JP2012242490A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner that has improved fixability, heat-resistant storage stability, and image quality.SOLUTION: Toner is obtained by coating mold-release-agent-containing porous particles containing a mold release agent at least with a melting point of 60°C or more inside the porous holes on the surface of toner base particles containing a binder resin and colorant. A developing device 40 of a process cartridge attached to an image forming apparatus is charged with developer formed by containing the toner, and the developing device 40 is attached to the image forming apparatus body to form images by an electrophotographic method.

Description

  The present invention relates to an image forming toner used to visualize an electrostatic latent image on an image carrier in an electrophotographic process such as an electrophotographic apparatus or an electrostatic recording apparatus.

  As an electrophotographic method, many methods are known. In general, an electrostatic latent image forming step for forming an electric latent image on a photoconductor using a photoconductive substance by using various means, A developing step of developing a latent image using toner to form a toner image, a transferring step of transferring the toner image to a transfer material such as paper, and heating, pressurizing, heating and pressurizing the toner image transferred to the transfer material; The process includes a fixing process for fixing the transfer material with a solvent vapor or the like, and a cleaning process for removing the toner remaining on the photoreceptor.

  Conventionally, fine particles having an average primary particle size of several nanometers to several tens of nanometers have been used as external additives for toners, and they are hydrophobized from the viewpoints of imparting chargeability, imparting fluidity, imparting hydrophobicity, etc. Silica fine particles that have been treated are used, and hydrophobized surface-treated titanium oxide is generally used from the standpoints of maintaining chargeability under temperature and humidity environment conditions and suppressing fluctuations in retained charge. Has been.

By using a plurality of external additives as described above and adjusting the addition ratio, stability and performance in the electrophotographic process are improved.
For example, a toner including toner base particles and an external additive containing non-spherical amorphous silica particles (major axis: 40 to 180 nm) is known (see Patent Document 1). In the example of Patent Document 1, an example in which hydrophobic titanium, hydrophobic silica, and non-spherical silica are used in combination as external additives is shown. According to such a toner, the rolling phenomenon of the external additive on the surface of the toner base particles and the burying of the external additive due to external stress can be prevented, and excellent cleaning can be achieved even with a small amount of external additive. Property, image quality, and durability.
Further, there is known an image forming toner in which the specific surface area of toner particles after externally adding hydrophobic fine powder to toner base particles is defined (see Patent Document 2). In the example of Patent Document 2, an example in which hydrophobic silica alone or a combination of hydrophobic silica and hydrophobic titanium is used as an external additive is shown. According to such a toner, the external additive is not buried due to the stirring of the developer at the time of use, and there is little change in fluidity and charging characteristics, and good transferability and cleaning properties are maintained for a long period of time. Is prevented, and there is no fluctuation such as image unevenness.
There is also known an electrostatic charge developing toner in which a residual alcohol component in a toner including a structure in which a crystalline polyester resin and a release agent are in contact is defined (see Patent Document 3). According to this toner, a decrease in the charge amount after being left in a high-temperature and high-humidity environment is suppressed, and the fixability is also improved.
Further, a toner is known that includes organic particles having pores on the surface of colored particles (toner base particles) (see Patent Document 4). According to the toner described in Patent Document 4, image deterioration is suppressed, and the life of the image forming apparatus and the developer is extended.

However, with the addition of various characteristics of the toner base particles that are taken in order to cope with the high performance, high speed, long life, etc. required in recent image formation, the conventional external additive adhesion method remains as it is. There is an increased possibility of defects, and there is a need for the development of new response technologies.
When designing a toner based on the conventional technology as described above, for example, a method of increasing the amount of wax added in the toner in order to work efficiently at the time of fixing, a method of arranging the wax near the surface of the toner base particles Or, in order to reduce the energy at the time of fixing, when using a method that encapsulates a crystalline material and lowers the energy at the time of fixing and melting, it becomes susceptible to the heat etc. accompanying the external pressure and environment, In some cases, a phenomenon that wax exudes on the surface of the photoconductor or a residual trace component (for example, a low molecular alcohol component) at the time of manufacture oozes out on the surface of the photoconductor. In addition, a toner component (for example, resin, external additive, wax, etc.) that should not remain essentially adheres to the surface of the photoreceptor and grows with time, and this causes an adverse effect on the image, or Irregularities due to minute residues are generated on the surface of the photoreceptor. Due to the adhesion of the toner component, for example, a cleaning blade that is physically in contact with the toner component may be lifted or a defect may be caused in the blade edge portion, thereby causing problems such as a reduction in cleaning performance. Alternatively, adhesion and remaining on the surface of the photoconductor may cause subtle unevenness and image defects on the output image.
In recent years, there has been a strong demand for low power consumption of electrophotographic equipment from the viewpoint of environmental considerations. To reduce power used in fixing units that consume particularly high power, that is, to ensure fixing performance at low temperatures, toner base particles The base resin itself tends to use a material that is soft or very sensitive to temperature, and this tends to decrease durability against external pressure during toner storage. That is, when designing the toner by the conventional technique as described above, the toner is easily affected by the external pressure, the heat associated with the environment, and the like, and the durability is lowered with respect to the external pressure during storage of the toner. . A decrease in the durability of the base particles with respect to the physical external pressure leads to exudation of the contained release agent component, which makes toner design difficult.
In addition to the content in the toner particles, the location of the release agent is important. Considering the fixing performance, the release agent is preferably present in the vicinity of the toner particle surface. On the other hand, the release agent exudes due to external stress. In view of the above, it is preferable that the toner particles are present in the deeper layer of the toner particles than in the vicinity of the toner surface. In consideration of the fixing property of the recording medium (paper, other recording materials), it is preferable that the content of the release agent is increased and the toner particles are uniformly present on the entire surface without being biased to a part of the toner particle surface. However, this requirement has conflicting properties such that it is difficult to increase the amount of the release agent in view of the safety in the toner design, which makes it difficult to produce toner particles.
In addition, when toner base particles are granulated (polymerized toner) using a chemical process (method using an oil phase / water phase), it is necessary to select a release agent that can be used in the chemical process. However, the design freedom of the toner base particles is limited.

  The present invention has been made in view of the above prior art, and an object of the present invention is to provide a toner having improved flexibility in designing toner base particles and improved fixing performance, heat resistant storage stability and image quality.

As a result of diligent investigations, the present inventors have determined that a release agent component is supported by external additive particles covering the toner surface rather than depending on the release performance of the toner base particles. The present inventors have found that the release agent component oozes out on the toner surface only when the temperature at which the toner melts is given, and can avoid the conventional problems.
That is, the above-described problem is a toner including toner base particles containing a binder resin and a colorant and an external additive that covers the surface of the toner base particles, and the external additive has a melting point of at least 60 ° C. or more. This is solved by a toner characterized by having release agent-containing porous particles containing a mold agent inside the porous pores.

  According to the present invention, it is possible to provide a toner having an increased design flexibility of toner base particles and improved fixing performance, heat resistant storage stability and image quality.

FIG. 2 is a schematic diagram illustrating a configuration example of a process cartridge that is detachable from an image forming apparatus main body.

  As described above, the toner in the present invention is a toner including toner base particles containing a binder resin and a colorant and an external additive that covers the surface of the toner base particles, and has at least a melting point as the external additive. It is characterized by having release agent-containing porous particles containing a release agent at 60 ° C. or higher inside the porous pores.

  With the toner configuration of the present invention, the release agent is freed from the conventional problems (the amount of the release agent present in the toner base particles, the control of the position of the release agent, etc.), and in the external addition step of the release agent-containing porous particles. Can be accurately controlled, and the position of the release agent coincides with the position of the release agent-containing porous particles, so that the release agent can be uniformly present on the entire surface of the toner base. . That is, it does not depend on the release performance of the toner base particles (for example, the release agent component and the amount added), but porous particles (particularly hard porous particles that do not have large deformability due to physical external pressure). By covering the toner surface with a release agent-containing porous particle in which a release agent component having a melting point of 60 ° C. or higher is supported inside the pores, the release agent component does not easily bleed out even when external pressure is applied, Only when a temperature at which the release agent melts (liquefies) is given, a state in which the release agent component appears on the toner surface can be created. As a result, the degree of freedom in designing the toner base particles is increased, and the fixing performance (for example, cold offset property, hot offset property, etc.), heat resistant storage property, and image quality are maintained in a well-balanced manner. If the toner of the present invention is used in an electrophotographic process such as an electrophotographic apparatus or an electrostatic recording apparatus, an image having no transfer failure, a ground image, etc. is suppressed, and an image having excellent image graininess and sharpness is long-term. Over a stable range.

Next, the best mode for carrying out the present invention will be described.
As described above, the present invention comprises a toner base particle containing a binder resin and a colorant and a release agent-containing porous particle as an external additive. In addition, a release agent, a charge control agent, and the like may be contained. The toner configuration of the present invention will be described below. In the present invention, the “toner base particles” may be referred to as “colored particles”.
[External additive]
<Releasing agent-containing porous particles>
In the present invention, the release agent contained in the release agent-containing porous particles has a melting point of 60 ° C. or higher. Most preferably, it is 60 degreeC or more and 85 degrees C or less. If the melting point is less than 60 ° C., blocking tends to occur when the toner is stored, and heat resistant storage stability may be reduced. If the melting point exceeds 85 ° C., the low-temperature fixability tends to be impaired.
Here, the melting point is the temperature of the endothermic peak at which the endothermic amount is maximized (referred to as “maximum endothermic peak temperature”) in a differential heat curve obtained by differential scanning calorimetry (DSC).

