JP4234022B2 - Toner, developer, developing device, and image forming apparatus - Google Patents

Description

  The present invention relates to a toner and a developer used for image formation in an electrostatic copying process such as a copying machine, a facsimile machine, and a printer, and further relates to a developing device and an image forming apparatus using the developer.

  An electrophotographic image forming method includes a charging step for applying a charge to the surface of a photoconductor as an image carrier, an exposure step for exposing the charged photoconductor surface to form an electrostatic latent image, and a photoconductor A developing process for supplying toner to the electrostatic latent image formed on the surface and developing; a transfer process for transferring the toner image on the surface of the photoreceptor to the surface of the transfer body; and a fixing process for fixing the toner image on the surface of the transfer body; And a cleaning step for removing toner remaining on the surface of the image carrier after the transfer step.

  In recent years, color image forming apparatuses using an electrophotographic method have become widespread, and further high definition of printed images has been demanded due to the fact that digitized images can be easily obtained. ing. As higher resolution and gradation of images are being studied, as a toner-side improvement that visualizes latent images, further spheroidization and smaller particle size have been studied in order to form high-definition images. ing. Since toners produced by the pulverization method have limitations in these properties, polymerized toners produced by suspension polymerization method, emulsion polymerization method, dispersion polymerization method, etc. that can be made spherical or reduced in particle size are employed. It's getting on.

  The toner having a nearly spherical shape is easily affected by the lines of electric force in the electrostatic development method, and is faithfully developed along the lines of electric force of the electrostatic latent image on the photosensitive member. When reproducing minute latent image dots, fine line reproducibility is enhanced because it is easy to obtain a dense and uniform toner arrangement. In addition, since the electrostatic transfer system has a smooth surface, good powder flowability, and low adhesion between toner particles or between toner particles and a photoreceptor, it is easily affected by lines of electric force. High transferability due to easy transfer faithfully along the lines of electric force.

However, at the same particle size, the closer the toner shape is to a true spherical shape, the smaller the surface area of the toner particles compared to the irregular toner, which can be effectively used for friction charging by contact with a friction charging member such as a magnetic carrier or a developer regulating member. There are few surfaces. In addition, when it is spherical, slipping is likely to occur on the surface of the friction charging member, and the charging speed and charging level are lowered. For this reason, the amount of the charge control agent added to the toner surface is required to be a certain amount or more.
In addition, as the toner particle size is reduced to improve the reproducibility of minute dots, the triboelectric chargeability decreases. Therefore, it is an important issue to balance these chargeability, developability, and transferability. Yes.

  Various proposals have been made to control the shape of spherical and small toner particles. As an index indicating the shape of the toner, shape factors SF-1 and SF-2 are often used. The shape factor SF-1 is an index representing the degree of roundness of the toner particles, and SF-2 is an index representing the degree of unevenness of the toner particles. The shape of the toner is controlled by defining one or both of the shape factors SF-1 and SF-2, and the above-described charging property, developing property, transfer property, or cleaning can be performed even when the toner has a spherical shape or a small particle size. (See, for example, Patent Documents 1 to 3).

Patent Document 4 defines the range of the shape factor of the toner particles and also defines the surface area ratio represented by the following formula.
Surface area ratio = ρ × D _50p × S
Here, ρ is the specific gravity (g / m ³ ) of the toner particles, D _50p is the number average particle diameter (m) of the toner particles, and S is the BET specific surface area (m ³ / g) of the toner particles. This surface area ratio represents the unevenness of toner particles on a scale different from the above-described shape factor. When the surface area ratio exceeds the specified range, the degree of unevenness on the surface of the toner particles increases, and external additives added to the toner particles gradually enter the recesses of the toner particles over time, and chargeability is maintained over a long period of time. The transferability cannot be maintained.

JP-A-9-179331 JP-A-10-142835 JP 11-327197 A JP 2001-51444 A

  As described above, attempts have been made to improve the chargeability, developability, transferability, or cleaning properties by controlling the shape of the toner particles, but all of them roughly grasp the surface shape of the toner particles. There are no microscopic irregularities.

