JP2007079223A - Toner, developer, toner charged container, process cartridge, apparatus and method for image forming - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner that comprises the mixture of a polymerization toner manufactured by a polymerization method and a pulverization toner manufactured by a pulverizing method, that has favorable charging property while keeping cleaning property, and that can form a favorable visible image over a long period, and to provide a developer using the toner, a toner charged container, a process cartridge, and an apparatus and a method for image forming. <P>SOLUTION: The toner is produced by mixing a polymerization toner manufactured by a polymerization method and a pulverization toner manufactured by a pulverization method, wherein the polymerization toner shows the average circularity of 0.93 to 0.99, the pulverization toner shows average circularity of 0.85 to 0.93, and the ratio (Dv/Dn) of the volume average particle size (Dv) to the number average particle size (Dn) in the mixture toner is 1.40 or less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a toner suitably used for a laser beam printer, a facsimile, a digital copy, and the like, and a developer, a toner-containing container, a process cartridge, an image forming apparatus, and an image forming method using the toner.

  Conventionally, an electric latent image or a magnetic latent image is developed (visible image) with toner. The toner used for this development is generally colored particles containing a colorant, a charge control agent, and other additives in a binder resin. The toner production methods are roughly classified into a pulverization method and a polymerization method. In the pulverization method, a colorant, a charge control agent, an anti-offset agent, etc. are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting toner composition is pulverized and classified to produce a toner. is doing.

  According to the pulverization method, it is possible to produce a toner having excellent properties to some extent, but there are limitations on the selection of the toner material. For example, a toner composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable apparatus. From such a request, the melt-mixed composition must be made sufficiently brittle. For this reason, in fact, when the toner composition is pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, A fine powder having a diameter of 5 μm or less and a coarse powder having a diameter of 20 μm or more must be removed by classification, which has a disadvantage that the yield becomes very low. In the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. Such uneven dispersion of the compounding agent may adversely affect the fluidity, developability, durability, image quality, and the like of the toner.

  In recent years, in order to solve the problems in these pulverization methods, for example, toner particles are produced by a suspension polymerization method (see Patent Document 1). However, although the toner particles obtained by the suspension polymerization method are spherical, there is a drawback that the cleaning property is poor. In development and transfer with a low image area ratio, there is little transfer residual toner, and cleaning defects do not become a problem. However, untransferred images were formed due to high image area ratios such as photographic images, as well as poor paper feed. Toner may be generated on the photoconductor as untransferred toner, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. Furthermore, the low-temperature fixability is not sufficient, and a lot of energy required for fixing is required.

  On the other hand, a method of obtaining irregular toner particles by associating resin fine particles obtained by an emulsion polymerization method is disclosed (see Patent Document 2). However, in the toner particles obtained by this emulsion polymerization method, the surfactant remains in a large amount not only on the surface but also inside the particles even after the water washing step, and the environmental stability of toner charging is impaired. The charge amount distribution is widened, and the background stain of the obtained image becomes poor. Further, the remaining surfactant may contaminate the photoreceptor, the charging roller, the developing roller, and the like, and the original charging ability may not be exhibited.

In addition, the polymer toner having a spherical shape has a drawback that it is inferior in cleaning property. For this reason, conventionally, proposals have been made to make the toner shape potato-like or indefinite, and to add a cleaning aid. However, the former tends to cause non-uniform chargeability due to inferior toner fluidity compared to the spherical toner, and the latter tends to cause photoconductor contamination due to detachment from the toner. Is not provided with satisfactory means.
In addition, just mixing the spherical toner obtained by the polymerization method and the pulverized toner obtained by the pulverization method may result in significant background stains and toner scattering, which are still at a practical level. It is the current situation that has not reached.

Japanese Patent Laid-Open No. 9-43909 Japanese Patent No. 2537503

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention is a mixture of a polymerized toner manufactured by a polymerization method and a pulverized toner manufactured by a pulverization method, and maintains good cleaning properties while maintaining good cleanliness and provides a good visible image for a long time. It is an object of the present invention to provide a toner that can be formed over a wide area, a developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method.

Means for solving the problems are as follows. That is,
<1> A toner obtained by mixing a polymerized toner produced by a polymerization method and a pulverized toner produced by a pulverization method,
The average circularity of the polymerized toner is 0.93 to 0.99, the average circularity of the pulverized toner is 0.85 to 0.93, and the volume average particle diameter (Dv) in the mixed toner is The toner is characterized in that the ratio (Dv / Dn) to the number average particle diameter (Dn) is 1.40 or less.
<2> The toner according to <1>, wherein a mixing mass ratio of the polymerized toner and the pulverized toner (polymerized toner: pulverized toner) is 20: 1 to 1: 1.
<3> The volume average particle diameter (Dv) of the polymerized toner is 3 to 9 μm, and the volume average particle diameter (Dv) of the pulverized toner is 5 to 20 μm. Toner.
<4> The toner according to any one of <1> to <3>, wherein the acid value of the binder in the polymerized toner and the pulverized toner is 1 to 35 mgKOH / g.
<5> The toner according to any one of <1> to <4>, wherein the glass transition temperature (Tg) of the binder in the polymerized toner and the pulverized toner is 50 to 70 ° C.
<6> The binder in the polymerized toner contains the modified polyester resin (i) and the unmodified polyester resin (ii), and the mixing mass ratio ((i) / (ii)) is 5/95. The toner according to any one of <1> to <5>, which is 80/20.
<7> The toner according to any one of <1> to <6>, wherein the polymerized toner contains a charge control agent, and the charge control agent is a fluororesin.
<8> The toner according to <7>, wherein the fluororesin is a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer represented by the following general formula (1).
However, in the general formula (1), Rf represents a perfluoro group. m and n represent a positive integer.
<9> At least one selected from the group consisting of resin fine particles on the surface and / or inside of a polymerized toner, and the resin fine particles selected from vinyl resin fine particles, polyurethane resin fine particles, epoxy resin fine particles, and polyester resin fine particles The toner according to any one of <1> to <8>.
<10> The toner according to <9>, wherein the resin fine particles have a volume average particle diameter of 5 to 2,000 nm.
<11> A toner solution is prepared by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an organic acid compound in an organic solvent. Thereafter, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium. The toner according to any one of <1> to <10>, wherein the toner is produced by forming an adhesive substrate into particles and removing the organic solvent.
<12> The toner according to <11>, wherein the organic solvent is removed under at least one of reduced pressure and heating.
<13> The toner according to <11>, wherein the organic solvent is removed by filtration.
<14> A developer comprising the toner according to any one of <1> to <13> and a carrier.
<15> A toner-containing container filled with the toner according to any one of <1> to <13>.
<16> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to <13> to be a visible image And a developing means for forming a process cartridge.
<17> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image according to <1> to <13> Development means for forming a visible image by developing using any of the toners, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium The image forming apparatus is characterized in that the developing unit has a toner recycling mechanism.
<18> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and using the toner according to any one of <1> to <13>, At least a development step for developing and forming a visible image, 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 image forming method is characterized in that the developing step includes a toner recycling step.

The toner of the present invention is a mixture of a polymerized toner produced by a polymerization method and a pulverized toner produced by a pulverization method,
The average circularity of the polymerized toner is 0.93 to 0.99, the average circularity of the pulverized toner is 0.85 to 0.93, and the volume average particle diameter (Dv) of the mixed toner is The ratio (Dv / Dn) to the number average particle diameter (Dn) is 1.40 or less.
In the toner of the present invention, a polymerized toner produced by a polymerization method and a pulverized toner produced by a pulverization method are mixed, and while maintaining the cleaning property, the chargeability is good and a good visible image is obtained. Can be formed over a long period of time

  The developer of the present invention contains the toner of the present invention. When an image is formed by electrophotography using the developer of the present invention, the chargeability is good and a good visible image can be obtained.