The release agent used in the production of the release agent-containing porous particles is not particularly limited, but plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, ozokerite, Mineral waxes such as cercin, petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene wax, synthetic waxes such as esters, ketones, ethers, etc. You may use together.
Other release agents include 12-hydroxy stearamide, stearamide, phthalic anhydride, fatty acid amides such as chlorinated hydrocarbons, polyacrylates such as poly n-stearyl methacrylate and poly n-lauryl methacrylate. Examples include a low molecular weight crystalline polymer such as a homopolymer or a copolymer (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate), a crystalline polymer having a long-chain alkyl group in the side chain, and the like. .

  As the porous particles having porous pores of the core material constituting the release agent-containing porous particles (hereinafter sometimes referred to as “release agent-containing porous body” or “porous body”), The material is not limited as long as it has resistance to physical external pressure and the release agent component contained therein is difficult to bleed out even when external pressure is applied, but the hard particles, especially porous particles made of inorganic materials, preferable. Examples of such organic material particles include silica particles, hydroxyapatite particles, hydrotalcite particles, and the like.

For such a porous body, for example, porous silica particles (Nippon Aerosil: AEROPERL 300/30) are selected as the core material of the porous body, and carnauba wax (carnauba wax C1 made by Kato Yoko) is selected as the release agent. When it does, it can manufacture as follows.
AEROPERL 300/30 is put into the melt of carnauba wax C1, and the pressure is reduced while keeping the temperature in a molten state. Ensure that the release agent component is sufficiently impregnated inside the pores of the material. In this impregnation step, it is preferable to control the amount of the carnauba wax C1 adhering to the surface portion of the porous silica particles as much as possible, and to control the carnauba wax C1 so as to be impregnated therein as much as possible. That is, the weight ratio of AEROPERL 300/30 and the carnauba wax C1 melt to be added is preferably 10: 1 to 3: 1.

Since the porous particles encapsulating the carnauba wax obtained as described above are in a slightly aggregated attached state, it is necessary to crush to the primary particle level (average particle size of about 100 nm). Such crushing can be performed using, for example, a scramjet mill (MN-30 manufactured by Tokuju Factory).
The scramjet mill can perform nano-level ultrafine grinding by collision of particles using high-pressure gas. Since the crushing nozzles are arranged at positions equally divided in the circumference inside the cylindrical mill, and one or more of them are the raw material supply nozzles, concentric vortices can be created. Since the concentric swirl vortex can be formed inside the mill by the high-pressure jet stream, the scram jet is characterized by a sharp particle size distribution. In addition, since the scramjet uses interparticle collisions, there are few particle collisions with the mill wall surface. Therefore, a fine powder obtained by pulverization using a scramjet is preferable because it has low contamination due to the mill wall surface being scraped. In addition, when there is a possibility that the release agent component remains on the particle surface as described above, since a light mutual polishing effect is exhibited on the particle surface, the effect of removing the release agent remaining on the porous particle surface is also obtained. Obtained at the same time.

<Other external additives other than release agent-containing porous particles>
The external additive in the toner of the present invention includes release agent-containing porous particles containing at least a release agent having a melting point of 60 ° C. or more inside the porous pores, but may contain other external additives. Absent. Examples of such external additives include silicon oxide (silica) and titanium oxide. Hydrophobic silica and hydrophobic titanium oxide that have been subjected to hydrophobic treatment are particularly preferably used. Specific examples thereof include, for example, hydrophobic silica treated with hexamethyldisilazane, rutile-type titanium oxide subjected to hydrophobic treatment with isobutyl, and the like.
Here, the hydrophobic silica is not limited, but has functions such as imparting charging property, imparting fluidity, imparting hydrophobicity, etc., and fine particles having an average primary particle size of about 8 nm to 120 nm are preferably used. It is done. The external addition amount [content (weight ratio)] of the hydrophobic silica is preferably 0.5% by weight to 8% by weight with respect to the total amount of the toner base particles. When the amount is less than 0.5% by weight, there are problems such as a decrease in toner fluidity and a decrease in chargeability, and a tendency to easily cause a change in environment, particularly a decrease in charge under high humidity conditions. On the other hand, when the amount exceeds 8% by weight, the silica not adhering to the surface of the toner base is likely to be liberated, and the liberated silica adheres to the carrier surface and inhibits the charge imparting function or adheres firmly to the surface of the photoreceptor. Such a phenomenon as so-called silica filming may be caused.
Hydrophobic titanium oxide is not limited, but has functions such as maintaining chargeability under temperature / humidity environmental conditions and suppressing variation in retained charge amount. The average primary particle size is about 12 nm to 55 nm. These fine particles are preferably used. The external addition amount [content (weight ratio)] of the hydrophobic titanium oxide is preferably 0.2% by weight to 5% by weight with respect to the total amount of the toner base particles. If it is less than 0.2% by weight, the function of suppressing the difference in charge amount under different environmental conditions expected for titanium oxide will not be exhibited, and there will be a problem in the stability of the output image, particularly the image density. When the amount exceeds 5% by weight, excessive addition causes a phenomenon such as a decrease in toner resistance, a decrease in charge amount, and a broadening of the charge amount distribution, and the toner is scattered on the white paper portion and the image density is not stable. This causes a problem.

In order to improve the fluidity, storage stability, developability, and transferability of the toner, a general powder mixer may be used when an external additive is added to and mixed with the toner base particles (colored particles). However, it is preferable to adjust the internal temperature by installing a jacket or the like. In order to change the load history applied to the external additive, the external additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Also, a strong load may be given first, then a relatively weak load, or vice versa. Examples of the mixer include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, and a Henschel mixer.
As described above, the content (weight ratio) of the release agent-containing porous particles is preferably 2% or more and 10% or less with respect to the total amount of the toner base particles. If the content (weight ratio) of the release agent-containing porous particles is less than 2%, a sufficient release effect cannot be obtained, and if it exceeds 10%, filming on the surface of the photoreceptor and deterioration of storage characteristics at high temperatures are caused. In some cases, system problems other than image characteristics such as aggregation of the developer in the developing device are easily manifested.

[Toner base particles]
The toner base particles in the present invention are formed by a pulverization method, an emulsion polymerization method in which an oil phase is emulsified, suspended, or aggregated in an aqueous medium to form particles, a suspension polymerization method, a polymer suspension method, or the like. That is, toner base particles obtained by pulverizing and classifying a melt-kneaded product obtained by charging a mixture containing a toner component in a melt-kneader, or toner components [for example, binder resin and / or Or a toner material liquid (oil phase) in which a toner material containing a binder resin precursor and a colorant (if necessary, a toner material containing a release agent) is dissolved or dispersed in an organic solvent is contained in an aqueous medium (aqueous phase). After being emulsified or dispersed by using a method, it is possible to use those formed by removing the solvent. In the present invention, the “toner material” may be referred to as a “toner composition”.

<Binder resin>
The binder resin contained in the toner base particles constituting the toner of the present invention is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, homopolymers of styrene such as polystyrene, poly (p-chlorostyrene), polyvinyltoluene and the like, and substituted products thereof, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer Styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-methacrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate Copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene- Isoprene copolymer, styrene-male Styrene copolymer such as acid ester copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polyester, polyurethane, epoxy resin, polyvinyl butyral, polyacrylic acid, rosin, modified A rosin, a terpene resin, a phenol resin, an aliphatic or aromatic hydrocarbon resin, an aromatic petroleum resin and the like can be mentioned, and these can be used alone or in combination.
Among the binder resins, polyester is preferable. The binder resin may be derived from a binder resin precursor, and a binder resin precursor capable of producing a modified polyester containing an ester bond and a bond unit other than the ester bond is preferably used. As the resin precursor capable of producing such a modified polyester, those containing a compound having an active hydrogen group and a polyester having a functional group capable of reacting with the active hydrogen group of the compound can be preferably used. Examples of the modified polyester include those containing an ester bond and a urea bond. That is, as a binder resin and / or a binder resin precursor, unmodified polyester, a modified polyester containing an ester bond and a bond unit other than the ester bond, or a resin precursor capable of producing the modified polyester, and a crystalline polyester A resin material selected from is preferably used.

(Unmodified polyester)
As the binder resin, a so-called unmodified polyester (unmodified polyester) that does not contain a bond unit other than an ester bond can be used.
And such an unmodified polyester, a binder resin precursor having the ester bond, a modified polyester containing an ester bond and a bond unit other than the ester bond, or a resin precursor capable of producing the modified polyester, and a crystal A binder resin (toner binder) component can be formed by combining a reactive polyester. For example, unmodified polyester and modified polyester (for example, urea-modified polyester) can be contained as a toner binder component.
By using the unmodified polyester together with the modified polyester, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to using the modified polyester alone. The modified polyester and unmodified polyester are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, the polyester component constituting the modified polyester and the component constituting the unmodified polyester are preferably similar.