  In view of the above problems, the present invention controls the fine irregularities on the surface of the toner particles so that the charging property, the developing property, and the transfer property are compatible even with the toner having a spherical shape and a small particle size. It is an object of the present invention to provide a toner and a developer, and a developing device and an image forming apparatus using these.

In order to solve the above problems, the present invention provides a toner comprising at least a binder resin and a colorant, and the toner includes a polyester prepolymer having at least a functional group containing a nitrogen atom, a polyester, and a colorant. The toner material solution in which the release agent is dissolved or dispersed in an organic solvent is cross-linked and / or elongated in an aqueous medium , granulated in a liquid medium containing resin fine particles, and the toner surface After the granulation step in the liquid medium is made to adhere to the resin fine particles, the toner particles in the liquid medium are added at a temperature of 25 to 50 ° C. at 25 to 50 ° C. either before or after the washing or solvent removal step. It is a toner obtained by passing through an aging step of aging for from 23 to 23 hours and having inorganic fine particles attached to toner base particles having the following surface properties.
(1) The surface roughness Ra is 1 to 30 nm.
(2) The standard deviation RMS of the surface roughness is 10 to 90 nm.
(3) The number of convex portions having a height difference of 10 nm or more from the bottom of the concave portion to the top of the convex portion is 1 to 20 / μm.

The present invention, in the toner, the average circularity of the toner particles are toner 0.93 to 1.00.
The present invention, in the toner, the ratio of toner particles of a circularity of less than 0.93 is toner 30% or less.
The present invention is the one in Kano toner, the toner having a volume average particle diameter (Dv) of a 2.0 to 6.0 [mu] m, further the ratio Dv / Dn between the number average particle diameter (Dn) 1.00 The toner is ˜1.40.

The present invention is the one in Kano toner, the surface roughness of the toner (Ra) and the ratio Ra of the volume average particle diameter (Dv) (nm) / Dv (μm) is in the toner of 0.2 to 6.0 is there.
The present invention is the one in Kano toner shape factor SF-2 of toner is in the range of 100 to 140, the ratio Ra of the surface roughness (Ra) and the shape factor SF-2 (nm) / SF-2 Is a toner in the range of 0.007 to 0.30.

The present invention, in the any Kano toner, the toner is the toner base particle surfaces, vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicone resins, phenol resins, melamine resins, The toner includes at least one of urea resin, aniline resin, ionomer resin, and polycarbonate resin.

The present invention, the toner odor Te, granulated in a liquid medium containing resin fine particles of the body volume average particle size of 20 to 150 nm, a toner in which the fine resin particles on the toner surface can be obtained by adhering.
The present invention, in the toner, the shape of the resin fine particles are toner is spherical.

The present invention, the Te either Kano toner odor, Ru toner der release agent is contained.

The present invention relates to a developer for developing an electrostatic latent image formed on the latent image bearing member, the developer, the one and Kano toner, a two-component developer comprising a magnetic carrier.
The present invention is a developer for developing an electrostatic latent image formed on a latent image carrier, and the developer is a one-component developer using any of the toners described above .

The present invention relates to a developing device for developing and developing an electrostatic latent image on a latent image carrier by carrying and conveying the developer by the developer carrier and applying an alternating electric field at a position facing the latent image carrier. The developing device is a developing device using any one of the developers.
According to the present invention, a latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and the surface of the latent image carrier that is charged is exposed based on image data, An exposure unit for writing an electrostatic latent image; a developing unit for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier; and a visible image on the surface of the latent image carrier; a transfer unit for transferring the transfer member, in an image forming apparatus and a fixing unit configured to fix the visible image on the transfer member, an image forming apparatus the developing device is the developing device.

  According to the present invention, the surface properties of the toner particles are finely controlled, so that the toner has excellent charge reproducibility, transferability, and the like even with a small particle size and spheroidized toner excellent in dot reproducibility. Thus, a toner and a developer that form a high-quality image can be provided. Further, the image forming apparatus using the developer containing the toner of the present invention can provide a high-quality image with excellent chargeability, developability, transferability, excellent reproducibility of minute dots, and the like.