  The toner-containing container of the present invention contains the toner of the present invention in a container. When an image is formed by electrophotography using the toner contained in the toner-containing container of the present invention, as a result, the chargeability is good and a good visible image is obtained.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge can be attached to and detached from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that the cleaning property is excellent, the charging property is good, and a good visible image can be obtained.

  An image forming apparatus according to the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using toner. Developing means for developing a visible image by development, transfer means for transferring the visible image to a recording medium, fixing means for fixing the transfer image transferred to the recording medium, and the electrostatic latent image carrier The electrostatic latent image carrier is the electrostatic latent image carrier of the present invention. In the image forming apparatus of the present invention, since the electrostatic latent image carrier of the present invention is used as the electrostatic latent image carrier, the cleaning property is good, the durability is high over a long period of time, and A high-quality image can be obtained.

  The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image. At least a developing step, a transferring step for transferring the visible image to a recording medium, a fixing step for fixing the transferred image transferred to the recording medium, and a cleaning step for cleaning the electrostatic latent image carrier. The electrostatic latent image carrier is the electrostatic latent image carrier of the present invention. In the image forming method of the present invention, since the electrostatic latent image bearing member of the present invention is used as the electrostatic latent image bearing member, the cleaning property is good, and the image having high durability and high image quality over a long period of time. Can be formed.

  The process cartridge of the present invention has at least an electrostatic latent image carrier and developing means for developing a latent image formed on the electrostatic latent image carrier using toner to form a visible image. Since the electrostatic latent image carrier of the present invention is used as the electrostatic latent image carrier, scratch resistance, high wear resistance, surface resistance does not decrease in a high humidity environment, In addition, high durability and high-quality images can be obtained over a long period of time even in high-temperature environments found in high-speed processes, etc., and even when blade cleaning or the like is performed, the wear of the electrostatic latent image carrier is extremely slightly suppressed. The property is also good.

  According to the present invention, the conventional problems can be solved, and the chargeability is maintained while maintaining the cleaning property by mixing the polymerized toner manufactured by the polymerization method and the pulverized toner manufactured by the pulverization method. A toner capable of forming a good and good visible image over a long period of time, and a developer, a toner-containing container, a process cartridge, an image forming apparatus, and an image forming method using the toner can be provided.

(toner)
The toner of the present invention is obtained by mixing a polymerized toner produced by a polymerization method and a pulverized toner produced by a pulverization method, and further has other configurations as necessary.

  The mixing mass ratio of the polymerized toner and the pulverized toner (polymerized toner: pulverized toner) is preferably 20: 1 to 1: 1, and more preferably 15: 1 to 5: 1. When the mixing mass ratio is within the above range, it is possible to obtain a mixed toner capable of forming a good visible image over a long period of time while maintaining good cleaning properties and good chargeability.

The average circularity of the polymerized toner is 0.93 to 0.99, preferably 0.96 to 0.99. If the average circularity of the polymerized toner is less than 0.93, the effect of improving the image quality due to the spherical shape, which is the merit of the polymerized toner, may be reduced. However, it may cause a cleaning failure.
The average circularity of the pulverized toner is 0.85 to 0.93, preferably 0.85 to 0.91. If the average circularity of the pulverized toner is less than 0.85, abnormal toner pulverization may occur in the developing device due to an excessively deformed shape. The assisting effect may be reduced, resulting in poor cleaning.
Here, the average circularity of the toner is, for example, an optical detection band method in which a suspension containing toner is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).

The volume average particle diameter (Dv) of the polymerized toner is 3 to 9 μm, preferably 4 to 8 μm. When the volume average particle size of the polymerized toner is less than 3 μm, the charging performance may become unstable, and when it exceeds 9 μm, the dot reproducibility may be lowered, that is, the image quality may be lowered.
The volume average particle diameter (Dv) of the pulverized toner is 5 to 20 μm, and preferably 5 to 15 μm. If the volume average particle size of the pulverized toner is less than 5 μm, the effect of assisting the cleaning property of the polymerized toner may be reduced, resulting in poor cleaning. If it exceeds 20 μm, the dot reproducibility decreases, that is, the image quality decreases. It may become.
The ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the mixed toner is 1.40 or less, preferably 1.05 to 1.2. When the Dv / Dn exceeds 1.40, the toner particle size distribution is wide, and the charge distribution is also widened. When the developer is deteriorated due to image formation over time, background stains and toner scattering may occur.
Here, the volume average particle diameter and the ratio (Dv / Dn) of the volume average particle diameter to the number average particle diameter are determined using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can be measured.

  The toner of the present invention is not particularly limited as long as the material satisfies the above conditions, and can be appropriately selected from known ones according to the purpose. The method is preferred. The polymerized toner includes a suspension polymerization method, an emulsion polymerization method, a polymer suspension method and the like in which an oil phase is emulsified, suspended or aggregated in the following aqueous medium to form toner base particles.

<Pulverized toner>
The pulverization method is a method of obtaining the toner base particles by, for example, melting and kneading a toner material containing at least a binder and a colorant, and pulverizing and classifying the toner material. In the case of the pulverization method, for the purpose of setting the average circularity of the toner to 0.85 to 0.93, the shape may be controlled by applying a mechanical impact force to the obtained toner base particles. Good. In this case, the mechanical impact force can be applied to the toner base particles using a device such as a hybridizer or mechanofusion.

  The above toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial continuous kneader, a biaxial continuous kneader, or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikekai Tekko Co., Ltd. Preferably used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature is performed with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

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

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

  Further, in order to improve the fluidity, storage stability, developability and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner base particles produced as described above. For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

  The toner material contains at least a binder, a colorant, and a release agent, and further contains other components as necessary.

The binder is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, a homopolymer of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and a substituted product thereof. Styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-dichloromethacrylic acid Acid methyl copolymer, starene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene Copolymer, styrene-acrylonitrile Styrene copolymers such as ril-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic resin, acrylic resin, methacrylic resin, polyacetic acid Vinyl, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, rosin, modified rosin, terpene resin, coumaroindene resin, aliphatic or aliphatic hydrocarbon resin, aromatic petroleum resin Chlorinated paraffin, paraffin wax, and the like. These may be used alone or in combination of two or more.
Among these, a polyester resin is particularly preferable.

The polyester resin is usually obtained by a polycondensation reaction between a polyhydric alcohol compound and a polycarboxylic acid compound.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO), trihydric or higher polyhydric alcohol (TO), and among these, (DIO) alone or (DIO) and a small amount. A mixture with (TO) of is preferred.

Examples of the dihydric alcohol (DIO) include alkylene glycol (eg, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); Alkylene ether glycol (eg, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol (eg, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.) Bisphenols (eg, bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxides of the above alicyclic diols (eg, ethylene oxide, propylene oxide) Side, butylene oxide, etc.) adducts; alkylene oxide (ethylene oxide of the bisphenols, propylene oxide, and the like butylene oxide, etc.) adducts.
Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferred. Combinations of alkylene oxide adducts of bisphenols and alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Is particularly preferred.

  Examples of the trihydric or higher polyhydric alcohol (TO) include 3 to 8 or higher polyhydric aliphatic alcohols (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); 3 And higher phenols (for example, trisphenol PA, phenol novolac, cresol novolak, etc.); alkylene oxide adducts of the above trivalent polyphenols and the like.

Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC), trivalent or higher polyvalent carboxylic acid (TC), (DIC) alone, and (DIC) and a small amount of (TC). And mixtures thereof are preferred.
Examples of the divalent carboxylic acid (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid). , Terephthalic acid, naphthalenedicarboxylic acid, etc.).
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polyvalent carboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid, pyromellitic acid, etc.). The polyvalent carboxylic acid (PC) may be reacted with polyhydric alcohol (PO) using the above acid anhydrides or lower alkyl esters (eg, methyl ester, ethyl ester, isopropyl ester, etc.). Good.

  The ratio of the polyhydric alcohol (PO) to the polyvalent carboxylic acid (PC) is preferably an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH] of 2/1 to 1/1. 1.5 / 1 to 1/1 are more preferable, and 1.3 / 1 to 1.02 / 1 are particularly preferable.

  The polycondensation reaction between the polyhydric alcohol (PO) and the polycarboxylic acid (PC) is heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the pressure is reduced as necessary. The produced water is distilled off to obtain a polyester resin having a hydroxyl group. The hydroxyl value of the polyester resin is preferably 5 or more. The acid value of the polyester resin is usually preferably from 1 to 30, and more preferably from 5 to 20. By giving an acid value as described above, it becomes easy to be negatively charged, and furthermore, at the time of fixing onto a recording paper, the affinity between the recording paper and the toner is good and the low-temperature fixability is improved. However, when the acid value exceeds 30, there is a tendency to deteriorate with respect to the stability of charging, particularly environmental fluctuation.

The weight average molecular weight (Mw) of the polyester resin is preferably 10,000 to 400,000, and more preferably 20,000 to 200,000. When the weight average molecular weight is less than 10,000, the offset resistance may be deteriorated, and when it exceeds 400,000, the low-temperature fixability may be deteriorated.
Here, the weight average molecular weight of the polyester resin is measured by, for example, gel permeation chromatography (GPC).

The binder preferably has an acid value of 1 to 35 mgKOH / g, more preferably 1 to 25 mgKOH / g.
The binder preferably has a glass transition temperature (Tg) of 50 to 70 ° C.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
The waxes are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include animal and plant waxes such as rice wax, candelilla wax, carnauba wax, lanolin; paraffin wax, microcrystalline wax, Petroleum and other petroleum wax; low density polyethylene, high density polyethylene, polyethylene copolymer, polypropylene, polypropylene copolymer, acid value-modified polyethylene, acid-modified polyethylene, graft-modified polyethylene with aromatic monomers, pyrolysis-type low Examples thereof include olefinic waxes such as density polyethylene and pyrolytic polypropylene. These may be used alone or in combination of two or more.

  Moreover, as said wax, a commercial item can be used, for example, HNP (product number: 1, 3, 9, 10, 11, 12), SP (product number: 0145, 1035, 3040, 3035, 0110), Hi. -Mic (part number: 2095, 1080, 3080, 1070, 2065, 1045, 2045), POLYCOAT (part number: 1025, 1455, 2255, 3030, 3155), NEOPALAX (part number: 2545, 3240), PALVAX (part number: 1230, 1335, 1430), CARTOWAX-3025, BONTEX (part numbers: 0011, 2266), S-0750, OX (part numbers: 261BN, 0550, 2251, 1949), NSP-8070, NPS (part numbers: L-70, 6010, 9210) ), HAD (Part No .: 5080, 670), WEISSEN-0453, JP-1500, LUVAX (part number: 1266, 2191, 1151, 0321), EMUSTAR (part number: 0001, 042X, 0135, 0136, 0164, 358) (manufactured by Nippon Wax Co., Ltd.), High wax (Part No .: 800P, 400P, 200p, 100P, 720P, 410P, 420P, 320P, 210P, 220P, 110P, 405MP, 310MP, 320MP, 210MP, 220MP, 4051E, 4052E, 4202E, 1105A, 2203A, 1120H, 1140H 1160H, NL100, NL200, NL500, NL800, NP055, NP105, NP505, NP805) (manufactured by Mitsui Petrochemical Co., Ltd.) and the like can be used.

  The addition amount of the wax as the release agent is preferably 2 to 7 parts by mass with respect to 100 parts by mass of the binder resin. If the addition amount is less than 2 parts by mass, sufficient releasability cannot be exhibited, and hot offset may occur at the time of toner fixing, and if it exceeds 7 parts by mass, too much wax will come out on the toner surface. As a result, the wax content in the toner fine powder increases, and as a result, the variation in glossiness of the visible image (toner image) may increase. Moreover, when there is too much content of wax, hot offset may generate | occur | produce.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used alone or in combination of two or more.
The content of the colorant in the toner is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.

  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, styrene copolymer, polymethyl methacrylate resin, polybutyl Methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polypropylene resin, polyester resin, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin and the like. These may be used individually by 1 type and may use 2 or more types together.

-Charge control agent-
The charge control agent is not particularly limited, and a positive or negative charge control agent can be appropriately selected and used depending on whether the charge charged on the photoconductor is positive or negative.
As the negative charge control agent, for example, a resin or compound having an electron donating functional group, an azo dye, a metal complex of an organic acid, or the like can be used. Specifically, Bontron (product numbers: S-31, S-32, S-34, S-36, S-37, S-39, S-40, S-44, E-81, E-82, E -84, E-86, E-88, A, 1-A, 2-A, 3-A) (above, manufactured by Orient Chemical Industry Co., Ltd.)), Kaya Charge (part numbers: N-1, N-2), Kaya Set Black (Part No .: T-2, 004) (Nippon Kayaku Co., Ltd.), Eisenspiron Black (T-37, T-77, T-95, TRH, TNS-2) FCA-1001-N, FCA-1001-NB, FCA-1001-NZ (manufactured by Fujikura Kasei Co., Ltd.), and the like.
Examples of the positive charge control agent include basic compounds such as nigrosine dyes, cationic compounds such as quaternary ammonium salts, and metal salts of higher fatty acids. Specifically, Bontron (part numbers: N-01, N-02, N-03, N-04, N-05, N-07, N-09, N-10, N-11, N-13, P -51, P-52, AFP-B) (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415, TP-4040 (above, manufactured by Hodogaya Chemical Co., Ltd.), Copy Blue PR, Copy Charge ( Product number: PX-VP-435, NX-VP-434) (manufactured by Hoechst), FCA (Product number: 201, 201-B-1, 201-B-2, 201-B-3, 201-PB, 201-PZ, 301) (above, manufactured by Fujikura Kasei Co., Ltd.), PLZ (product numbers: 1001, 2001, 6001, 7001) (above, manufactured by Shikoku Kasei Kogyo Co., Ltd.), and the like.
These may be used alone or in combination of two or more.

  The addition amount of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited. However, with respect to 100 parts by mass of the binder resin. 0.1-10 mass parts is preferable and 0.2-5 mass parts is more preferable. When the addition amount exceeds 10 parts by mass, the chargeability of the toner is too large, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is reduced, and the image density is increased. If the amount is less than 0.1 parts by mass, the charge rise and charge amount are insufficient, and the toner image may be easily affected.

  In addition to the binder resin, the release agent, the colorant, and the charge control agent, the toner material includes inorganic fine particles, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, and the like as necessary. Can be added.

<Polymerized toner>
The suspension polymerization method is an oil-soluble polymerization initiator, emulsification described later in an aqueous medium in which a colorant, a release agent, and the like are dispersed in a polymerizable monomer and a surfactant and other solid dispersant are contained. Emulsified and dispersed by the method. Thereafter, a polymerization reaction is performed to form particles, and then wet processing for attaching inorganic fine particles to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.
Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and other acids, acrylamide, Surface of toner particles by using methacrylamide, diacetone acrylamide or their methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, acrylates with methacrylates such as dimethylaminoethyl methacrylate, methacrylates, etc. in part Functional groups can be introduced into
Further, by selecting a dispersant having an acid group or a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

  As the emulsion polymerization method, a water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by a usual emulsion polymerization method. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, wet processing of inorganic fine particles described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer that can be used in the suspension polymerization method.