(Modified polyester)
The modified polyester contains at least an ester bond and a bond unit other than the ester bond in the molecular structure. Such a modified polyester is obtained by reaction of a so-called resin precursor capable of producing a modified polyester, which contains a compound having an active hydrogen group and a polyester having a functional group capable of reacting with the active hydrogen group of the compound. Can do.
Examples of the polyester having a functional group capable of reacting with an active hydrogen group include a polyester prepolymer having an isocyanate group or an epoxy group. A polyester having a functional group capable of reacting with such an active hydrogen group is easily synthesized by reacting a conventionally known isocyanate agent or epoxidizing agent (a compound having an isocyanate group or an epoxy group) with the base polyester. can do.
For example, if a modified polyester (modified polyester containing an ester bond and a urea bond) obtained by subjecting a polyester having an isocyanate group (polyester prepolymer) to an elongation reaction with a compound having an active hydrogen group (such as amines) is included in the binder resin, The difference between the minimum fixing temperature and the hot offset occurrence temperature can be widened, and the effect of improving the mold release width is also exerted. In addition, by coexisting urea-modified polyester as the modified polyester, the toner having the toner base particles of the present invention has good heat-resistant storage stability even when the glass transition point is low as compared with known polyester-based toners. Show the trend.

  As the isocyanate agent, as described later, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurates; the polyisocyanate was blocked with a phenol derivative, oxime, caprolactam, etc. And a combination of two or more of these. Moreover, epichlorohydrin etc. can be mentioned as the representative example as an epoxidizing agent.

(Crystalline polyester)
As described above, a crystalline polyester can be contained as a binder resin having an ester bond of the base particles constituting the toner of the present invention.
The crystalline polyester is obtained by reaction of an alcohol component and an acid component, and is a polyester having at least a melting point. Examples of the crystalline polyester include, but are not limited to, for example, saturated aliphatic diol compounds having 2 to 12 carbon atoms, particularly 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, Alcohol component selected from 1,10-decanediol and 1,12-dodecanediol or derivatives thereof, and a dicarboxylic acid having 2 to 12 carbon atoms having a double bond (C = C bond), or carbon number 2-12 saturated dicarboxylic acids, especially fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, and 1,12-dodecane Crystalline polyesters synthesized by reaction with dicarboxylic acid components selected from diacids or their derivatives are preferred.
By using crystalline polyester, for example, while maintaining the releasability function at the time of fixing without deteriorating, the problem of contamination of the carrier and charging member due to the wax existing on the surface of the toner having the base particles is suppressed. Results.

As the dispersed particle diameter of the crystalline polyester in the toner base particles, the ratio of the major axis diameter to the minor axis diameter is preferably 3 or more, and the major axis diameter is preferably 0.2 μm or more and 3.0 μm or less. When the major axis diameter / minor axis diameter ratio is less than 3 and the particle diameter is less than 0.2 μm, the crystallinity is hardly exhibited and the effect of low-temperature fixing is hardly obtained, and the effect of imparting charging may not be sufficiently obtained. On the other hand, if the crystal diameter is too large and exceeds 3.0 μm, the shape of the toner is greatly distorted and pulverized inside the machine. In addition, it tends to come out on the toner surface, and in extreme cases, it exists independently outside the toner. Due to the deterioration of the surface properties of the toner, the carrier can be contaminated and sufficient chargeability cannot be maintained for a long time. There is a risk of impairing environmental stability, such as contamination of machine parts.
Moreover, it is preferable that the endothermic peak temperature measured by the differential scanning calorimetry (DSC) of the said crystalline polyester is 50 degreeC or more and 150 degrees C or less.
When the endothermic peak temperature is less than 50 ° C., the toner aggregates during high-temperature storage, heat resistant storage stability deteriorates, and blocking tends to occur at the temperature inside the developing device. On the other hand, when the endothermic peak temperature exceeds 150 ° C., the fixing lower limit temperature becomes high, so that the low temperature fixability cannot be obtained.
The content of the crystalline polyester is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the base particles. When the content is less than 1 part by weight, the low-temperature fixing effect may not be sufficiently obtained. When the content exceeds 30 parts by weight, the amount of crystalline polyester present on the outermost surface of the toner is too large, so that the photosensitive member. In addition, the image quality may be deteriorated due to contamination of other members, the fluidity of the developer may be lowered, and the image density may be lowered. Further, the surface property of the toner is deteriorated, the carrier is contaminated and sufficient chargeability cannot be maintained for a long time, and further, environmental stability may be hindered.

[Colorant]
The colorant used as the toner material in the present invention is not particularly limited and can be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), Cadmium yellow, Yellow iron oxide, Ocher, Yellow lead, Titanium yellow, Polyazo yellow, Oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, cadmium mercury red, antimony , Permanent Red 4R, Para Red, Physe Red, p-Chloro-o-Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkans Fast Rubin B, Brilliant Scarlet G, Resol 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 Light Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigolet B, Thioindigo Maroon, Oil Red, 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, None Metal 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, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Lithbon and the like can be used, and these can be used alone or in combination.

The content of the colorant in the toner base particles (colored particles) is preferably 1 to 15% by weight, and more preferably 3 to 10% by weight.
The colorant may be used as a master batch combined with a resin. The resin used in the masterbatch is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, a homopolymer of styrene or a substituted product thereof, a styrene copolymer, or polymethyl methacrylate , Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid, rosin, modified rosin, terpene resin, aliphatic hydrocarbon Resins, alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffins and the like can be mentioned, and these can be used alone or in combination.

[Release agent]
As the toner material of the toner base particles, a release agent can be used as necessary, and is not particularly limited and can be appropriately selected from known ones according to the purpose. In the toner of the present invention, since the release agent-containing porous particles are externally added to the surface of the toner base particles, the degree of freedom in designing the toner base particles is increased, and the release agent content in the toner base particles is minimized. The fixing performance (cold offset property, hot offset property, etc.), heat resistant storage stability and image quality are effectively improved in a balanced manner.
Examples of the release agent used for the toner base particles include those mentioned above as the release agent used for producing the release agent-containing porous particles.

[Charge control agent]
As the toner material constituting the toner base particles, a charge control agent can be used as necessary. 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 (product number: T-2, 004) (above, Nippon Kayaku Co., Ltd.)), Eisenspiron black (T-37, T-77, T-95, TRH, TNS-2) (above, Hodogaya Chemical Industry Co., Ltd.), FCA-1001-N, FCA-1001-NB, FCA-1001-NZ (manufactured by Fujikura Kasei Co., Ltd.) and the like can be used alone or in combination.
As the positive charge control agent, for example, basic compounds such as nigrosine dyes, cationic compounds such as quaternary ammonium salts, metal salts of higher fatty acids, and the like can be used. 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 (part numbers: 1001, 2001, 6001, 7001) (above, manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like. can do.

  The amount of addition of the charge control agent is determined by the method of producing the colored particles including the type of the binder resin and the dispersion method, and is not uniquely limited. 0.1 to 10% by weight, preferably 0.2 to 5% by weight. When the addition amount exceeds 10% by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, the image The concentration may decrease. On the other hand, if the addition amount is less than 0.1% by weight, the charge rising property and the charge amount are not sufficient, and the toner image may be easily affected.

[Method for producing toner base particles]
The production method of the toner base particles (colored particles) can be appropriately selected according to the purpose. Specific methods include (I): pulverization method, (II): emulsification of oil phase in aqueous medium ( (Emulsion polymerization method), suspension polymerization, aggregation, emulsion polymerization method for forming colored particles, suspension polymerization method, polymer suspension method and the like. The production method (II) is preferably used to obtain spherical colored particles having a controlled particle size distribution.

[Crushing method (I)]
When toner base particles (colored particles) are obtained by the pulverization method (I), first, a mixture in which toner materials constituting the colored particles are mixed is charged into a melt kneader and melt kneaded.
As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. Specifically, a KTK type twin screw extruder (Kobe Steel Co., Ltd.), a TEM type extruder (Toshiba Machine Co., Ltd.), a twin screw extruder (Cay Kay), a PCM type twin screw extruder (Ikegai Iron Works) And Kneader (manufactured by Busus). The melt kneading is preferably performed under appropriate conditions so that the molecular chain of the binder resin is not broken. Specifically, if the melt-kneading temperature is too high above the softening point of the binder resin, cutting may become severe, and if it is too low, melt-kneading may not proceed.
Next, the kneaded material obtained by melt kneading is pulverized. When the kneaded product is pulverized, it is preferable that the kneaded product is coarsely pulverized and then finely pulverized. Specifically, a method of pulverizing by colliding with a collision plate in a jet stream, a method of pulverizing particles by colliding with each other in a jet stream, a method of pulverizing in a narrow gap between a mechanically rotating rotor and a stator, etc. It is preferable to use it.
Furthermore, the pulverized pulverized product is classified to adjust the particle size within a predetermined range. In classification, for example, fine particles are removed by a cyclone, a decanter, a centrifugal separator, or the like. Furthermore, colored particles are obtained by removing coarse particles and aggregated particles using a sieve of 250 mesh or more.

[Polymerization method (II)]
When toner base particles (colored particles) are obtained by the polymerization method (II), for example, a toner material containing a binder resin and / or a binder resin precursor and a colorant (if necessary, a release agent) is used as an organic solvent. The base particles are obtained through a step of preparing a toner material liquid (oil phase) by dissolving or dispersing in an aqueous solution and a step of emulsifying or dispersing the oil phase in an aqueous medium (aqueous phase) and then removing the solvent.
In the present invention, the colored particles contain a compound having an active hydrogen group in an organic solvent and a polyester having a functional group capable of reacting with the active hydrogen group of the compound (hereinafter referred to as prepolymer (A)). Obtained by reacting a compound having an active hydrogen group with a prepolymer (A) after dispersing a solution or dispersion obtained by dissolving or dispersing a product in an aqueous medium containing resin particles. Is preferred.

