described fixing means.

(Other processes / other means)
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and is performed by a neutralization unit. As the charge eliminating means, it is sufficient if a charge eliminating bias can be applied to the electrostatic latent image carrier, and it can be appropriately selected from known static eliminators. For example, a charge eliminating lamp or the like can be used.

  The cleaning step is a step of removing residual toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit. There are no particular limitations on the cleaning means, and it is sufficient that residual toner remaining on the electrostatic latent image carrier can be removed, and it can be appropriately selected from known cleaners. For example, a magnetic brush cleaner, static An electric brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, a web cleaner, or the like can be used.

  The recycling step is a step of recycling the residual 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 a recycle means, A well-known conveyance means etc. are mentioned.

  The control process is a process for controlling each of the above-described processes, and is 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. For example, a device such as a sequencer or a computer can be used.

(Image forming device)
With reference to FIG. 1, an aspect of an image forming apparatus that performs the above-described image forming method will be described.

  The image forming apparatus 100 includes a photosensitive drum 10 as an electrostatic latent image carrier, a charging roller 20 as a charging unit, an exposure device 30 as an exposure unit, a developing device 40 as a developing unit, and an intermediate transfer member. 50, a cleaning device 60 as a cleaning means having a cleaning blade, and a static elimination lamp 70 as a static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of the arrow by three rollers 51 that are arranged on the inner side and stretch the intermediate transfer member 50. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50.

  The intermediate transfer member 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof. Further, a transfer roller 80 serving as a transfer unit capable of applying a transfer bias for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material is disposed to face the transfer sheet.

  Further, around the intermediate transfer member 50, a corona charger 52 for applying a charge to the toner image on the intermediate transfer member 50, a contact portion between the photosensitive drum 10 and the intermediate transfer member 50, and the intermediate transfer member. 50 and the contact portion of the transfer paper 95.

  The developing device 40 includes an endless developing belt 41 as a developer carrier, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. Configured. Each color developing unit 45 includes a developer container 42, a developer supply roller 43, and a developing roller 44. Further, the developing belt 41 is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photosensitive drum 10.

  In the image forming apparatus 100 shown in FIG. 1, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image).

  The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer body 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photosensitive drum 10 is removed by the cleaning device 60, and the charge on the photosensitive drum 10 is temporarily removed by the charge eliminating lamp 70.

  With reference to FIG. 2, another aspect of the image forming apparatus that performs the above-described image forming method will be described. The same constituent members are denoted by the same reference numerals as in FIG.

  The image forming apparatus 100 shown in FIG. 2 does not include the developing belt 41 and is shown in FIG. 1 except that the color developing units 45Y to 45K are arranged directly opposite to each other around the photosensitive drum 10. The image forming apparatus 100 has the same configuration. Even in such a configuration, the same effects as those of the above-described image forming apparatus and image forming method can be realized.

  With reference to FIG. 3, another aspect of the image forming apparatus that performs the above-described image forming method will be described. An image forming apparatus 100 shown in FIG. 3 is a tandem color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400. Is done.

  The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and rotates clockwise (in the direction of the arrow in the figure).

  An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. Further, four image forming units 18 of yellow, cyan, magenta, and black are arranged opposite to each other on the intermediate transfer member 50 stretched by the support roller 14 and the support roller 15 along the conveyance direction. A tandem developing device 120 is disposed.

  As shown in FIG. 4, the tandem developing device 120 includes each color image forming means 18. Each color image forming means 18 includes a photosensitive drum 10, a charger 60 that uniformly charges the photosensitive drum 10, and an electrostatic latent image formed on each photosensitive drum 10 with each color toner (black toner, yellow toner). Toner, magenta toner, cyan toner) to form each color toner image, a developing device 61, a transfer charger 62 for transferring each color toner image onto the intermediate transfer member 50, and a photosensitive drum cleaning device. 63 and a static eliminator 64.

  An exposure device 21 is disposed in the vicinity of the tandem developing device 120. The exposure device 21 exposes the tandem developing device 120 to form an electrostatic latent image on the photosensitive drum 10. In FIG. 4, L indicates exposure from the exposure apparatus 21.

  A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. It is possible.

  A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.

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

  Next, full color image formation (color copying) in the image forming apparatus 100 including the tandem type developing device 120 will be described.

  First, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300. close.