  In the present invention, among these, since the selectivity of the resin is high, the low-temperature fixability is high, the granulation property is excellent, and the particle size, the particle size distribution, and the shape can be easily controlled. The toner is preferably obtained by emulsifying or dispersing a toner material dissolved or dispersed in an aqueous medium and granulating the toner.

The toner material solution is obtained by dissolving the toner material in a solvent, and the toner material dispersion liquid is obtained by dispersing the toner material in a solvent.
Examples of the toner material include an adhesive base obtained by reacting an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, a binder resin, a release agent, and a colorant. And other components such as resin fine particles and a charge control agent as necessary.

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

There is no restriction | limiting in particular as a weight average molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 1,000 or more are preferable and 2,000-10,000,000 are more preferable. 3,000 to 1,000,000 are particularly preferred.
When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

The storage elastic modulus of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10,000 dyne / cm ² , Usually, it is 100 ° C. or higher, and preferably 110 to 200 ° C. When the (TG ′) is less than 100 ° C., the hot offset resistance may be deteriorated.
The viscosity of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (Tη) at which a measurement frequency of 20 Hz is 1,000 poise is usually 180 ° C. or lower. Yes, 90-160 degreeC is preferable. When the (Tη) exceeds 180 ° C., the low-temperature fixability may be deteriorated.
Therefore, from the viewpoint of achieving both hot offset resistance and low-temperature fixability, the (TG ′) is preferably higher than the (Tη). That is, the difference (TG′−Tη) between (TG ′) and (Tη) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. The larger the difference, the better.
Further, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability, the (TG′−Tη) is preferably 0 to 100 ° C., more preferably 10 to 90 ° C., and still more preferably 20 to 80 ° C.

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

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

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

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

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

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

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

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

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

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

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

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

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

The trihydric or higher polyol (TO) is preferably a trihydric or higher polyhydric alcohol, for example, a trihydric or higher polyhydric aliphatic alcohol, a trihydric or higher polyphenol, or a trihydric or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the trivalent or higher polyphenols alkylene oxide adducts include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trivalent or higher polyphenols.

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

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

The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.

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

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

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

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

There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate and diphenyl ether-4,4′-diisocyanate. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, and the like.
These can 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 group are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and 4/1 to 1.2 / 1. Is more preferable, and 3/1 to 1.5 / 1 is particularly preferable.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

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

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

  The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 1,000 to 30,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 1,500-15,000 are more preferable. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.

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

--Binder resin--
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, although a polyester resin etc. are mentioned, Undenatured polyester resin (unmodified polyester resin) is especially preferable.
When the unmodified polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of a polyol (PO) and a polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure that is compatible with each other. It is preferable in terms of resistance to 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). 1,000 is more preferable. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Therefore, as described above, the content of the component having the weight average molecular weight (Mw) of less than 1,000. Is required to be 8 to 28% by mass. On the other hand, when the weight average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the unmodified polyester resin is usually preferably 50 to 70 ° C. When the glass transition temperature is less than 50 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 35.0 mgKOH / g, and more preferably 10 to 35.0 mgKOH / g. Generally, it becomes easy to be negatively charged by giving the toner an acid value.
When the unmodified polyester resin is contained in the toner material, a mixing mass ratio of a polymer (for example, a urea bond-forming group-containing polyester resin) capable of reacting with an active hydrogen group-containing compound and the unmodified polyester resin ( The polymer / unmodified polyester resin) is preferably 5/95 to 80/20, more preferably 10/90 to 25/75.
When the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Glossiness may deteriorate.
As content of the said non-modified polyester resin in the said binder resin, 50-100 mass% is preferable, for example, 70-95 mass% is more preferable, 80-90 mass% is still more preferable. When the content is less than 50% by mass, the low-temperature fixability and the glossiness of the image may be deteriorated.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used alone or in combination of two or more.

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

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

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

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

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a mold release agent, a charge control agent, a fluid improvement agent, a cleaning property improvement agent, a magnetic material, etc. are mentioned. .

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

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
When the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1,000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

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

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, a fluorine resin is preferable, and the fluorine resin is represented by the following general formula (1). Preferred examples thereof include tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers.
However, in the general formula (1), Rf represents a perfluoro group. m and n represent a positive integer.

Examples of the fluororesin include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer. Examples thereof include a polymer, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene, chlorotrifluoroethylene-ethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, or a mixture thereof.
The molecular weight, molecular weight distribution, crystallinity, melting point, etc. of the fluororesin fine powder are not limited to the characteristics of the fine powder.
The addition amount of the fluororesin is preferably 0.05 to 10% by mass, and more preferably 0.1 to 8% by mass with respect to the toner.

Examples of the other charge control agents include triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus Examples thereof include simple substances or compounds thereof, tungsten simple substances or compounds thereof, fluorine-based activators, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. These may be used alone or in combination of two or more.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), Fourth 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, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups, carbo Sill group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded together with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

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

-Resin fine particles-
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate. Examples of the resin include vinyl resins. Among these, vinyl resins are particularly preferable.
These may be used alone or in combination of two or more. Among these, at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin is preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). "; Manufactured by Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.
The volume average particle diameter of the resin fine particles is preferably 5 to 2,000 nm, and more preferably 20 to 200 nm. When the volume average particle size is less than 5 nm, it may be difficult to produce a polymerized toner, and when it exceeds 2,000 nm, it may also be difficult to produce a polymerized toner.

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

  Examples of the toner include toners produced by a known suspension polymerization method, emulsion aggregation method, emulsion dispersion method, etc., and can react with an active hydrogen group-containing compound and the active hydrogen group-containing compound. The toner material containing the polymer is dissolved in an organic solvent to prepare a toner solution, and then the toner solution is dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing solution is prepared in the aqueous medium. A toner obtained by reacting a compound with a polymer capable of reacting with the active hydrogen group-containing compound to form an adhesive substrate in the form of particles and removing the organic solvent is preferred.

-Toner solution-
The toner solution can be prepared by dissolving the toner material in the organic solvent.

-Organic solvent-
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, and methyl isobutyl ketone. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used alone or in combination of two or more.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.

-Dispersion-
The dispersion is prepared by dispersing the toner solution in an aqueous medium.
When the toner solution is dispersed in the aqueous medium, a dispersion (oil droplets) made of the toner solution is formed in the aqueous medium.

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

The toner solution is preferably dispersed in the aqueous medium with stirring.
The dispersion method is not particularly limited and may be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction disperser. High pressure jet disperser, ultrasonic disperser, and the like. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 3,000 to 30,000 rpm is preferable, 5,000 to 20,000 rpm is more preferable, and the dispersion time is preferably 0.1 to 5 minutes in the case of a batch method, and the dispersion temperature is under pressure. 0-150 degreeC is preferable and 40-98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

As an example of the method for producing the toner, a method for obtaining the toner by forming the adhesive base material in the form of particles will be described below.
In the method of granulating the toner by forming the adhesive base material in the form of particles, for example, the preparation of an aqueous medium phase, the preparation of the toner solution, the preparation of the dispersion, the addition of the aqueous medium, etc. Synthesis of a polymer (prepolymer) capable of reacting with an active hydrogen group-containing compound, synthesis of the active hydrogen group-containing compound, etc.).