[Toner Production Method]
Using the toner base particle surface obtained in (I) or (II) as an external additive, a release agent-containing porous particle containing at least a release agent having a melting point of 60 ° C. or more inside the porous pores. As described in the external additive, the toner of the present invention is produced by coating with a mixer (for example, a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, etc.). The As the external additive, other external additives such as hydrophobic silica and hydrophobic titanium oxide are coated as necessary.

In the present invention, the toner base particles preferably have a volume average particle diameter (Dv) of 3.0 μm or more and less than 6.0 μm.
The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner base particles is preferably 1.05 or more and 1.25 or less.
When the volume average particle diameter (Dv) is smaller than 3.0 μm, it is disadvantageous for transferability and cleaning property. When the volume average particle diameter is smaller than the range of the present invention, in the case of a two-component developer (consisting of toner and carrier), the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is lowered When used as a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. On the other hand, when the volume average particle diameter (Dv) of the toner base particles is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image and the balance of the toner in the developer is reduced. In many cases, the toner particle size fluctuates greatly.
The same applies when the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is larger than 1.25. Further, when Dv / Dn is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount, but the toner cannot be sufficiently charged or the cleaning property is improved. May worsen.

  Here, as the toner material (toner composition), a compound having an active hydrogen group and a polyester having a functional group capable of reacting with the active hydrogen group of the compound [sometimes referred to as prepolymer (A). The toner production method will be described by taking as an example the case where toner base particles (colored particles) are formed using a resin precursor containing a resin (a resin precursor capable of producing a modified polyester).

  The prepolymer (A) is obtained by further reacting a polyester resin (polyester resin having an active hydrogen group) comprising a polycondensate of the polyol (1) and the polycarboxylic acid (2) with the polyisocyanate (3). be able to. Examples of the active hydrogen group include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like, and an alcoholic hydroxyl group is preferable.

  Examples of the polyol (1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F) 4,4′-dihydroxybiphenyls such as bisphenol S, 3,3′-difluoro-4,4′-dihydroxybiphenyl; bis (3-fluoro-4-hydroxypheny ) Methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5 -Difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), bis (hydroxy) such as 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Phenyl) alkanes; Bis (4-hydroxyphenyl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether, etc .; Alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) addition of the above alicyclic diols Products; alkylene oxides of the above bisphenols (ethylene oxide, pro For example, alkylene oxides of 2 to 12 carbon atoms and alkylene oxides of bisphenols, particularly preferred are alkylene oxides of bisphenols. The adduct is used in combination with an alkylene glycol having 2 to 12 carbon atoms.

Further, as the trivalent or higher polyol (1), a trivalent or higher polyhydric aliphatic alcohol (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (trisphenol PA) , Phenol novolac, cresol novolac, etc.); alkylene oxide adducts of the above-mentioned trihydric or higher polyphenols.
In addition, the said polyol can be individual or can use 2 or more types together, and is not limited above.

  Examples of the polycarboxylic acid (2) 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, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5 -Trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoro Propane, 2,2'-bis (trifluoromethyl) -4,4'- Phenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl) -3,3′-biphenyldicarboxylic acid, hexafluoroisopropylidene Dendiphthalic anhydride, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

Furthermore, as polycarboxylic acids having 3 or more valences, aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), anhydrides of the above aromatic polycarboxylic acids, lower alkyl esters (methyl esters) , Ethyl ester, isopropyl ester, etc.).
In addition, the said polycarboxylic acid can be used individually or in combination of 2 or more types, It is not limited to the above.

  Regarding the ratio of the polyol (1) and the polycarboxylic acid (2) when synthesizing the polyester resin, the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH] is usually 2/1. To 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1.

  The peak molecular weight of the polyester resin is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. When the peak molecular weight is less than 1000, the heat resistant storage stability may be lowered, and when it exceeds 10,000, the low-temperature fixability may be lowered.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates, phenol derivatives, oximes, caprolactam, etc. May be blocked. In addition, these can use 2 or more types together.

  Regarding the ratio of the polyisocyanate (3) and the polyester resin having an active hydrogen group when synthesizing the prepolymer (A), the equivalent ratio [NCO] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester resin having a hydroxyl group is used. ] / [OH] is usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1, and more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, the low-temperature fixability may be deteriorated. When it is less than 1, the content of urethane groups and / or urea groups in the modified polyester resin is decreased, and offset resistance is reduced. May decrease.

The content of the component derived from polyisocyanate (3) in the prepolymer (A) is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. %. When the content is less than 0.5% by weight, the offset resistance may be lowered, and when it exceeds 40% by weight, the low-temperature fixability may be lowered.
The number of isocyanate groups per molecule of the prepolymer (A) is usually 1 or more, preferably 1.5 to 3, more preferably 1.8 to 2.5. When the number of isocyanate groups is less than 1, the molecular weight of the modified polyester resin is lowered, and offset resistance may be lowered.

  In the present invention, amines (B) can be used as the compound having an active hydrogen group capable of reacting with the prepolymer (A) (elongating agent and / or crosslinking agent). As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), amino group blocked B1 to B5 (B6) Etc.

Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.); alicyclic diamines ( 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, isophoronediamine, etc .; aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododecylene) Amine) and the like.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetraamine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of B1 to B5 (B6) in which an amino group is blocked include B1 to B5 and ketimine compounds and oxazoline compounds obtained from ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

  Furthermore, a terminator can be used in the extension reaction and / or the cross-linking reaction as necessary, and the molecular weight of the modified polyester resin can be adjusted. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking these (ketimine compounds).

  Regarding the ratio of the prepolymer (A) to the amines (B) when the prepolymer (A) and the amines (B) are reacted, the isocyanate group [NCO] of the prepolymer (A) and the amines (B) The equivalent ratio [NCO] / [NHx] of the amino group [NHx] is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1 2/1 to 1 / 1.2. When [NCO] / [NHx] is larger than 2 or smaller than 1/2, the molecular weight of the resulting modified polyester resin is decreased, and the hot offset resistance may be lowered.

  The organic solvent in which the toner material (toner composition) is dissolved or dispersed is preferably volatile with a boiling point of less than 100 ° C., since it can be easily removed later. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Examples include ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. These can be used alone or in combination of two or more. Particularly preferred are ester solvents such as methyl acetate and ethyl acetate, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride. The toner composition may be dissolved or dispersed at the same time, but is usually dissolved or dispersed independently, and the organic solvents used at that time may be different or the same, but considering the subsequent solvent treatment, Is preferred.

  The toner composition solution or dispersion [toner material liquid (oil phase)] preferably has a resin concentration of 40 to 80% by weight. When the resin concentration exceeds 80% by weight, it becomes difficult to dissolve or disperse and the viscosity becomes high and it is difficult to handle. On the other hand, if it is less than 40% by weight, the amount of toner produced is reduced. When mixing the polyester resin and the prepolymer, they may be mixed in the same solution or dispersion, or may be prepared separately, but considering the solubility and viscosity of each, separate dissolution Alternatively, it is preferable to prepare a dispersion.

  The colorant may be dissolved or dispersed alone, or may be mixed in a polyester resin solution or dispersion. If necessary, a dispersion aid or a polyester resin may be added, or a master batch may be used.

  As an aqueous medium (aqueous phase), water alone may be used, but a solvent miscible with water may be used in combination. Examples of the solvent miscible with water include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like. The amount of the aqueous medium used relative to 100 parts by weight of the toner composition is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. When the amount of the aqueous medium used is less than 50 parts by weight, the dispersion state of the toner composition may be deteriorated. Moreover, when it exceeds 2000 weight part, it is not economical.

When the toner composition solution or dispersion is dispersed in the aqueous medium, it is preferable to disperse the inorganic dispersant or the resin particles in the aqueous medium in advance. Thereby, the particle size distribution can be narrowed and stably dispersed.
As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used.
Further, as the resin forming the resin particles, any resin can be used as long as it can form an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin, For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like can be mentioned. These resins may be used in combination of two or more. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles can be easily obtained.

Although the method of manufacturing the aqueous dispersion of resin particles is not particularly limited, the following (a) to (h) can be mentioned.
(A) In the case of a vinyl resin, an aqueous dispersion of resin particles is directly produced by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method using a monomer as a starting material.
(B) In the case of a polyaddition or condensation resin such as a polyester resin, a polyurethane resin, and an epoxy resin, a precursor (monomer, oligomer, etc.) or a solution thereof is dispersed in an aqueous medium in the presence of a suitable dispersant, After that, the resin particles are cured by heating or adding a curing agent to produce an aqueous dispersion of resin particles.
(C) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it is preferably a precursor (monomer, oligomer, etc.) or a solution thereof (liquid). ) After a suitable emulsifier is dissolved therein, water is added to carry out phase inversion emulsification.
(D) Resin produced in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) After pulverizing and classifying using a fine pulverizer, resin particles are obtained, and then dispersed in water in the presence of an appropriate dispersant.
(E) A resin solution prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is sprayed in the form of a mist. Thus, the resin particles are obtained and then dispersed in water in the presence of a suitable dispersant.
(F) A resin solution obtained by dissolving a resin prepared in advance in a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. The resin particles are precipitated by adding a solvent or by cooling a resin solution previously dissolved in a solvent by heating, and after removing the solvent to obtain resin particles, in a water-based medium in the presence of an appropriate dispersant. Disperse.
(G) A resin solution prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is used as an appropriate dispersant. After the dispersion in an aqueous medium, the solvent is removed by heating, decompression or the like.
(H) An appropriate emulsifier is added to a resin solution prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.). After dissolving, water is added and phase inversion emulsified.