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

  Based on the image information of black, yellow, magenta, and cyan, the exposure device 21 forms an electrostatic latent image corresponding to each color on the photosensitive drum 10 of the tandem developing device 120. Each color electrostatic latent image is developed by each color developing device 61 of the tandem developing device 120 to become each color toner image.

  The formed black toner image, yellow toner image, magenta toner image, and cyan toner image are successively transferred (primary transfer) to the intermediate transfer member 50 that is rotated and moved by the support rollers 14, 15, and 16. A composite color image (color transfer image) is formed on the body 50.

  In the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet is fed by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, abutted against the registration roller 49, and stopped. Alternatively, the sheets (recording paper) on the manual feed tray 51 are fed out, separated one by one by the separation roller 58, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.

  The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.

  Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed.

  The sheet (recording paper) onto which the composite color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25. Then, the combined color image (color transfer image) is fixed on the sheet (recording paper) by heat and pressure by the fixing device 25. Thereafter, the sheet (recording paper) is switched by a switching claw 55 and discharged by a discharge roller 56 and is stacked on a discharge tray 57. Alternatively, the sheet is switched by the switching claw 55 and reversed by the sheet reversing device 28 and led to the transfer position again. After the image is recorded on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  In the image forming apparatus and the image forming method of the present embodiment, the developer containing the above-described toner as a developer, that is, various properties as a toner such as fluidity and fixability are excellent and excellent in low temperature fixability and heat resistance. Since a developer containing a toner that is compatible with storage stability is used, it is possible to realize power saving and shortening of standby time. In addition, high-quality images can be obtained efficiently even under low-temperature fixing conditions.

<Comparison of Examples and Comparative Examples>
Hereinafter, comparison results between the above-described electrophotographic toner examples (1 to 3) of the present invention and comparative examples (1 to 3) will be described with reference to the tables.

Example 1
The toner of Example 1 was produced by the following process.

  In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, dibutyl 2 parts by mass of tin oxide was added and reacted at 230 ° C. for 8 hours under normal pressure. Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg to synthesize an unmodified polyester.

  The obtained unmodified polyester had a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 5,600, and a glass transition temperature (Tg) of 55 ° C.

  The polyalkylene glycol ester compound was prepared by mixing 200 parts by mass of polyethylene glycol distearic acid (melting point: 56 ° C., Mw = 6000), 400 parts by mass of an unmodified polyester resin, and 800 parts by mass of ethyl acetate. ”; Manufactured by Imex Co., Ltd.), and the polyalkylene glycol ester compound was dispersed in 3 passes under the condition that the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / s, and 80% by volume of 0.5 mm zirconia beads were filled. And a polyalkylene glycol ester compound dispersion was prepared. In addition, it was 0 mass% when the solubility of the polyalkylene glycol ester compound in the ethyl acetate which is a dispersion | distribution solvent was measured at 25 degreeC.

  1000 parts by weight of water, 540 parts by weight of carbon black “trade name Printex 35” (manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5) and 1200 parts by weight of the above-mentioned unmodified polyester Mixing was performed using a mixer (Mitsui Mining Co., Ltd.). The mixture was kneaded with two rolls for 30 minutes in an environment of 150 ° C., then cooled by rolling and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

  In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 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, Trimellitic anhydride (22 parts by mass) and dibutyltin oxide (2 parts by mass) were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined. The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,600, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.

  Next, 411 parts by mass of intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with an active hydrogen group-containing compound) was synthesized. The free isocyanate content of the obtained prepolymer was 1.60% by mass, and the solid content concentration of the prepolymer (after standing at 150 ° C. for 45 minutes) was 50% by mass.

  In a reaction vessel equipped with a stir bar and a thermometer, 30 parts by mass of isophoronediamine and 70 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (active hydrogen group-containing compound). The amine value of the obtained ketimine compound (active hydrogen machine-containing compound) was 423.

  In a beaker, 15 parts by mass of a prepolymer, 60 parts by mass of unmodified polyester, 130 parts by mass of ethyl acetate, and 100 parts by mass of a polyalkylene glycol ester compound dispersion were stirred and dissolved. Next, 10 parts by weight of carnauba wax (molecular weight = 1,800, acid value = 2.5, penetration = 1.5 mm (40 ° C.)) and 10 parts by weight of master batch were charged, and a bead mill (“Ultra Visco” Mill "; manufactured by Imex Co., Ltd.), a raw material solution was prepared by three passes under the condition that the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / s, and 80% by volume of 0.5 mm zirconia beads were filled, 2.7 parts by mass of ketimine was added and dissolved to prepare a toner material solution or dispersion.