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The toner solution is prepared by adding, in the organic solvent, the active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, the colorant, the release agent, the charge control agent, and the unmodified. A toner material such as a polyester resin can be dissolved or dispersed. In order to form an inorganic oxide particle-containing layer within 1 μm from the toner surface, inorganic oxide particles such as silica, titania and alumina are added.
In the toner material, components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound are added when the resin fine particles are dispersed in the aqueous medium in the preparation of the aqueous medium phase. The toner solution may be added and mixed in the aqueous medium, or may be added to the aqueous medium phase together with the toner solution when the toner solution is added to the aqueous medium phase.

The dispersion can be prepared by emulsifying or dispersing the previously prepared toner solution in the previously prepared aqueous medium phase. When the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an elongation reaction or a crosslinking reaction during the emulsification or dispersion, the adhesive base material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). A toner solution is emulsified or dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are subjected to an extension reaction or the like in the aqueous medium phase. (2) The toner solution is emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance, to form a dispersion, and in the aqueous medium phase Or (3) the active hydrogen group after the toner solution is added and mixed in the aqueous medium. The organic compound is added to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive base material by the emulsification or dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

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

In the preparation of the dispersion, if necessary, a dispersant is used from the viewpoint of stabilizing the dispersion (oil droplets made of the toner solution) and sharpening the particle size distribution while obtaining a desired shape. Is preferred.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a sparingly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used alone or in combination of two or more. 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 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 perfluorooctanesulfonyl glutamate, 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 ester and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Florad FC-93, FC-95, FC-98, FC -129 (manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F-191, F-812, F- 833 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); 100, F150 (manufactured by Neos) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, and perfluoroalkyl (carbon number 6 to 10) sulfonamidopropyltrimethylammonium salts. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (Asahi Glass Co., Ltd.); Florad FC-135 (Sumitomo 3M Co., Ltd.); Unidyne DS-202 (Daikin Industries Co., Ltd.), Megafuck F-150, F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products);

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

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

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

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

  The organic solvent is removed from the obtained dispersion (emulsified slurry). The organic solvent is removed by (1) a method of gradually raising the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets, and (2) spraying the emulsified dispersion in a dry atmosphere. A method in which the water-insoluble organic solvent in the oil droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation, (3) a method by filtration, and (4) a method under reduced pressure. , Etc.

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

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

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

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

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

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

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D50)) of 10 to 200 μm, and more preferably 40 to 100 μm.
When the average particle size (volume average particle size (D50)) is less than 10 μm, in the distribution of carrier particles, there are many fine powder systems, and the magnetization per particle may be lowered, causing carrier scattering, If it exceeds 200 μm, the specific surface area may decrease and toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be particularly poor.

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

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, 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. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

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

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

When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.
In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

Since the developer of the present invention contains the toner of the present invention, it is possible to prevent the occurrence of photoconductor filming, and to stably form excellent clear high-quality images without fluctuations in image unevenness. Can do.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention comprises the toner or the developer of the present invention contained in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a toner container main body and a cap etc. are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral unevenness is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Particularly preferred.
The material of the toner container main body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable. Among them, for example, a polyester resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, a polychlorinated resin is preferable. Preferred examples include vinyl resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a toner to produce a visible image. A developing unit to be formed, and further includes other units such as a charging unit, a developing unit, a transfer unit, a cleaning unit, and a discharging unit, which are appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably mounted on various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably mounted on the image forming apparatus of the present invention described later.

Here, for example, as shown in FIG. 1, the process cartridge includes a photoreceptor 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and other units as necessary. It has. In FIG. 1, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.
As the photoreceptor 101, the same one as an image forming apparatus described later can be used. An arbitrary charging member is used for the charging means 102.
Next, the image forming process using the process cartridge shown in FIG. 1 will be described. The photoconductor 101 is charged on the surface by charging by the charging means 102 and exposure 103 by the exposure means (not shown) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the exposure image is formed. The electrostatic latent image is developed with toner by the developing unit 104, and the toner development is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  The image forming apparatus of the present invention is constructed by integrally combining the electrostatic latent image carrier and the components such as a developing device and a cleaning device as a process cartridge, and this unit can be attached to and detached from the apparatus main body. It may be configured. Further, at least one of a charger, an image exposure device, a developing device, a transfer or separation device, and a cleaning device is integrally supported together with an electrostatic latent image carrier to form a process cartridge, and is detachably attached to the apparatus main body. One unit may be detachable using guide means such as a rail of the apparatus main body.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention 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 further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. A recycling process, a control process, and the like.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image bearing member (sometimes referred to as “electrophotographic photosensitive member” or “photosensitive member”) is not particularly limited in terms of material, shape, structure, size, etc. Although it can be selected as appropriate, the shape is preferably a drum shape, and examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. . Among these, amorphous silicon and the like are preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method, or the like is applied on the support. A photoconductor having a photoconductive layer made of a-Si (hereinafter sometimes referred to as “a-Si-based photoconductor”) can be used. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

The electrostatic latent image can be formed, for example, by charging the surface of the electrostatic latent image carrier and then exposing it like an image, and by the electrostatic latent image forming means. .
The electrostatic latent image forming unit includes, for example, at least a charger that charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise.

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

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. In the case of using a magnetic brush, the magnetic brush is composed of various ferrite particles such as Zn—Cu ferrite as a charging member, a non-magnetic conductive sleeve for supporting it, and a magnet roll included therein. Or, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound or attached to a metal or other conductive core. To make a charger.
The charger is not limited to the contact charger as described above. However, since an image forming apparatus in which ozone generated from the charger is reduced is obtained, a contact charger is used. preferable.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the latent electrostatic image bearing member charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developing unit capable of contacting or non-contacting the toner or the developer with the electrostatic latent image is provided, and includes the toner container according to the present invention. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the 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. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. 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 toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

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

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. The number of the transfer means may be one, or two or more.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

-Fixing Step and Fixing Unit The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium. Alternatively, the toners of the respective colors may be simultaneously formed in a state where they are laminated.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. 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 in the heating and pressing means is usually preferably 80 to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

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

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

  Next, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

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

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

  In the image forming apparatus 100 shown in FIG. 2, for example, 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 toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. A tandem image forming apparatus 100 shown in FIG. 4 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 4. 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. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem 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. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22.
In the tandem image forming apparatus 100, 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. Yes.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, 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 the document is set on the contact glass 32 of the scanner 300. 400 is closed.

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

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image-corresponding image (L in FIG. 5), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. Developing with color toner (black toner, yellow toner, magenta toner and cyan toner) to form a toner image with each color toner, and intermediate transfer of the toner image 50 includes a transfer charger 62 for transferring the toner image on the toner image 50, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the 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 residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming method and the image forming apparatus of the present invention, since the toner of the present invention is used that can form a good visible image over a long period of time while maintaining the cleaning property, the charging property is good. An image can be formed efficiently.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.

(Production Example 1)
<Preparation of Polymerized Toner A>
-Synthesis of organic fine particle emulsion-
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 14 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 137 parts of styrene, methacrylic acid When 138 parts and 1.2 parts of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Next, 30 parts of a 1% aqueous solution of ammonium persulfate was added, and the mixture was aged at 71 ° C. for 6 hours, and an aqueous dispersion of vinyl resin (styrene salt copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate) A fine particle dispersion 1 ”was prepared.
The obtained [Fine Particle Dispersion 1] was measured with a particle size distribution measuring apparatus (“LA-920”, manufactured by Horiba, Ltd.) using a laser light scattering method. The volume average particle size was 0.18 μm. . A portion of this [fine particle dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin component was 150 ° C.