  In addition, a surfactant or the like may be used as necessary in order to emulsify and disperse the toner composition solution or dispersion in an aqueous medium. Surfactants include alkylbenzene sulfonate, α-olefin sulfonate, anionic surfactants such as phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, alkyl Quaternary ammonium salt type cationic surfactants such as trimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol derivative, etc. Nonionic surfactants such as alanine, dodecyl bis (aminoethyl) glycine, bis (octylaminoethyl) glycine, and N-alkyl-N, N-dimethylammonium betaine.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be increased in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, perfluorooctanesulfonyl glutamate disodium, 3- [ω-fluoroalkyl (C6 to C11) oxy. ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid and Its metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2 -Hydroxyethyl) perfluorooctane Sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. . Further, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, etc. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

  Further, the dispersed droplets may be stabilized by a polymer protective colloid. Polymeric protective colloids include acids (acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, etc.); (Meth) acrylic monomer (β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxy methacrylate) Propyl, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylol acetate Rilamide, N-methylol methacrylamide, etc.); vinyl alcohol or ethers with vinyl alcohol (vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc.); esters of vinyl alcohol and compounds containing a carboxyl group (vinyl acetate, Vinyl propionate, vinyl butyrate, etc.); acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds; acid chlorides (acrylic acid chloride, methacrylic acid chloride, etc.); those having a nitrogen atom or its heterocyclic ring ( Homopolymers or copolymers such as vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, etc .; polyoxyethylenes (polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxy) Propylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl ester, etc.); celluloses (methyl cellulose) , Hydroxyethyl cellulose, hydroxypropyl cellulose, etc.) can be used.

  In addition, when using a compound that can be dissolved in an acid or alkali such as calcium phosphate salt as the dispersion stabilizer, the calcium phosphate salt is dissolved from the colored particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Can be removed. In addition, it can be removed by an operation such as enzymatic degradation. When a dispersant is used, it can be used in a state where the dispersant remains on the surface of the colored particles, but it is preferable to remove it by washing from the charged surface of the toner.

  The dispersion method is not particularly limited, and known methods such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the average particle size of the dispersion 2 to 20 μm, a high-speed shearing method is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1000 to 30000 rpm, and preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature at the time of dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method of gradually raising the temperature of the whole system under normal pressure or reduced pressure and evaporating and removing the organic solvent in the droplets can be employed. It is also possible to spray the emulsified dispersion in a dry atmosphere to remove the organic solvent in the droplets and to evaporate and remove the surfactant. As the dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like can be used, but various airflows heated to a temperature equal to or higher than the boiling point of the organic solvent are generally used. . At this time, the processing time can be shortened by using a spray dryer, a belt dryer, a rotary kiln or the like.

  The amines (B) may be mixed in an organic solvent before dispersing the toner composition in the aqueous medium, or may be added to the aqueous medium. The time required for the reaction of the prepolymer (A) and the amines (B) is appropriately selected depending on the reactivity of the prepolymer (A) and the amines (B), but is usually 1 minute to 40 hours, preferably Is 1 to 24 hours. The reaction temperature is usually 0 to 150 ° C., preferably 20 to 98 ° C. In addition, a well-known catalyst can be used as needed.

  A known method is used for the step of washing and drying the colored particles dispersed in the aqueous medium. That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion-exchanged water at room temperature to about 40 ° C., and if necessary, pH adjusted with acid or alkali, The process of solid-liquid separation is repeated several times. Thereby, after removing impurities, surfactants and the like, colored particles are obtained by drying with an air flow dryer, a circulation dryer, a vacuum dryer, an oscillating fluid dryer or the like. At this time, the fine particle component may be removed by centrifugation or the like, and after drying, a desired particle size distribution can be obtained using a known classifier as necessary.

  The developer used in the image forming development step may be either a one-component developer composed of the toner of the present invention alone or a two-component developer composed of the toner of the present invention and a carrier. In the case of using in a high-speed printer or the like corresponding to the above, it is preferable to use a two-component developer from the viewpoint of life. The mixing ratio of the toner and the carrier in the two-component developer is preferably 1 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier.

  When toner is used as a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the particle size of the toner, and the member such as blades for filming the toner on the developing roller and thinning the toner The toner is not fused to the toner, and good and stable developability and image can be obtained even when the developing device is used for a long time (stirring). Further, in the case of the two-component developer using the toner of the present invention, even if the toner balance for a long period of time is performed, the fluctuation of the toner particle size in the developer is small, and it is good even for long-term stirring in the developing device. And stable developability can be obtained.

There is no restriction | limiting in particular in a carrier, Although it can select suitably according to the objective, It is preferable to have a core material and the resin layer which coat | covers a core material.
The core material is not particularly limited and can be appropriately selected from known materials. For example, 50 to 90 emu / g manganese-strontium (Mn-Sr) -based material, manganese-magnesium (Mn-Mg) A high-magnetization material such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) is preferable from the viewpoint of securing image density. In addition, it is possible to weaken the hitting of the toner that is in a spiked state to the photosensitive member, and it is advantageous for improving the image quality. The weakly magnetized material is preferred. These can be used individually or in mixture of 2 or more types.
The weight average particle diameter of the core material is preferably 10 to 200 μm, and more preferably 40 to 100 μm. When the weight average particle size is less than 10 μm, the fine powder component of the carrier increases, and the magnetization per particle may be lowered and carrier scattering may occur. When the weight average particle size exceeds 150 μm, the specific surface area decreases, and the toner May occur, and the reproducibility of the solid portion may be deteriorated particularly in a full color having many solid portions.

  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 resins Resin, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer weight of vinylidene fluoride and vinyl fluoride Examples thereof include fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride, and non-fluorinated monomers, silicone resins, and the like, which can be used alone or in combination of two or more.

  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, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. Examples of the polystyrene resin include polystyrene and styrene-acrylic copolymer. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester-based resin include polyethylene terephthalate and polybutylene terephthalate.

  You may add conductive powder etc. to a resin layer as needed. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle size of the conductive powder is preferably 1 μm or less. When the average particle size exceeds 1 μm, it may be difficult to control the electric resistance.

The resin layer is formed by, for example, preparing a coating solution by dissolving a silicone resin or the like in a solvent, then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. can do. Examples of the application method include a dipping method, a spray method, and a brush coating method.
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and butyl acetate.
The baking is not particularly limited and may be either an external heating method or an internal heating method. For example, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or the like, The method to use etc. are mentioned.

  The content of the resin layer in the carrier is preferably 0.01 to 5.0% by weight. If the content is less than 0.01% by weight, the resin layer may not be uniformly formed on the surface of the core material. If the content exceeds 5.0% by weight, the resin layer becomes too thick and the carriers are Granulation may occur.

  The developer 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. Further, the developer can be used in a form accommodated in a developer container.

  The image forming method includes a step of charging at least the surface of the image carrier, and a step of developing an electrostatic latent image formed on the charged image carrier using a developer including the toner of the present invention. A step of transferring a toner image formed on the image carrier to an image support (transfer medium), and fixing the heat and pressure of the transferred toner image by a roller-like or belt-like fixing member. And a step of obtaining a fixed image on an image support (transfer medium). Moreover, you may further have the other process suitably selected as needed, for example, a static elimination process, a cleaning process, a recycle process, a control process, etc. As a means for carrying out the image forming method, an image forming apparatus having at least an image carrier (photoconductor), a charging device, an exposure device, a developing device, a transfer device, and a fixing device is used. As other means appropriately selected as necessary, for example, a static eliminator, a cleaning device, a recycling device, a control device, and the like can be further included.

The process cartridge integrally supports the image carrier and at least the developing means for converting the electrostatic latent image formed on the image carrier into a visible image using the toner of the present invention, and is attached to and detached from the image forming apparatus main body. Freely configured. The process cartridge may further support other means appropriately selected as needed.
The schematic diagram of FIG. 1 shows a configuration example of a process cartridge that is detachable from the main body of the image forming apparatus. The process cartridge includes an image carrier (photosensitive member) 10 and includes a charging device 20, an exposure device 30, a developing device 40, a cleaning device 60, and a transfer device 80. These members can be the same as those used in the image forming apparatus described later.

Hereinafter, each process and means in the image forming apparatus will be described in more detail.
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the photoreceptor. The electrostatic latent image can be formed, for example, by applying a voltage to the surface of the photoconductor using a charging device and then charging the surface uniformly and then exposing the image like an image using an exposure device. it can.
The material, shape, structure, size and the like of the photoreceptor are not particularly limited and can be appropriately selected from known ones, but the shape is preferably a drum shape. Examples of the photoreceptor include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors (OPC) such as polysilane and phthalopolymethine. Amorphous silicon photoreceptors are preferable in terms of long life. .

The charging device is not particularly limited and can be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roll, brush, film, rubber blade, Examples thereof include a non-contact charger using corona discharge such as corotron and scorotron. The charging device is preferably arranged in contact or non-contact with the photoreceptor, and charges the surface of the photoreceptor by applying a DC voltage and an AC voltage in a superimposed manner.
The charging device is a charging roller that is disposed in close proximity to the photoconductor via a gap tape, and charges the surface of the photoconductor by applying a DC voltage and an AC voltage superimposed on the charging roller. Those that do are preferred.