Hereinafter, embodiments of the present invention will be described.
The toner of the present invention comprises at least a binder resin and a colorant, and is formed by adhering inorganic fine particles to toner base particles having the following surface properties.
(1) The surface roughness Ra is 1 to 30 nm.
(2) The standard deviation RMS of the surface roughness is 10 to 90 nm.
(3) The number of convex portions on the surface irregularities having a height difference of 10 nm or more is 1 to 20 / μm.

  The surface properties of the toner base particles can be analyzed using an atomic force microscope (AFM). AFM accurately scans and controls either a probe or a sample in a three-dimensional direction with a scanner using a piezoelectric element, detects the force acting between the probe and the sample as an interaction, and obtains an uneven image on the sample surface Is. While scanning the sample surface (XY plane) with the probe, the sample surface is traced while feedback controlling the distance (Z-axis height) of the probe from the sample so as to keep the above-mentioned interaction constant. In the present embodiment, the surface properties of the toner base particles are defined by tracing a 1 μm square and examining the three-dimensional surface roughness of the toner particle surface.

  The surface roughness Ra is defined by a three-dimensional average roughness with respect to the center plane (that is, a plane in which the volume of the irregularities formed by the surface shape at the plane is equal above and below the plane). Is done.

ここで、Ｚ_ｃｐは中心面のＺ値、Ｚ_ｉは各データポイントのＺ値、Ｎはデータポイントの数を示す。

Here, Z _cp is the Z value of the center plane, Z _i is the Z value of each data point, and N is the number of data points.

  The standard deviation RMS of the surface roughness is the standard deviation of the Z values of all data points and is expressed by the following formula II.

ここで、Ｚ_ａｖｅは全Ｚ値の平均値、Ｚ_ｉは各データポイントのＺ値、Ｎはデータポイントの数を示す。

Here, Z _ave is the average value of all Z values, Z _i is the Z value of each data point, and N is the number of data points.

The surface roughness Ra is an average surface roughness, and is the same as long as the volume of the unevenness formed by the center plane and the surface shape is equal, whether it is rough unevenness or fine unevenness. On the other hand, the standard deviation RMS has a larger value when there are many fine irregularities, and can represent the density of the irregularities.
In the toner of the present invention, the surface roughness Ra of the toner base particles is 1 to 30 nm. When the surface roughness Ra is less than 1 nm, the unevenness of the surface of the toner base particles is too small, and slipping occurs at the time of frictional charging due to contact with a frictional charging member such as a magnetic carrier or a developer regulating member. Cannot be obtained. On the other hand, when Ra exceeds 30 nm, the irregularities of the toner base particle surface are large, the fluidity of the toner is deteriorated, and the transferability is lowered.
The standard deviation RMS of the surface roughness of the toner base particles is 10 to 90 nm. When the standard deviation RMS of the surface roughness is less than 10 nm, the surface of the toner base particles is rough, and good friction charging due to contact with the friction charging member cannot be performed. On the other hand, if the RMS exceeds 90 nm, the irregularities on the surface of the toner base particles become dense, and the fluidity of the toner decreases.

  In the toner base particles, the number of convex portions having a height difference from the bottom of the concave portion to the top of the convex portion of 10 nm or more is 1 to 20 / μm. When the number of the convex portions is less than 1 / μm, the surface of the toner base particles is too smooth, and slipping easily occurs at the time of tribocharging, and good triboelectric chargeability cannot be obtained. Moreover, the space | interval of a convex part and a convex part is wide, Therefore It becomes easy to enter inorganic fine particles in a recessed part. If the number of the convex portions exceeds 20 / μm, the toner base particles have too many irregularities, the fluidity of the particles is lowered, and good transferability cannot be obtained.

The toner of the present invention is obtained by adding inorganic fine particles to the toner base particles having the surface properties described above. Examples of inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, oxidation Examples thereof include chromium, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. By using any one of these or some inorganic fine particles in combination, the fluidity, developability and chargeability of the toner particles can be improved.
The primary particle diameter of the inorganic fine particles is preferably 5 × ¹⁰ -3 ~2μm, it is particularly preferably 5 × ¹⁰ -3 ~0.5μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5 wt% of the toner, and particularly preferably 0.01 to 2.0 wt%.