-Preparation of aqueous phase-
990 parts of water, 80 parts of “fine particle dispersion 1”, 38 parts of 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.), 90 parts of ethyl acetate, and tetrafluoroethylene- 0.6 parts of perfluoroalkyl vinyl ether copolymer (number average particle diameter of primary particles 0.15 μm) was mixed and stirred to obtain a milky white liquid. This is designated as “aqueous phase 1”.

-Synthesis of low molecular weight polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 224 parts of bisphenol A ethylene oxide 2-mole adduct, 561 parts of bisphenol A propylene oxide 3-mole adduct, 217 parts of terephthalic acid, 46 parts of adipic acid, And 3 parts of dibutyltin oxide were added and reacted at 230 ° C. under normal pressure for 7 hours. Next, after 5 hours of reaction at a reduced pressure of 10 to 15 mmHg, 42 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. and normal pressure for 5 hours to obtain “low molecular weight polyester 1”.
The obtained “low molecular polyester 1” had a number average molecular weight (Mn) of 2,200, a weight average molecular weight (Mw) of 6,600, a glass transition temperature (Tg) of 41 ° C., and an acid value of 22 mgKOH / g.

-Synthesis of prepolymer-
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 685 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 281 parts of terephthalic acid, trimellitic anhydride 24 parts and 3 parts of dibutyltin oxide were added and reacted at 230 ° C. under normal pressure for 10 hours. Next, the reaction was performed at a reduced pressure of 10 to 15 mmHg for 8 hours to synthesize “intermediate polyester 1”.
The resulting “intermediate polyester 1” has a number average molecular weight (Mn) of 2,200, a weight average molecular weight (Mw) of 9,400, a glass transition temperature (Tg) of 61 ° C., an acid value of 10.0 mgKOH / g, and a hydroxyl value. 45.

Next, 414 parts of “intermediate polyester 1”, 86 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 8 hours. “Prepolymer 1” was synthesized.
The mass% of free isocyanate in the obtained “prepolymer 1” was 1.53%.

-Synthesis of ketimine-
In a reaction vessel equipped with a stir bar and a thermometer, 176 parts of isophoronediamine and 73 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 8 hours to synthesize “ketimine compound 1”. The amine value of the obtained “ketimine compound 1” was 410.

-Preparation of master batch-
42 parts of carbon black as a pigment (manufactured by Cabot, Regal 400R), polyester resin as a binder resin (manufactured by Sanyo Chemical Industries, RS-801, acid value 10, weight average molecular weight (Mw) = 20,000, glass 63 parts of a transition temperature (Tg) = 64 ° C. and 30 parts of water were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This is kneaded with two rolls set at a roll surface temperature of 135 ° C. for 70 minutes, and pulverized to a size of 1 mm in diameter with a pulverizer,
[Masterbatch 1] was produced.
Next, using this master batch pigment, a toner was prepared by the following method.

-Preparation of oil phase-
In a container equipped with a stirring bar and a thermometer, 375 parts of “low molecular polyester 1”, 110 parts of carnauba wax, 20 parts of a charge control agent (salicylic acid metal complex E-84, manufactured by Orient Chemical Industries), ethyl acetate 949 Then, the temperature was raised to 80 ° C. with stirring, maintained at 80 ° C. for 10 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of “Masterbatch 1” and 510 parts of ethyl acetate were charged in the container and mixed for 1 hour to prepare “Raw material solution 1”.
Next, 1324 parts of “raw material solution 1” was transferred into the container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads. The carbon black and the wax were dispersed under the conditions of 80% by volume and 3 passes. Next, 1,324 parts of a 65% ethyl acetate solution of “low molecular weight polyester 1” was added, and one pass was performed with a bead mill under the above conditions to prepare “pigment and wax dispersion 1”.
The solid content concentration (130 ° C., 30 minutes) of the obtained “Pigment and Wax Dispersion 1” was 50%.

-Emulsification and solvent removal-
“Pigment and wax dispersion 1” (648 parts), “Prepolymer 1” (152 parts) and [Ketimine compound 1] (7.6 parts) are placed in a container, and TK homomixer (manufactured by Tokushu Kika Co., Ltd.) is used at 5 at 5,000 rpm. After mixing for 1 minute, 1,200 parts of “Aqueous Phase 1” was added to the container and mixed with a TK homomixer at 14,000 rpm for 40 minutes to prepare “Emulsion Slurry 1”.
Next, the “emulsion slurry 1” is put into a container in which a stirrer and a thermometer are set, and after desolvation at 30 ° C. for 10 hours, aging is performed at 45 ° C. for 6 hours to obtain “dispersion slurry 1” It was.
The obtained “dispersed slurry 1” had a volume average particle size of 5.75 μm and a number average particle size of 5.0 μm as measured by Coulter Multisizer II (manufactured by Nikka Machine Co., Ltd.).

-Cleaning and drying-
[Emulsified slurry 1] 100 parts were filtered under reduced pressure, and then washed and dried as follows.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 13,000 rpm for 10 minutes), and then filtered.
(2) 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 13,000 rpm), and then filtered under reduced pressure. This ultrasonic alkali cleaning was performed again (two ultrasonic alkali cleanings).
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 13,000 rpm for 10 minutes), and then filtered.
(4) 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at a rotation speed of 13,000 rpm) and then filtered twice to prepare a filter cake.
Next, the obtained filter cake was dried at 45 ° C. for 48 hours in a circulating drier, sieved with an opening of 75 μm mesh, a volume average particle diameter (Dv) of 5.1 μm, and an average circularity of 0.97. Toner base particles were obtained by a polymerization method. This is designated as Polymerized Toner A1.

(Production Example 2)
-Production of Polymerized Toner A2-
A polymerized toner A2 having a volume average particle size of 6.2 μm and an average circularity of 0.98 was produced in the same manner as in Production Example 1 except that the ultrasonic alkali cleaning was performed once in Production Example 1.

(Production Example 3)
-Production of Polymerized Toner A3-
A polymerized toner A3 having a volume average particle size of 5.5 μm and an average circularity of 0.95 was produced in the same manner as in Production Example 1 except that “Emulsion slurry 1” was aged at 40 ° C. for 10 hours in Production Example 1. did.

(Production Example 4)
-Production of Polymerized Toner A4-
In Production Example 1, a volume average particle diameter of 3.9 μm and an average circular shape were obtained in the same manner as in Production Example 1, except that 30 minutes was mixed at 13,000 rpm for the TK homomixer rotation speed when obtaining “emulsified slurry 1”. Polymerized toner A4 having a degree of 0.98 was produced.

(Production Example 5)
-Production of Polymerized Toner A5-
Polymerization with a volume average particle size of 4.5 μm and an average circularity of 0.98 in the same manner as in Production Example 1 except that the acid value of “Intermediate Polyester 1” was adjusted to 4.0 mgKOH / g in Production Example 1. Toner A5 was produced.

(Production Example 6)
-Production of Polymerized Toner A6-
In Production Example 1, except that the glass transition temperature (Tg) of “Intermediate Polyester 1” was adjusted to 52 ° C., a volume average particle size of 6.0 μm and an average circularity of 0.97 were obtained in the same manner as in Production Example 1. Polymerized toner A6 was produced.

(Production Example 7)
-Production of Polymerized Toner A7-
In Production Example 1, polyester resin particles having a volume average particle diameter of 30 nm (glass transition temperature (Tg) = 70 ° C., weight average molecular weight (Mw) = 11,000) were used as resin fine particles, and the solvent was removed by reduced pressure. In the same manner as in Production Example 1, a polymerized toner A7 having a volume average particle size of 5.8 μm and an average circularity of 0.99 was produced.