  An aqueous medium phase was prepared by mixing and stirring 306 parts by mass of ion-exchanged water, 265 parts by mass of a 10% by mass tricalcium phosphate suspension, and 0.2 parts by mass of sodium dodecylbenzenesulfonate, and dissolving them uniformly.

  150 parts by mass of the aqueous medium phase is put in a container, and stirred at a rotational speed of 12,000 rpm using a TK type homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The mixture was mixed for 10 minutes to prepare an emulsification or dispersion (emulsion slurry).

  100 parts by mass of the emulsified slurry was charged into a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min.

  After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. To the obtained filter cake, 20 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.

  To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. Furthermore, 20 mass parts of 10 mass% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes) and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtered twice to obtain a final filter cake.

  The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh of 75 μm to obtain toner base particles of Example 1.

(Example 2)
Manufactured in the same production process as in Example 1, except that the amount of polyalkylene glycol ester compound dispersion added in the preparation of toner material dissolution or dispersion in Example 1 was changed from 100 parts by mass to 200 parts by mass. Thus, toner base particles of Example 2 were obtained.

(Example 3)
In Example 1, except that the polyethylene glycol distearic acid (melting point 56 ° C., Mw = 6000) used in the preparation of the polyalkylene glycol ester compound dispersion was changed to polyethylene glycol dibehenic acid (melting point 61 ° C., Mw = 18000). Was produced by the same production process as in Example 1 to obtain toner base particles of Example 3.

  In addition, when the solubility of the polyalkylene glycol ester compound with respect to the organic solvent was measured at 25 degreeC, it was 0 mass%.

(Comparative Example 1)
Manufactured in the same production process as in Example 1 except that the amount of polyalkylene glycol ester compound dispersion added in the dissolution or dispersion of the toner material in Example 1 was changed from 100 parts by mass to 0 parts by mass. Thus, toner base particles of Comparative Example 1 were obtained.

(Comparative Example 2)
In Example 1, except that the polyethylene glycol distearic acid (melting point 56 ° C. Mw = 6000) used in the preparation of the polyalkylene glycol ester compound dispersion was changed to polyethylene glycol dibehenic acid (melting point 45 ° C. Mw = 4000). The toner base particles of Comparative Example 2 were obtained by the same manufacturing process as in Example 1.

(Comparative Example 3)
In Example 1, except that the polyethylene glycol distearic acid (melting point 51 ° C., Mw = 2000) used in the preparation of the polyalkylene glycol ester compound dispersion was changed to polyethylene glycol distearic acid (melting point 61 ° C., Mw = 4000). The toner base particles of Comparative Example 3 were obtained by the same manufacturing process as in Example 1.

  In addition, it was 10 mass% when the solubility of the polyalkylene glycol ester compound with respect to the organic solvent was measured at 25 degreeC.

(Manufacture of toner)
For 100 parts by mass of the obtained toner base particles of Examples 1 to 3 and Comparative Examples 1 to 3, 1.0 part by mass of hydrophobic silica (“H2000”; manufactured by Clariant Japan Co., Ltd.) as an external additive was added to Henschel. Using a mixer (manufactured by Mitsui Mining Co., Ltd.), the process of mixing at a peripheral speed of 30 m / s for 30 seconds and resting for 1 minute was carried out for 5 cycles, sieved with a mesh of 35 μm, and the toners of Examples 1-3 and Comparative Examples 1-3 Manufactured.

  Next, to 100 parts by mass of toluene, 100 parts by mass of a silicone resin (“organostraight silicone”, 5 parts by mass of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black were added, and a homomixer was added. A coating layer forming solution was prepared by dispersing the coating layer forming solution on a surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 50 μm using a fluid bed type coating apparatus. Produced.

(Tg measurement result)
For each of the obtained toners of Examples 1 to 3 and Comparative Examples 1 to 3, Tg at the first temperature increase was measured. Table 1 shows the measurement results of Tg.

  Tg was measured using a DSC system (differential scanning calorimeter) (“DSC-60”; manufactured by Shimadzu Corporation). Specifically, about 5.0 mg of each toner (sample) was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Subsequently, the sample was heated from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere, and a DSC curve was measured (created) with a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation). Using the analysis program in the DSC-60 system, the melting point was calculated from the intersection of the tangent line between the curve before the inflection point of the resin (or toner) and the curve after the inflection point. Simultaneously, the melting point (Tm) of the polyalkylene glycol ester compound was determined from the peak value derived from the polyalkylene glycol ester compound.