The average circularity of the toner particles is preferably 0.93 to 1.00 from the viewpoint of obtaining high image quality because of excellent dot reproducibility and good transferability. Such a toner having a high average circularity is liable to slip on the surface of a frictional charging member such as a magnetic carrier, which is disadvantageous in terms of charging speed and charging level. However, by having the surface properties of the toner particles according to claim 1, a sufficient triboelectric chargeability can be obtained, and a toner excellent in developability and transferability can be obtained.
When the average circularity is less than 0.93 and the toner has a shape separated from the spherical shape, it is difficult to obtain a high-quality image having sufficient transferability or dust. Such irregularly shaped particles have many points of contact with the smooth medium on the photoreceptor and the charge concentrates on the tip of the protrusion, so van der Waals force and mirror force are more than those with relatively spherical particles. Wearing power is high. For this reason, in the electrostatic transfer process, the spherical particles are selectively moved in the toner in which the amorphous particles and the spherical particles are mixed, and the character portion and the line portion image are lost. Further, the remaining toner has to be removed for the next development step, and there arises a problem that a cleaning device is necessary and the toner yield (the ratio of toner used for image formation) is low.
The circularity of the toner is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, the measurement is performed using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 mL of water from which impure solids are removed in advance is added, 0.1 to 0.5 mL of a surfactant is added as a dispersant, and about 0.1 to 9.5 g of a measurement sample is further added. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the concentration and dispersion of the dispersion are set to 3,000 to 10,000 / μL, and the shape and distribution of the toner are measured.

  In addition to the above average circularity range, the toner of the present invention preferably has a ratio of toner particles having a circularity of less than 0.93 of 30% or less. A toner having a large variation in circularity such that the ratio exceeds 30% is not preferable because the charging speed and level are widened and the charge amount distribution is widened.

The toner has a volume average particle diameter Dv of 2.0 to 6.0 μm and a ratio Dv / Dn to the number average particle diameter Dn of 1.00 to 1.40. The volume average particle size is preferably 3.0 to 6.0 μm and Dv / Dn 1.00 to 1.15. By using such a toner, any of heat resistant storage stability, low temperature fixability, and hot offset resistance can be obtained. In particular, when used in a full-color copying machine, excellent glossiness of an image can be obtained.
In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. In addition, when the volume average particle size is smaller than the range of the present invention, in the two-component developer, the toner is fused to the surface of the magnetic carrier during long-term stirring in the developing device, and the charging ability of the magnetic carrier is reduced. 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.
In addition, these phenomena are greatly related to the content of fine powder. Particularly, when the particle diameter of the toner exceeds 3%, the adhesion to the magnetic carrier and the stability of charging at a high level are hindered. Become.
Conversely, when the volume average particle diameter of the toner 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 performed. In many cases, the variation in the particle diameter of the toner increases.
On the other hand, if Dv / Dn exceeds 1.40, the charge amount distribution becomes wide and the resolving power decreases, which is not preferable.

  The average particle size and particle size distribution of the toner can be measured using a Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). In the present invention, a Coulter counter TA-II type was used and connected to an interface (manufactured by Nikka Giken) and a PC9801 personal computer (manufactured by NEC) to output the number distribution and volume distribution.

  The ratio Ra (nm) / Dv (μm) between the surface roughness Ra of the toner and the volume average particle diameter Dv is preferably 0.2 to 6.0. When the ratio is less than 0.2, the unevenness is small relative to the particle size of the toner particles, so that the toner particles are likely to slip on the surface of the friction charging member, and the chargeability is lowered. On the other hand, when the above ratio exceeds 6.0, the unevenness is large with respect to the particle diameter of the toner particles, so that the toner particles are strongly slid with the frictional charging member and easily spent.