(Production Example 8)
-Production of Polymerized Toner AZ1-
A polymerization toner AZ1 having an average circularity of 0.89 and a volume average particle size of 5.0 μm was produced in the same manner as in Production Example 1 except that “Emulsion slurry 1” was aged at 35 ° C. for 3 hours in Production Example 1. .

(Production Example 9)
-Production of Polymerized Toner AZ2-
In Production Example 1, a volume average particle size of 3.1 μm, an average was obtained in the same manner as in Production Example 1, except that the TK homomixer at the time of obtaining “Emulsion slurry 1” was mixed at 5,000 rpm for 15 minutes. Polymerized toner AZ2 having a circularity of 0.98 was produced.

(Production Example 10)
-Production of Polymerized Toner AZ3-
In Production Example 1, except that the glass transition temperature (Tg) of “Intermediate Polyester 1” was adjusted to 43 ° C., a volume average particle size of 2.8 μm and an average circularity of 0.89 were obtained in the same manner as in Production Example 1. Polymerized toner AZ3 was produced.

(Production Example 11)
-Production of Polymerized Toner AZ4-
In Production Example 1, the volume average was obtained in the same manner as in Production Example 1 except that the same amount of chromium-containing azo dye (S-34, manufactured by Orient Chemical Co., Ltd.) was used instead of the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. A polymerization toner AZ4 having a particle size of 3.9 μm and an average circularity of 0.97 was produced.

(Production Example 12)
-Preparation of pulverized toner B1-
1,200 parts of water and 540 parts of carbon black (MA60, manufactured by Mitsubishi Chemical Corporation) are thoroughly stirred with a flasher. 1,200 parts of polyester resin (acid value 13, hydroxyl value 25, number average molecular weight (Mn) 4500, Mw / Mn = 4.0, glass transition temperature (Tg) 60 ° C.) is added to this, and 30 ° C. at 30 ° C. Kneaded for a minute. Thereafter, 1000 parts of xylene was added, and then kneaded for 1 hour, after removing water and xylene, rolled and cooled, and pulverized with a pulverizer to obtain a master batch pigment (MB-1).

  Next, 600 parts of water and C.I. I. Pigment Blue 15: 3 water-containing cake (solid content 50%) 1,200 parts was thoroughly stirred with a flasher. 1,200 parts of polyester resin (acid value 13, hydroxyl value 25, number average molecular weight (Mn) 4500, Mw / Mn = 4.0, glass transition temperature (Tg) 60 ° C.) is added to this, and 30 parts at 150 ° C. are added. Kneaded for a minute. Thereafter, 1,000 parts of xylene was added, and then kneaded for 1 hour, after removing water and xylene, rolled and cooled, pulverized with a pulverizer, and then passed twice with a three-roll mill to obtain a master batch pigment ( MB-2).

Subsequently, 100 parts of a polyester resin (acid value 13 mgKOH / g, hydroxyl value 25, number average molecular weight (Mn) 4500, Mw / Mn = 4.0, glass transition temperature (Tg) 60 ° C.), the master batch (MB-1) ) 5 parts and 0.5 part of the master batch (MB-2) were mixed with a mixer, melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled.
Next, a turbo counter jet mill pulverizer (manufactured by Turbo Kogyo Co., Ltd., rotating blade rotation speed: 7500 rpm, feed amount 1.2 kg / hr) and wind classifying by swirling flow (DS classifier, manufactured by Nippon Pneumatic Industrial Co., Ltd.) Thus, toner base particles having a volume average particle diameter of 8.9 μm were prepared.
Next, with respect to 100 parts by mass of the obtained toner base particles, 0.9 part by mass of a charge control agent (TN-105 manufactured by Hodogaya Chemical Co., Ltd.) and 0.5 part by mass of hydrophobic silica (H2000, manufactured by Clariant Japan Co., Ltd.) Using a Q mixer manufactured by Mitsui Mine, mixing at 6,000 rpm for 10 minutes while heating at an appropriate temperature, a “pulverized toner B1” was produced.
The average circularity of the obtained ground toner B1 was 0.91 as measured by a flow type particle image analyzer FPIA-2000 manufactured by Sysmex Corporation.

(Production Example 13)
-Preparation of pulverized toner B2-
600 parts of water, and C.I. I. 1,200 parts of Pigment Yellow 17 water-containing cake (solid content 50%) was thoroughly stirred with a flasher. 1,200 parts of polyester resin (acid value 13, hydroxyl value 25, number average molecular weight (Mn) 4500, Mw / Mn = 4.0, glass transition temperature (Tg) 60 ° C.) is added to this, and 30 ° C. at 30 ° C. After kneading for 1 minute, 1,000 parts of xylene was added and kneaded for 1 hour, after removing water and xylene, rolling and cooling, pulverization with a pulverizer, and two passes with 3 rolls to prepare a master batch pigment.

Next, 100 parts of a polyester resin (acid value 15, hydroxyl value 25, number average molecular weight (Mn) 4500, Mw / Mn = 4.0, glass transition temperature (Tg) 62 ° C.), and 5 parts of the master batch pigment were added. After mixing with a mixer, the mixture was melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, it is pulverized with a turbo counter jet mill pulverizer (manufactured by Turbo Kogyo Co., Ltd., rotating blade rotation speed: 7700 rpm, feed amount 1.3 kg / hr), and air classification by swirling flow (DS classifier, manufactured by Nippon Pneumatic Industrial Co., Ltd.) ) To produce toner base particles having a volume average particle size of 9.8 μm.
Mitsui Mine was charged with 1.1 parts by mass of a charge control agent (TN-105, manufactured by Hodogaya Chemical Co., Ltd.) and 0.5 parts by mass of hydrophobic silica (H2000, manufactured by Clariant Japan) with respect to 100 parts by mass of the obtained toner base particles. The mixture was mixed at 6,000 rpm for 10 minutes while heating at an appropriate temperature with a Q mixer manufactured to prepare pulverized toner B2 having a volume average particle size of 7.5 μm.
The average circularity of the obtained ground toner B2 was 0.90 as measured by a flow type particle image analyzer FPIA-2000 manufactured by Sysmex Corporation.

(Production Example 14)
-Production of pulverized toner B3-
In Production Example 12, the volume average particle size is 17.2 μm and the average circularity is 0.88 in the same manner as in Production Example 12 except that the feed rate of the turbo counter jet mill pulverizer is 3.5 kg / hr. A pulverized toner B3 was produced.

(Production Example 15)
-Production of pulverized toner B4-
A pulverized toner B4 having a volume average particle diameter of 8.8 μm and an average circularity of 0.89 was produced in the same manner as in Production Example 12, except that the polyester resin having an acid value of 29 mgKOH / g was used in Production Example 12. .

(Production Example 16)
-Preparation of pulverized toner B5-
In Production Example 12, a pulverized toner B5 having a volume average particle diameter of 7.9 μm and an average circularity of 0.85 was obtained in the same manner as in Production Example 12, except that a polyester resin having a glass transition temperature (Tg) of 67 ° C. was used. Was made.

(Production Example 17)
-Preparation of pulverized toner BZ1-
In Production Example 12, the volume average particle size is 7.5 μm and the average circularity is 0.83, as in Production Example 12, except that the rotation speed of the rotating blades of the turbo counter jet mill crusher is 11,000 rpm. A pulverized toner BZ1 was prepared.

(Production Example 18)
-Preparation of pulverized toner BZ2-
In Production Example 12, the volume average particle diameter is 25.3 μm and the average circularity is 0.88 in the same manner as in Production Example 12 except that the feed rate of the turbo counter jet mill pulverizer is 7.5 kg / hr. A pulverized toner BZ2 was produced.