(Manufacture of developer)
5 parts by mass of each of the toners of Examples 1 to 3 and Comparative Examples 1 to 3 which have been treated with the external additive and 95 parts by mass of the carrier are ball mill mixed, and each two-component development of Examples 1 to 3 and Comparative Examples 1 to 3 is performed. An agent was produced.

  Each developer obtained was evaluated for fixability (hot offset resistance and low temperature fixability), heat resistant storage stability, fluidity, and copy blocking property. The evaluation results are shown in Table 2.

  In this evaluation, the silicone oil application mechanism was removed from the fixing unit of the tandem color electrophotographic apparatus (“Imagio Neo C350”; manufactured by Ricoh Co., Ltd.), and the oil-less fixing method was modified. And a plain paper (“TYPE 6000 <70W> Y eyes”; manufactured by Ricoh Co., Ltd.) were used. The tandem color electrophotographic apparatus can continuously print 35 sheets of A4 size paper per minute. At this time, the linear velocity of the fixing roller was set to 125 mm / s, and the evaluation was performed by changing the roller temperature.

(Fixability / Hot offset property)
Using a tandem color electrophotographic apparatus, a solid image of each color of yellow, magenta, cyan, and black is developed on a plain paper with a single color of 0.85 ± 0.3 mg / cm ² of toner. Adjusted. The obtained image was fixed by changing the temperature of the heating roller, the fixing temperature at which hot offset occurs (offset generation temperature) was measured, and the hot offset property was evaluated according to the following evaluation criteria.

Evaluation criteria ◎: 210 ° C or higher ○: Less than 210 ° C 190 ° C or higher △: Less than 190 ° C 170 ° C or higher ×: Less than 170 ° C

(Fixability / Low-temperature fixability)
Using a tandem color electrophotographic apparatus, plain paper was set and a copy test was performed. The fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a dedicated cloth pad becomes 70% or more was set as the minimum fixing temperature, and the low-temperature fixing property was evaluated according to the following evaluation criteria.

Evaluation criteria A: Less than 100 ° C ○: Less than 120 ° C 100 ° C or more △: Less than 140 ° C 120 ° C or more ×: 140 ° C or more

(Heat resistant storage stability)
Each toner was filled in a 50 ml glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., the penetration (mm) was measured by a penetration test (JIS K2235-1991), and the heat resistant storage stability was evaluated according to the following evaluation criteria.

  In addition, it shows that heat resistance preservability is excellent, so that the value of penetration is large, and in the case of 5 mm or less, possibility of a problem in use is high.

Evaluation criteria ○: Needle penetration 25 mm or more △: Needle penetration 15 mm or more and less than 25 mm ×: Needle penetration less than 15 mm

(Liquidity)
Using a powder tester (manufactured by Hosokawa Micron Corporation) as a measuring device, set vibro chute, packing, space ring, sieve (3 types / upper>middle> lower), and osaver in this order on the vibration table, and then with a knob nut Fixed and operated the shaking table. Detailed conditions are as follows.

Measurement condition: Opening of sieve (upper): 75μm
Flute opening (middle): 45 μm
Flute opening (bottom): 22 μm
Swing scale: 1mm
Sampling amount: 10g
Vibration time: 30 seconds

  After measurement under the above conditions, the degree of aggregation (%) of the toner was calculated based on the following mathematical formulas 1 to 4, and fluidity was evaluated according to the following evaluation criteria.

Ａ（％）＝（上段のフルイに残った粉体重量／試料採取量）×１００
・・・式（３）
Ｂ（％）＝（中段のフルイに残った粉体重量／試料採取量）×１００
・・・式（４）
Ｃ（％）＝（下段のフルイに残った粉体重量／試料採取料）×１００
・・・式（５）
凝集度（％）＝Ａ＋Ｂ＋Ｃ ・・・式（６）

A (%) = (weight of powder remaining on upper screen / sample amount) × 100
... Formula (3)
B (%) = (weight of powder remaining on middle stage sieve / sample amount) × 100
... Formula (4)
C (%) = (weight of powder remaining on lower screen / sample collection fee) × 100
... Formula (5)
Aggregation degree (%) = A + B + C (6)

Evaluation criteria ◎: Aggregation degree is less than 5% ○: Aggregation degree is less than 10% △: Aggregation degree is less than 20% ×: Aggregation degree is 20% or more

(Copy blocking)
1,000 standard images with an image area ratio of 7% were output continuously, the adhesion state between sheets was visually observed, and evaluated based on the following criteria.