  The exposure apparatus is not particularly limited as long as it can image-wise expose the surface of the photoreceptor charged by the charging apparatus, and can be appropriately selected according to the purpose. Examples thereof include a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of a photoreceptor.

The development step is a step of forming a visible image by developing the electrostatic latent image with a developer including the toner of the present invention using a developing device.
The developing device is not particularly limited as long as it can be developed using the developer, and can be appropriately selected from known ones. For example, the developing device accommodates the developer of the present invention, and an electrostatic latent image. And a developer carrying member capable of being contacted or contacted in a non-contact manner, and a developer-containing container (developer container) is preferably provided detachably.
The developing device may be either a dry developing method or a wet developing method, and may be either a single color developing device or a multicolor developing device. For example, the developer is charged by friction stirring. Examples include a stirrer and a rotatable magnet roller. In the developing device, for example, the toner and the carrier are mixed and stirred, 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 photoconductor, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the photoconductor by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a visible image is formed on the surface of the photoreceptor. Note that an alternating electric field is preferably applied when the toner is moved to the surface of the photoreceptor.

The transfer process is a process in which a visible image is transferred to a transfer target using a transfer device. After the primary transfer of the visible image onto the intermediate transfer member using the intermediate transfer member, the visible image is transferred to the transfer target. A mode in which secondary transfer is performed on a transfer body is preferred. In addition, a primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer member using two or more colors, preferably full color toner, as the toner, and the composite transfer image on the transfer target An embodiment having a secondary transfer step of transferring is preferable. The visible image can be transferred by charging the photoconductor using, for example, a transfer charger.
The transfer device preferably has a primary transfer device that transfers a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer device that transfers the composite transfer image onto a transfer target. The transfer device (primary transfer device, secondary transfer device) preferably has at least a transfer device that peels and charges the visible image formed on the photosensitive member toward the transfer target. There may be one transfer device or two or more transfer devices. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. Examples thereof include a transfer belt.
The transfer target is not particularly limited and can be appropriately selected from known recording media (recording paper).

The fixing step is a step of fixing the visible image transferred to the transfer target using a fixing device, and may be fixed for each color toner each time it is transferred to the transfer target. The toners may be fixed simultaneously at the same time in a state where the toners are laminated.
The fixing device is not particularly limited and may be appropriately selected according to the purpose. However, a fixing device that is heat-pressed and fixed using a known fixing member is preferable. The fixing member is preferably in the form of a roller or a belt, and examples thereof include a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller and an endless belt. At this time, it is preferable that heating temperature is 80-200 degreeC normally.
The fixing device has a heating element having a heating element, a film in contact with the heating element, and a pressure member in pressure contact with the heating element via the film, and an unfixed image is formed between the film and the pressure member. It is possible to use means for heating and pressurizing and fixing the transferred material to be transferred.
Depending on the purpose, for example, a known optical fixing device may be used together with the fixing device or instead of the fixing device.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the photoconductor using a neutralization device.
The neutralization device is not particularly limited, and may be any one as long as it can apply a neutralization bias to the photosensitive member, and can be appropriately selected from known neutralization devices. Examples thereof include a neutralization lamp.

The cleaning step is a step of removing toner remaining on the photoreceptor using a cleaning device.
The cleaning device is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected from known cleaners. For example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller A cleaner, a blade cleaner, a brush cleaner, a web cleaner, etc. are mentioned.

The recycling process is a process in which the toner removed in the cleaning process is recycled to the developing device using a recycling apparatus.
There is no restriction | limiting in particular in a recycling apparatus, For example, a well-known conveyance means etc. are mentioned.

A control process is a process of controlling each process using a control device.
The control device is not particularly limited as long as the movement of each step can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  Hereinafter, the present invention will be described in more detail with reference to examples. The form of the present invention is not limited to this. Unless otherwise specified, parts and percentages are based on weight.

[Oil phase / aqueous phase-preparation of toner base particles by emulsification method]
<Synthesis of fine particle dispersion>
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 11 parts of sodium salt Eleminol RS-30 (manufactured by Sanyo Chemical Industries), methacrylic acid ethylene oxide adduct sulfate, 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added 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 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 1] was obtained. The weight average particle diameter of the [fine particle dispersion 1] measured by LA-920 was 105 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin component was 59 ° C., and the weight average molecular weight was 150,000.

<Adjustment of water phase>
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Chemical Industries), and 90 parts of ethyl acetate were mixed and stirred to give a milky white liquid. Got. This is designated [Aqueous Phase 1].

<Synthesis of low molecular weight polyester>
229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and dibutyltin Add 2 parts of oxide, react at normal pressure and 230 ° C for 8 hours, and further react for 5 hours at 10-15 mmHg reduced pressure. Then, put 44 parts of trimellitic anhydride into the reaction vessel and add 180 parts at 180 ° C and normal pressure. The reaction was performed for a while to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25 mgKOH / g.

<Synthesis of intermediate polyester and prepolymer>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2 mol adduct, 81 parts of bisphenol A propylene oxide 2 mol adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at normal pressure and 230 ° C. for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. [Prepolymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Synthesis of ketimine>
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418 mgKOH / g.

<Combination of master batch>
35 parts of water, 40 parts of phthalocyanine pigment FG7351 (manufactured by Toyo Ink Co., Ltd.) and 60 parts of polyester resin RS801 (manufactured by Sanyo Kasei Co., Ltd.) are mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and the mixture is 150 using two rolls. After kneading at 30 ° C. for 30 minutes, the mixture was cooled and rolled, and pulverized with a pulverizer to obtain [Masterbatch 1].

<Creation of oil phase>
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular polyester 1], 110 parts of carnauba wax, 22 parts of CCA (salicylic acid metal complex) E-84 (manufactured by Orient Chemical Co., Ltd.) and 947 parts of ethyl acetate are charged. The mixture was heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill, Ultra Visco Mill (manufactured by Imex), zirconia beads having a liquid feeding speed of 1 kg / hour, a disk peripheral speed of 6 m / second, and a particle diameter of 0.5 mm. The wax and phthalocyanine pigment were dispersed under the condition of 3 passes. Next, 1324 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 obtain [Pigment Dispersion Liquid 1]. The solid content concentration of [Pigment dispersion 1] (measurement conditions: 130 ° C., 30 minutes) was 50%.

<Emulsification>
[Pigment dispersion 1] 648 parts, [Prepolymer 1] 154 parts, [Ketimine compound 1] 6.6 parts are put in a container and mixed with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at 5000 rpm for 1 minute. Then, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13000 rpm for 20 minutes to obtain [Emulsified slurry 1].

<Shape control>
3. Selogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.) 3.15 parts is added little by little to 75.6 parts of ion-exchanged water being stirred at 2,000 rpm with a TK homomixer (made by Tokushu Kika). To do. Stir for 30 minutes while maintaining the addition at 20 ° C. 43.3 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) is added to the obtained serogen solution, and the mixture is added and stirred for 5 minutes while maintaining at 20 ° C. To this, 2000 parts of [Emulsified slurry 1] was added and mixed with TK homomixer at 2,000 rpm for 1 hour to obtain [Shape Control Slurry 1].

<Desolvent>
[Shape control slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].
<Washing to drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (12000 rpm for 10 minutes), and then filtered.
(2): 100 parts of 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with TK homomixer (12000 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 12000 rpm), and then filtered twice to obtain [Filter cake 1].
Using a circulating dryer, [Filtration cake 1] was dried at 45 ° C. for 48 hours and sieved with a mesh of 75 μm to obtain [Toner base particle A]. [Mother toner particle A] had a volume average particle diameter (Dv) of 5.71 μm.

[Preparation of toner base particles B by oil phase / water phase-emulsification method]
[Toner Base Particle B] was obtained in exactly the same process as the Toner Base Particle A except that 110 parts of Carnauba Wax was reduced to 50 parts during the Toner Base Particle A manufacturing process. The volume average particle diameter (Dv) of the toner base particles B is 5.83 μm.

[Preparation of toner base particles C by oil phase / water phase-emulsification method]
[Toner Base Particle C] was obtained in the same process as that of the toner base particle A except that no Carnauba wax was contained during the process of manufacturing the toner base particle A. The toner base particle C volume average particle diameter (Dv) is 5.98 μm.

[Preparation of toner base particles D by pulverization method]
Binder resin [Bisphenol-type polyester resin mainly composed of bisphenol A ethylene oxide adduct and terephthalic acid [weight average molecular weight = 1.1 × 10 ⁴ , number average molecular weight = 3.9 × 10 ³ , η (140 ° C) = 90 Pa · s, glass transition temperature (Tg) = 69 ° C.]] 100 parts by mass, high melt viscosity resin (terpene-modified novolak resin, weight average molecular weight = 2500, Tm = 165 ° C., η (140 ° C.) = 85 , 000 Pa · s) 20 parts by mass, carbon black (BPL, manufactured by Cabot) 5 parts by mass, charge control agent (Bontron E84, manufactured by Orient Chemical Co.), and low molecular weight polypropylene (viscose 660P, Sanyo Chemical Industries) 5 parts by mass) and 4 parts by mass of carnauba wax are put into an air-cooled two-roll mill and melt-kneaded for 15 minutes after the addition. And, after cooling, subjected to fine pulverization by a jet mill, and classified by air classifier to obtain "toner base particles D" volume average particle diameter (Dv) 6 [mu] m.