(Production Example 19)
-Preparation of ground toner BZ3-
In Production Example 12, the volume average particle size is 11.3 μm and the average circularity is 0.88 in the same manner as in Production Example 12, except that the feed amount of the turbo counter jet mill pulverizer is 5.4 kg / hr. A pulverized toner BZ3 was produced.

(Production Example 20)
-Preparation of pulverized toner BZ4-
A pulverized toner BZ4 having a volume average particle diameter of 6.7 μm and an average circularity of 0.89 was prepared in the same manner as in Production Example 12, except that a polyester resin having an acid value of 43 was used in Production Example 12.

(Examples 1-10 and Comparative Examples 1-5)
The toners of Examples 1 to 10 and Comparative Examples 1 to 5 were prepared by mixing the types and addition amounts of the polymerization toner and the pulverized toner shown in Table 1 using a Henschel mixer manufactured by Mitsui Mining Co., Ltd.
The ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the obtained mixed toner was measured with a particle size measuring device “Multisizer II” manufactured by Beckman Coulter. The results are shown in Table 1.

  Various properties of the obtained toners of Examples 1 to 10 and Comparative Examples 1 to 5 were evaluated as follows. The results are shown in Table 2.

<Chargeability>
5 g of each toner was mixed with 95 g of a ferrite carrier (manufactured by Kanto Denka Co., Ltd.), and this was mixed for 60 minutes with a TURBULA mixer manufactured by Willy A BACHOFENAG to produce a developer. Q / M of the obtained developer was measured with a blow-off device (N ₂ gas, discharged for 1 minute). This was considered to be chargeable and evaluated according to the following criteria.
〔Evaluation criteria〕
○: Chargeability is good. △: Actually usable level ×: Unusable level

<Cleanability>
Using a remodeling machine based on an image forming apparatus (Rigoh Co., Ltd., Imageo Neo C385), 100 solid images with an image density of 1.5 ± 0.1 were produced, and the 101st sheet was transferred from the photoconductor to the paper. At this timing, the power was turned off, the transfer residual toner on the photoconductor was transferred with a tape, the density of this transfer residual toner was measured with a Macbeth densitometer, and evaluated according to the following criteria.
〔Evaluation criteria〕
○: Transfer residual toner concentration (ID) 0.15 or less Δ: Transfer residual toner concentration (ID) 0.3 or less ×: Transfer residual toner concentration (ID) 0.31 or more

<Soil dirt>
Each developer whose chargeability was evaluated was set in a remodeling machine based on an image forming apparatus (manufactured by Ricoh Co., Ltd., Image Neo Neo C385). The background soil of the photoconductor was observed at 20 points with a magnifying glass and evaluated according to the following criteria.
〔Evaluation criteria〕
○: No soiling, good △: Within acceptable range ×: Outside practical range

<Toner scattering property>
Each developer evaluated for chargeability is set in a modified machine based on an image forming apparatus (Imagio Neo C385, manufactured by Ricoh Co., Ltd.), and the developer is stirred for 3 hours without toner replenishment, and after 3 hours. The scattered toner adhering to the release tape previously set on the upper part of the developing machine was observed with a loupe at 20 points and evaluated according to the following criteria.
〔Evaluation criteria〕
○: Toner scattering good △: Within allowable range ×: Out of practical range

<Image quality>
Each developer evaluated for chargeability is set in a modified machine based on an image forming apparatus (Imagio Neo C385 manufactured by Ricoh Co., Ltd.), and the developer is stirred for 3 hours without toner replenishment, and after 3 hours. Images were taken out and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Very good image quality ○: Good image quality △: Within acceptable range ×: Out of practical range

From the results in Table 2, Examples 1 to 10 have superior performances in terms of cleaning properties, charging properties, background dirt, scattering properties, and image quality as compared with Comparative Examples 1 to 5. Is recognized.

The toner of the present invention is a mixture of a polymerized toner produced by a polymerization method and a pulverized toner produced by a pulverization method, maintaining good cleaning properties and good chargeability, and providing a good visible image for a long time. Can be formed.
The developer, toner-containing container, process cartridge, image forming apparatus, and image forming method of the present invention using the toner of the present invention are suitably used for high-quality image formation.

FIG. 1 is a schematic view showing an example of the process cartridge of the present invention. FIG. 2 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 3 is a schematic view showing another example of the image forming apparatus of the present invention. FIG. 4 is a schematic view showing an example of the tandem type image forming apparatus of the present invention. FIG. 5 is a partially enlarged view of FIG.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developer 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Development roller Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Ejection Roller 57 Discharge tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 101 Photoconductor 102 Charging means 103 Exposure Means 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 110 Belt type image fixing device 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed capacity Set 145 Separating roller 146 Feeding path 147 Conveying roller 148 Feeding path 150 Copying device main body 200 Feeding table 210 Image fixing device 220 Heating roller 230 Pressure roller 300 Scanner 400 Automatic document feeder (ADF)

Claims (18)

A toner obtained by mixing a polymerized toner produced by a polymerization method and a pulverized toner produced by a pulverization method,
The average circularity of the polymerized toner is 0.93 to 0.99, the average circularity of the pulverized toner is 0.85 to 0.93, and the volume average particle diameter (Dv) in the mixed toner is A toner having a ratio (Dv / Dn) to a number average particle diameter (Dn) of 1.40 or less.   The toner according to claim 1, wherein a mixing mass ratio of the polymerized toner and the pulverized toner (polymerized toner: pulverized toner) is 20: 1 to 1: 1.   The toner according to claim 1, wherein the volume average particle diameter (Dv) of the polymerized toner is 3 to 9 μm, and the volume average particle diameter (Dv) of the pulverized toner is 5 to 20 μm.   The toner according to any one of claims 1 to 3, wherein the acid value of the binder in the polymerized toner and the pulverized toner is 1 to 35 mgKOH / g.   The toner according to any one of claims 1 to 4, wherein the glass transition temperature (Tg) of the binder in the polymerized toner and the pulverized toner is 50 to 70 ° C.   The binder in the polymerized toner contains the modified polyester resin (i) and the unmodified polyester resin (ii), and the mixing mass ratio ((i) / (ii)) is 5/95 to 80 / The toner according to claim 1, wherein the toner is 20.   The toner according to claim 1, wherein the polymerized toner contains a charge control agent, and the charge control agent is a fluororesin. The toner according to claim 7, wherein the fluororesin is a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer represented by the following general formula (1).
However, in the general formula (1), Rf represents a perfluoro group. m and n represent a positive integer.   A resin fine particle is contained in at least one of the surface and inside of the polymerized toner, and the resin fine particle is at least one selected from vinyl resin fine particles, polyurethane resin fine particles, epoxy resin fine particles, and polyester resin fine particles. The toner according to any one of 1 to 8.   The toner according to claim 9, wherein the resin fine particles have a volume average particle diameter of 5 to 2,000 nm.   A polymerized toner is prepared by dissolving or dispersing a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an organic acid compound in an organic solvent. A toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium for adhesion. The toner according to claim 1, wherein the toner is obtained by forming a conductive substrate into particles and removing the organic solvent.   The toner according to claim 11, wherein the organic solvent is removed under at least one of reduced pressure and heating.   The toner according to claim 11, wherein the organic solvent is removed by filtration.   A developer comprising the toner according to claim 1 and a carrier.   A toner-filled container filled with the toner according to claim 1.   An electrostatic latent image carrier, and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to claim 1 to form a visible image. A process cartridge having at least An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of claims 1 to 13 At least developing means for forming a visible image by developing the toner, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. ,
The image forming apparatus, wherein the developing unit has a toner recycling mechanism. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to any one of claims 1 to 13 to form a visible image At least a developing 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 image forming method, wherein the developing step includes a toner recycling step.