Evaluation criteria ◎: The sheets are separated one by one without any problem. ○: Only the lower stacked sheets need to be partially separated. △: Although they are separated, they must be placed above and below the stacked sheets. Difficult to separate ×: Partially adhered even if the stacked paper is squeezed up and down

<Evaluation of comparison results>
From Tables 1 and 2 showing the results of the evaluation tests described above, the following is clear.

  The toner / developer of Example 1 has excellent fluidity and heat-resistant storage stability, good fixability, and no copy blocking.

  Since the toner / developer of Example 2 has a higher polyalkylene glycol ester compound concentration than that of Example 1, it has an excellent minimum fixing temperature.

  The toner / developer of Example 3 uses a polyalkylene glycol ester compound of a type different from that of Example 1, but has the same characteristics as Example 1.

  The toner / developer of Comparative Example 1 is inferior in low-temperature fixability because the toner does not contain a polyalkylene glycol ester compound.

  Since the melting point of the polyalkylene glycol ester compound is low, the toner / developer of Comparative Example 2 has poor heat storage stability and fluidity.

  The toner / developer of Comparative Example 3 is inferior in heat resistant storage stability and fluidity because the polyalkylene glycol ester compound is dissolved in an organic solvent and is already compatible with the polyester resin during storage.

<Additional notes>
The above-described embodiment is merely an example of a preferred embodiment of the present invention, and is not intended to limit the embodiment of the present invention. Therefore, the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the scope of the invention.

1 is a diagram illustrating a configuration of an image forming apparatus. 1 is a diagram illustrating a configuration of an image forming apparatus. 1 is a diagram illustrating a configuration of a tandem type image forming apparatus. It is a figure which shows the structure of a tandem type developing device.

Explanation of symbols

  100 Image forming apparatus

Claims (7)

A toner containing at least a polyester resin and a colorant,
The toner is
^{_{R 1 COO- (CH 2 -CH 2}} -O) n -COR 2
Further containing a polyethylene glycol diester compound represented by (R ¹ , R ² is a linear alkyl group having 18 to 22 carbon atoms, n is an integer of 2 or more) ,
The polyethylene glycol diester compound has a melting point in the range of 50 ° C. or more and 100 ° C. or less, and is incompatible with the polyester resin at 50 ° C., is compatible with the polyester resin at 100 ° C., and has a weight. A toner having an average molecular weight of 6,000 to 18,000 . The toner according to claim 1, wherein a content of the polyethylene glycol diester compound is 1 to 20 parts by weight with respect to 100 parts by weight of the polyester resin. The toner according to claim 1, wherein the polyethylene glycol diester compound obtained by DSC measurement at the first temperature rise has a melting point of 50 ° C. or higher. A developer using the toner according to claim 1. Preparing an emulsion or dispersion obtained by emulsifying or dispersing 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 in an aqueous medium;
After the preparation, the active hydrogen group-containing compound and the polymer are reacted to form an adhesive base material, whereby the toner is granulated by obtaining particles containing at least the adhesive base material. Including
The adhesive substrate includes a polyester resin,
The toner is
R ¹ COO- (CH ₂ -CH ₂ -O) _n -COR ²
(R ¹ , R ² Further contains a polyethylene glycol diester compound represented by a linear alkyl group having 18 to 22 carbon atoms, n is an integer of 2 or more,
The polyethylene glycol diester compound has a melting point in the range of 50 ° C. or more and 100 ° C. or less, and is incompatible with the polyester resin at 50 ° C., is compatible with the polyester resin at 100 ° C., and has a weight. An average molecular weight is 3,000 to 20,000. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and a static image formed on the electrostatic latent image carrier using a developer. Developing means for developing an electrostatic latent image to form a visible image, transfer means for transferring a visible image formed on the electrostatic latent image carrier onto a recording medium, and transfer onto the recording medium An image forming apparatus comprising at least a fixing unit for fixing a transfer image,
An image forming apparatus, wherein the developer is the developer according to claim 4. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image using a developer to form a visible image, and the visible An image forming method for forming an image by performing at least a transfer step of transferring an image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium,
An image forming method, wherein the developer is the developer according to claim 4.

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