The toner preferably has a shape factor SF-2 in the range of 100 to 140 and a ratio Ra (nm) / SF-2 to the surface roughness Ra in the range of 0.007 to 0.30.
The shape factor SF-2 indicates the degree of unevenness of the shape of the toner, and a photograph of the toner is taken with a scanning electron microscope (S-800: manufactured by Hitachi, Ltd.), and this is taken as an image analyzer (LUSEX3: Nireco Corporation). To be analyzed and calculated. Compared with the analysis of the surface roughness Ra, the macro unevenness of the toner particles is analyzed. Specifically, as shown in the following formula III, a value obtained by dividing the square of the perimeter PERI of the figure formed by projecting the toner on the two-dimensional plane by the figure area AREA and multiplying by 100π / 4.
SF-2 = {(PERI) ² / AREA} × (100π / 4) Formula III
When the value of SF-2 is 100, macro unevenness does not exist in the toner shape, and as the SF-2 value increases, the toner shape unevenness becomes more prominent. When the value of SF-2 exceeds 140, the toner is scattered on the image and the image quality is lowered. Therefore, the range of 100 to 140 is preferable.
The ratio Ra (nm) / SF-2 between the surface roughness Ra representing fine irregularities on the toner particle surface and the shape factor SF-2 representing macro irregularities on the toner particle shape is 0.007 to 0.30. A range is preferred. The toner in this range has a moderately fine unevenness on the toner particle surface, so that the triboelectric chargeability is good, and the toner particle shape is also substantially spherical, so that the developability and transferability are excellent. A high-quality image can be provided.

  The toner of the present invention is produced by granulating in a liquid medium. The toner produced by the dry pulverization method has an irregular toner shape and a wide particle size distribution. Therefore, in order to narrow the circularity distribution and particle size distribution and narrow the toner charge amount distribution, the toner is preferably produced by granulating in a liquid medium. Specifically, a suspension polymerization method, an emulsion polymerization method, a dispersion polymerization method, or the like can be used to form droplets in a liquid medium and granulate.

In order to control the surface roughness Ra of the toner base particles, it is easy and preferable to use a method in which a resin different from the toner binder resin is attached to the surface of the toner base particles. As the resin different from the toner binder resin, any resin can be used as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. Examples thereof include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin, two or more of the above resins may be used in combination.
Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained. For example, vinyl resins are polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, (meth) acrylic acid-acrylic acid esters. Examples thereof include resins such as a polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer.

  When a toner composition dissolved or dispersed in an organic solvent using the above resin component is dispersed in an aqueous medium, the resin component adheres as fine particles around the existing oil droplets and coalesces the oil droplets. This contributes to the stabilization of dispersion, such as the production of oil droplets having a uniform particle size. Further, the surface roughness Ra of the toner base particles can be controlled by controlling the amount of the resin component to be added and the particle diameter of the resin fine particles to be formed.

  The volume average particle diameter of the resin fine particles is preferably in the range of 20 to 150 nm. If the particle size is outside this range, the granulation property of the toner and the adhesion of the resin fine particles to the toner surface are lowered, and the toner particle size cannot be controlled as follows, which is not preferable. When the volume average particle diameter of the resin fine particles is less than 20 nm, it is not preferable because it is difficult to control the particle of the toner having a sufficiently small particle diameter (volume average particle diameter of less than 10 μm) in the toner granulation step. Further, when the volume average particle diameter of the resin fine particles exceeds 150 nm, it is not preferable because it is difficult to control the toner particle having a sufficiently large particle diameter (volume average particle diameter of 1 μm or more) in the toner granulation step. The obtained toner has the resin fine particles attached thereto and can have a surface shape as described in claim 1.

The shape of the resin fine particles is not particularly limited as long as the surface shape of the toner as described in claim 1 can be formed. However, if the shape is spherical, toner granulating properties (average particle size, particle size distribution) In terms of shape control).
On the other hand, if the shape of the resin fine particles is any of a spindle shape, a disk shape, a spindle disk shape, an indeterminate flat plate shape, or a mixture of these, in terms of toner granulation properties, it is However, because of the irregular shape, the resin fine particles do not adhere uniformly to the toner core, and the exposed surface of the toner core increases, which increases the toner fixability. Can do.