[Production of release agent-containing porous body (release agent-containing porous particles) A]
AEROPERL 300/30 manufactured by Nippon Aerosil was selected as the core material (porous body: porous particles) of the release agent-containing porous body (release agent-containing porous particles). This porous material (AEROPERL 300/30) was put into a melt of carnauba wax (Yoyuki Kato, carnauba wax C1, melting point (measured by DSC): 79 ° C.), and the pressure was reduced while keeping the molten state. Stirring was performed under reduced pressure conditions so as to promote the substitution of the gas inside the compact with carnauba wax and to retain the release agent component inside the porous material. At this time, the weight ratio of the porous body (AEROPERL 300/30) to be introduced and the carnauba wax melt is kept so as to keep it inside as much as possible while suppressing the remaining of the carnauba wax on the surface of the porous particles. 10: 1 to 3: 1.

Since the release agent-containing porous particles contained in the carnauba wax obtained in the above are in a light aggregated adhering state, a scramjet mill (MN-30 manufactured by Deoksugaku Kosakusho Co., Ltd.) was used to break up the aggregated adhering substance. Again, it was crushed to the primary particle level.
That is, the scramjet apparatus can perform nano-level ultrafine pulverization by collision between particles using high-pressure gas. Since the crushing nozzles are arranged at positions equally divided in the circumference inside the cylindrical mill, and one or more of them are the raw material supply nozzles, concentric vortices can be created. Since the concentric swirl vortex can be formed inside the mill by the high-pressure jet stream, the scram jet is characterized by a sharp particle size distribution. In addition, since the scramjet uses interparticle collisions, there are few particle collisions with the mill wall surface. Therefore, a fine powder obtained by pulverization using a scramjet is preferable because it has low contamination due to the mill wall surface being scraped. In addition, when there is a possibility that a release agent component may remain on the particle surface as in this case, a slight mutual polishing effect is exhibited on the particle surface by scramjet mill grinding, and the removal effect of the porous particle surface residual release agent Was also obtained at the same time. By such pulverization, a release agent-containing porous body A having an average particle diameter of 100 nm was obtained.

[Production of release agent-containing porous body (release agent-containing porous particles) B]
The carnauba wax used in the mold release agent melt was changed to paraffin wax [C140, made by Nippon Seiwa Co., Ltd., melting point (measured by DSC): 61 ° C.] during the production process of the release agent-containing porous body A. In the same process as the release agent-containing porous body A, a release agent-containing porous body B having an average particle size of 86 nm was obtained.

[Production of release agent-containing porous body (release agent-containing porous particles) C]
Carnauba wax used in the mold release agent melt is replaced with microcrystalline wax [Hi-Mic 2065 made by Nippon Seiwa Co., Ltd., melting point (measured by DSC): 75 ° C.] during the production process of the release agent-containing porous material A A release agent-containing porous body C having an average particle size of 83 nm was obtained in the same process as in the release agent-containing porous body A except that.

[Production of release agent-containing porous body (release agent-containing porous particles) D]
Carnauba wax used in the mold release agent melt is replaced with Fischer-Tropsch (FT-100 manufactured by Shell, melting point (measured by DSC): 98 ° C.) during the production process of the release agent-containing porous body A. Obtained a release agent-containing porous body D having an average particle size of 96 nm in the same process as the release agent-containing porous body A.

[Production of release agent-containing porous body (release agent-containing porous particles) E]
In the production process of the release agent-containing porous body A, the carnauba wax used for the release agent melt is used instead of paraffin wax (paraffin wax 115 manufactured by Nippon Seiwa Wax, melting point (measured by DSC): 47 ° C.). Except for the above, a release agent-containing porous body E having an average particle size of 97 nm was obtained in the same process as the release agent-containing porous body A.

[Production of release agent-containing porous body (release agent-containing porous particles) F]
In the production process of the release agent-containing porous body A, the carnauba wax used in the release agent melt is replaced with paraffin wax [Nippon Seiwa Wax Paraffin Wax 120, melting point (measured by DSC): 50 ° C.]. Except for the above, a release agent-containing porous body F having an average particle diameter of 111 nm was obtained in the same process as the release agent-containing porous body A.

  About the average particle diameter of each said mold release agent containing porous body AF manufactured above, it measured using the particle size distribution measuring machine (product name UPA by Nikkiso Co., Ltd.) by a dynamic light scattering method, Based on this, number average particle size data was obtained.

<Creation of carrier>
Carrier used for preparation of developer and measurement of toner charge amount is 200 parts of silicone resin solution (manufactured by Shin-Etsu Chemical Co., Ltd.) and 3 parts of carbon black (manufactured by Cabot Corporation) in toluene with respect to 2500 parts of ferrite core material. The coating liquid dispersed in (1) was applied by a fluidized bed spray method to coat the surface of the core material, and then baked in an electric furnace at 300 ° C. for 2 hours. [Carrier] used had a relatively sharp particle size distribution and an average particle size of 30 to 60 μm.

Example 1
[Toner base particle A] 100 parts and 0.75 parts of rutile type titanium oxide hydrophobically treated with isobutyl having an average particle diameter of 15 nm were mixed with a Henschel mixer under the condition that the peripheral speed of the stirring blade was 35 m / second. Then, 0.8 parts of hydrophobic silica treated with hexamethyldisilazane having an average particle diameter of 8 nm was mixed with a Henschel mixer under the condition that the peripheral speed of the stirring blade was 35 m / sec. Thereafter, 2.0 parts of [Releasing Agent-Containing Porous Material A] was mixed with a Henschel mixer under the condition that the peripheral speed of the stirring blade was 35 m / second to prepare [Toner A1].
7 parts of [Toner A1] obtained and 93 parts of [Carrier] were mixed and stirred to prepare [Developer A1] having a toner concentration of 7 wt%.
Table 1 below shows the main components of the toner A1 (toner base particles, release agent-containing porous body).

(Example 2)
[Toner A2] to which a release agent-containing porous material A was externally added was prepared in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle B] in Example 1. [Developer A2] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner A2]. The main constitution of toner A2 (toner base particles, release agent-containing porous body) is shown in Table 1 below.

(Example 3)
[Toner A3] was prepared by externally adding a release agent-containing porous material A in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle D] in Example 1. Further, [Developer A3] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner A3]. The main constitution of toner A3 (toner base particles, release agent-containing porous material) is shown in Table 1 below.

Example 4
[Toner B1] to which a release agent-containing porous material B was externally added was prepared in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle B] in Example 1. [Developer B1] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner B1]. The main constitution of toner B1 (toner base particles, release agent-containing porous body) is shown in Table 1 below.

(Example 5)
[Toner B2] to which a release agent-containing porous body B was externally added was prepared in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle D] in Example 1. [Developer B2] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner B2]. Table 1 below shows the main components of the toner B2 (toner base particles, release agent-containing porous body).

(Example 6)
[Toner C1] to which a release agent-containing porous material C was externally added was prepared in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle B] in Example 1. [Developer C1] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner C1]. Table 1 below shows the main components of the toner C1 (toner base particles, release agent-containing porous body).

(Example 7)
[Toner C2] to which a release agent-containing porous material C was externally added was prepared in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle D] in Example 1. [Developer C2] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner C2]. Table 1 below shows the main components of the toner C2 (toner base particles, release agent-containing porous body).

(Example 8)
[Toner D1] to which a release agent-containing porous body D was externally added was prepared in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle B] in Example 1. [Developer D1] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner D1]. The main constitution of toner D1 (toner base particles, release agent-containing porous body) is shown in Table 1 below.

Example 9
[Toner D2] to which a release agent-containing porous body D was externally added was prepared in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle D] in Example 1. [Developer D2] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner D2]. Table 1 below shows the main components (toner base particles, release agent-containing porous body) of the toner D2.

(Comparative Example 1)
[Toner E1] to which a release agent-containing porous body E was externally added was prepared in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle B] in Example 1. [Developer E1] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner E1]. Table 1 below shows the main components (toner base particles, release agent-containing porous body) of the toner E1.

(Comparative Example 2)
[Toner E2] to which a release agent-containing porous material C was externally added was prepared in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle C] in Example 1. [Developer E2] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner E2]. The main constitution of toner E2 (toner base particles, release agent-containing porous body) is shown in Table 1 below.

(Comparative Example 3)
[Toner F1] was prepared by externally adding release agent-containing porous material F in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle A] in Example 1. [Developer F1] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner F1]. Table 1 below shows the main components (toner base particles, release agent-containing porous body) of the toner F1.

(Comparative Example 4)
[Toner F2] to which a release agent-containing porous material F was externally added was prepared in the same manner as in Example 1 except that [Toner Base Particle A] was used instead of [Toner Base Particle D] in Example 1. [Developer F2] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner F2]. Table 1 below shows the main components of the toner F2 (toner base particles, release agent-containing porous body).

(Comparative Example 5)
In [Example 1], [Toner G1] was prepared by adding [Toner Base Particle A] as it is and adding externally added large particle size silica [X-24 (manufactured by Shin-Etsu Chemical)] instead of the release agent-containing porous body A. [Developer G1] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner G1]. The main constitution of the toner G1 (toner base particles, release agent-containing porous body) is shown in Table 1 below.