Further, as a means for preventing the hot offset of the toner, which is a problem in the fixing step of the image forming process, a method in which a release agent is contained in the toner can be mentioned. The release agent contained in the toner is exposed to heat and pressure at the time of fixing, and the toner is deformed by the heat and pressure. Thus, the release agent is released from the fixing member. Such a release agent is preferably included without being exposed on the toner surface. This is because the wax exposed on the surface adheres to the surface of a frictional charging member such as a magnetic carrier and reduces the frictional charging property of the toner, or exhibits cohesiveness and deteriorates the toner fluidity.
Further, by using the above-described method of adhering the resin fine particles to the surface of the toner base particles, it becomes possible to give an effect that the release agent contained in the toner exudes only at the time of fixing, thereby controlling the surface roughness. In addition, problems such as a decrease in chargeability of the toner can be solved.

  As a release agent, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface. The effect on high temperature offset is exhibited without applying a release agent such as oil. Examples of such a wax component include the following. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline, And petroleum waxes such as petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .

  In the toner of the present invention, preferably, a toner material liquid in which at least a polyester prepolymer having a functional group containing a nitrogen atom, polyester, a colorant, and a release agent is dispersed in an organic solvent is contained in an aqueous solvent. It is a toner obtained by crosslinking and / or elongation reaction. Hereinafter, the constituent material of the toner and a suitable manufacturing method will be described.

(polyester)
The polyester is obtained by a polycondensation reaction between a polyhydric alcohol compound and a polycarboxylic acid compound.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable. Examples of the dihydric alcohol (DIO) 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, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyhydric alcohol (TO) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred. Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.
The polycondensation reaction between a polyhydric alcohol (PO) and a polycarboxylic acid (PC) is carried out in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and heated to 150 to 280 ° C. while reducing the pressure as necessary. The produced water is distilled off to obtain a polyester having a hydroxyl group. The hydroxyl value of the polyester is preferably 5 or more, and the acid value of the polyester is usually 1 to 30, preferably 5 to 20. By giving an acid value, it tends to be negatively charged, and furthermore, when fixing to a recording paper, the affinity between the recording paper and the toner is good and the low-temperature fixability is improved. However, when the acid value exceeds 30, there is a tendency to deteriorate with respect to the stability of charging, particularly environmental fluctuation.
The weight average molecular weight is 10,000 to 400,000, preferably 20,000 to 200,000. A weight average molecular weight of less than 10,000 is not preferable because offset resistance deteriorates. On the other hand, if it exceeds 400,000, the low-temperature fixability is deteriorated.

In addition to the unmodified polyester obtained by the above polycondensation reaction, the polyester preferably contains a urea-modified polyester. The urea-modified polyester is obtained by reacting a terminal carboxyl group or hydroxyl group of the polyester obtained by the above polycondensation reaction with a polyvalent isocyanate compound (PIC) to obtain a polyester prepolymer (A) having an isocyanate group. It is obtained by cross-linking and / or extending the molecular chain by the reaction of the amine with amines.
Examples of the polyvalent isocyanate compound (PIC) 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.); isocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.
The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.
The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

Next, as amines (B) to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4) ), Amino acid (B5), and amino acid block of B1 to B5 (B6).
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like. Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine. 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 the compound (B6) obtained by blocking the amino group of B1 to B5 include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). 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 more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

  The urea-modified polyester is produced by a one-shot method or the like. Polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and water generated while reducing the pressure as necessary. Distill off to obtain a polyester having a hydroxyl group. Subsequently, at 40-140 degreeC, this is made to react with polyvalent isocyanate (PIC), and the polyester prepolymer (A) which has an isocyanate group is obtained. Further, this (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a urea-modified polyester.

When reacting (PIC) and when reacting (A) and (B), a solvent may be used if necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to isocyanates (PIC), such as tetrahydrofuran (such as tetrahydrofuran).
In addition, in the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B), a reaction terminator can be used as necessary to adjust the molecular weight of the resulting urea-modified polyester. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).
The weight average molecular weight of the urea-modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester or the like is not particularly limited when the above-mentioned unmodified polyester is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. When the urea-modified polyester is used alone, its number average molecular weight is usually 2000-15000, preferably 2000-10000, more preferably 2000-8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