(Comparative Example 6)
In Example 1, [toner base particle A] is replaced with [toner base particle B], and the release agent-containing porous body A is replaced with a large particle size silica [X-24 (manufactured by Shin-Etsu Chemical)]. [Toner G2] was prepared, and [Developer G2] was prepared in the same manner as in Example 1 except that [Toner A1] was used instead of [Toner G2]. Table 1 below shows the main components of the toner G2 (toner base particles, release agent-containing porous body).

[Evaluation]
Evaluation of photoreceptor filming, image quality, image graininess, sharpness, and fixability (cold offset property, hot offset property) by using the image forming apparatus of the following form using the developer composed of the toner of the above examples and comparative examples. The heat resistant storage stability was evaluated. The conditions for the evaluation items will be described later. The evaluation results are shown in Table 1 below.

(Image forming device)
The form of the image forming apparatus used in the evaluation will be described.
A charging roller for charging a uniform charge on the photosensitive drum in proximity to or in contact with the periphery of the photosensitive drum as an image carrier, and an exposure unit for forming an electrostatic latent image on the photosensitive drum. An exposure device, a developing device that visualizes an electrostatic latent image into a toner image, a transfer belt that transfers the toner image onto transfer paper, a cleaning device that removes residual toner on the photosensitive drum, and a residual charge on the photosensitive drum There are disposed a static elimination lamp for eliminating static electricity, a photosensor for controlling the voltage applied by the charging roller and the toner concentration of the developer. Further, the toner of the embodiment or the comparative example is supplied to the developing device from the toner supply device through the toner supply port. The image forming operation is performed as follows. The photosensitive drum rotates counterclockwise. The photosensitive drum is neutralized by neutralizing light, and the surface potential is averaged to a reference potential of 0 to -150V. Next, it is charged by the charging roller, and the surface potential becomes around -1000V. Next, the surface potential of the portion (image portion) that is exposed by the exposure apparatus and irradiated with light is 0 to −200V. The toner on the sleeve adheres to the image portion by the developing device. The photosensitive drum on which the toner image is made rotates and moves, and the transfer paper is fed from the paper feeding unit at a timing such that the leading edge of the paper and the leading edge of the image coincide with each other on the transfer belt. The toner image on the surface is transferred to the transfer paper. Thereafter, the transfer paper is sent to the fixing unit, and the toner is fused to the transfer paper by heat and pressure and discharged as a copy. Residual toner remaining on the photoconductor drum is scraped off by a cleaning blade in the cleaning device, and then the photoconductor drum is in an initial state in which the residual charge is neutralized by the neutralizing light and there is no toner. Move on to the process.

(Evaluation item)
(1) Photoreceptor Filming Each developer was conditioned for 2 hours or more in a high temperature and high humidity environment of 30 ° C. and 85% RH. Under this environment, the developer was used, and the filming of the photosensitive member and the image quality of the transferred image were observed when 50,000 copies were made with a commercial copying machine (imageNEO450: Ricoh Co., Ltd., machine equipped with a recycling mechanism).
Judgment Criteria A: No photoconductor filming and good image quality O: Photoconductor has a small amount of filming but almost no decrease in image density Δ: Photoconductor has a small amount of filming and image density is also reduced Observed x: Many filming on the photosensitive member, and in addition to image density reduction, image blurring is noticeable, such as image blurring. (2) Image quality Image quality is image quality degradation after paper passing (specifically, Were comprehensively judged for transfer defects and background smudge images). The transfer failure was judged by passing 5000 sheets through an image forming apparatus (manufactured by Ricoh Co., Ltd.) and then passing a black solid image and visually ranking the transfer failure level of the image. For the background image, 5000 sheets are passed through an image forming apparatus (manufactured by Ricoh Co., Ltd.), and then a blank paper image is stopped during development, and the developer on the photoconductor after development is scotch tape (Sumitomo). 3M)), and the difference from the image density of the untransferred tape is measured by a spectrodensitometer (X-Rite) and quantitatively evaluated. If the difference is less than 0.30, A product having a value of 0.30 or more was regarded as defective. These two were evaluated as good when the image quality was good, ◯ when the image quality was not good but acceptable, and x when the image quality was poor.
(3) Image granularity and sharpness Using a digital full-color copying machine (imageColor 2800 manufactured by Ricoh), a photographic image was output in a single color, and the degree of granularity and sharpness was visually evaluated. In order from the best, “◎” is equivalent to offset printing, “○” is slightly worse than offset printing, “△” is much worse than offset printing, “×” is about the same as conventional electrophotographic images (very much Bad).
(4) Fixability evaluation Ricoh Co., Ltd., which uses a Teflon (registered trademark) roller as a fixing roller MF2200 Using a machine with a modified fixing unit, set Ricoh type 6200 paper on this to perform a copy test I did it. The cold offset temperature (fixing lower limit temperature) and the hot offset temperature (hot offset resistant temperature) were determined by changing the fixing temperature. The minimum fixing temperature of the conventional low-temperature fixing toner is about 140 to 150 ° C. The evaluation conditions for low-temperature fixing are as follows: the paper feed linear velocity is 120 to 150 mm / sec, the surface pressure is 1.2 kgf / cm ² , the nip width is 3 mm, and the high temperature offset is the evaluation condition for the paper feed linear velocity is 50 mm / sec. The surface pressure was set to 2.0 kgf / cm ² and the nip width was 4.5 mm. The criteria for each characteristic evaluation are as follows.
(1) Cold offset property (low temperature fixability: 5-grade evaluation)
◎ (good): less than 140 ° C., ○: 140-149 ° C., □: 150-159 ° C., Δ: 160-170 ° C., x (bad): 170 ° C. or higher (2) Hot offset property (five-step evaluation)
◎ (good): 201 ° C. or higher, ○: 200 to 191 ° C., □: 190 to 181 ° C., Δ: 180 to 171 ° C., × (bad): 170 ° C. or lower (5) Evaluation of heat resistant storage stability After storage for 8 hours, it was sieved with a 42 mesh screen for 2 minutes, and the residual rate on the wire mesh was regarded as heat resistant storage stability. A toner having better heat-resistant storage stability has a lower residual ratio. The following four levels were evaluated.
×: 30% or more △: 20-30%
○: 10 to 20%
(Double-circle): Less than 10% The evaluation result was performed by 4-step evaluation.

When a toner having a configuration satisfying the conditions of the present invention [having a release agent-containing porous particle containing at least a release agent having a melting point of 60 ° C. or higher as an external additive in the porous pores] is used , Fixing performance (cold offset property, hot offset property, etc.) and heat-resistant storage stability, reduction of photoconductor filming, good image quality (suppression of transfer failure and background image), image graininess and sharpness It can be seen that maintenance is achieved in a balanced and effective manner.
On the other hand, Comparative Examples 1 to 4 using release agent-containing porous particles containing a release agent having a melting point of less than 60 ° C. inside the porous pores, and base particles B without using the release agent-containing porous material In the case of Comparative Example 6 in which a large particle size silica is externally added to the surface, it can be seen that fixing performance (cold offset property, hot offset property, etc.) and heat-resistant storage stability cannot be achieved at the same time. In the case of Comparative Example 5 in which large particle size silica was externally added to the surface of the base particle A without using the release agent-containing porous particles, the evaluation results of the fixing performance and the heat-resistant storage stability were not evaluated as x. There is a concern that the surface of the image bearing member (photosensitive member) may be worn during long-term use.
According to the present invention, it is possible to provide an image forming toner that has both fixing performance and heat resistant storage stability for developing an electrostatic latent image on an image carrier in an electrophotographic apparatus, an electrostatic recording apparatus, and the like. Even in use, it is possible to form a high-quality image in which image deterioration such as transfer failure on the output image and background image is suppressed.

10 Image carrier (photoreceptor)
20 Charging Device 30 Exposure Device 40 Development Device 60 Cleaning Device 80 Transfer Device

JP 2007-279702 A JP 2007-156099 A JP 2008-116568 A JP 2007-248911 A

Claims (8)

  A toner comprising toner base particles containing a binder resin and a colorant and an external additive for coating the surface of the toner base particles, wherein a release agent having a melting point of 60 ° C. or higher is porous as the external additive A toner comprising release agent-containing porous particles contained in pores.   2. The toner according to claim 1, wherein the content of the release agent-containing porous particles is 2% or more and 10% or less by weight with respect to the total amount of the toner base particles.   A toner material liquid (oil phase) obtained by dissolving or dispersing a toner material containing a binder resin and / or a binder resin precursor and a colorant in an organic solvent is contained in an aqueous medium (aqueous phase). The toner according to claim 1, wherein the toner is formed by desolvation after emulsification or dispersion.   The binder resin and / or binder resin precursor is selected from a modified polyester containing at least an ester bond and a bond unit other than the ester bond, a resin precursor capable of producing the modified polyester, and a crystalline polyester. The toner according to claim 3, comprising a resin material.   The toner according to claim 4, comprising a compound having an active hydrogen group and a polyester having a functional group capable of reacting with the active hydrogen group of the compound as a resin precursor capable of forming the modified polyester. .   The toner according to claim 4, wherein the modified polyester contains at least an ester bond and a urea bond.   The toner according to claim 1, wherein the toner base particles have a volume average particle diameter (Dv) of 3.0 μm or more and less than 6.0 μm.   A step of charging at least the surface of the image carrier, a step of developing the electrostatic latent image formed on the charged image carrier using the toner according to any one of 1 to 7, and a step of A step of transferring the toner image formed on the image support to the image support, and a step of heating and pressing the transferred toner image by a roller-like or belt-like fixing member to obtain a fixed image on the image support. And an image forming method.

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