By using the unmodified polyester and the urea-modified polyester in combination, the low-temperature fixability and the gloss when used in the full-color image forming apparatus 100 are improved. Therefore, it is preferable to use the urea-modified polyester alone. In addition, polyester modified by chemical bonds other than urea bonds may be included.
The unmodified polyester and the urea-modified polyester are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, it is preferable that the unmodified polyester and the urea-modified polyester have a similar composition.
The weight ratio of unmodified polyester to urea-modified polyester is usually 20/80 to 95/5, preferably 70/30 to 95/5, more preferably 75/25 to 95/5, and particularly preferably 80 /. 20-93 / 7. When the weight ratio of the urea-modified polyester is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

The glass transition point (Tg) of the binder resin containing unmodified polyester and urea-modified polyester is usually 45 to 65 ° C, preferably 45 to 60 ° C. If it is less than 45 ° C., the heat resistance of the toner deteriorates, and if it exceeds 65 ° C., the low-temperature fixability becomes insufficient.
In addition, since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the heat-resistant storage stability tends to be good even when the glass transition point is low as compared with known polyester-based toners.

(Coloring agent)
As the colorant, all known dyes and pigments can be used. 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, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sayred, Parachlor Ortonito Aniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Lid Russian nin green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

(Charge control agent)
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.
The amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not limited to a specific one. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts 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 lowered, and the image density is lowered. Invite.

As the release agent and the inorganic fine particles, the substances described above can be used.
The charge control agent and the release agent may be melt-kneaded together with the masterbatch and binder resin, or may be added when dissolved and dispersed in an organic solvent.

Next, a toner manufacturing method will be described. Here, although a preferable manufacturing method is shown, it is not limited to this.
(Toner production method)
1) A toner material solution is prepared by dispersing a colorant, unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent in an organic solvent.
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.

Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  Further, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. , Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (Daikin Industries) Manufactured), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footgent F-300 (Neos), and the like.

  As the resin fine particles, the aforementioned substances can be used. In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

  As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, poly Xoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The dispersion method is not particularly limited, and known equipment 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. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, 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 during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

3) At the same time as the preparation of the emulsion, the amines (B) are added to cause a reaction with the polyester prepolymer (A) having an isocyanate group.
This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

  Either before or after the washing and solvent-removing steps, a step can be provided in which the emulsified dispersion is allowed to stand at a certain temperature for a certain period of time and the produced toner particles are aged. Thereby, toner particles having a desired particle diameter can be produced. The temperature of the aging step is preferably 25 to 50 ° C., and the time is preferably 10 minutes to 23 hours.

5) A charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner.
The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the spherical shape and the spindle shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. Can do.

  The toner of the present invention can be mixed with a magnetic carrier and used as a two-component developer. In this case, the carrier to toner content ratio in the developer is preferably 1 to 10 parts by weight of toner with respect to 100 parts by weight of carrier. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride and non- Monomers including a fluoro terpolymers such, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

Further, when preparing the developer, in order to improve the fluidity, storage stability, developability and transferability of the developer, the hydrophobic silica fine particles mentioned above are further listed in the developer produced as described above. Inorganic fine particles such as powder may be added and mixed. For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, or vice versa.
Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.

An image forming apparatus using the toner of the present invention as a developer will be described.
FIG. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present invention. The image forming apparatus 100 includes a document reading unit 20, an image forming unit 30, and a paper feeding unit 40. In the image forming unit 30, a photosensitive member 1 that is a latent image carrier, and a charging device 2, an exposure device 3, a developing device 4, a transfer device 6, a fixing device 7, and a cleaning device 8 are arranged around the photosensitive member 1. Has been. The surface of the photoreceptor 1 is uniformly charged by the charging device 2, an electrostatic latent image is formed on the charged surface by the exposure light of the exposure device 3, and toner having the same polarity as that of the formed latent image is developed by the developing device. Then, the toner image is supplied from 4 and developed, and then transferred onto a transported recording member such as paper by the transfer device 6. The recording member is then conveyed to the fixing device 7 where the toner is fixed on the recording member by heat and pressure. On the other hand, the toner remaining on the photoreceptor 1 after the transfer is removed by the cleaning device 8.

  For the developing device 4, a developer containing the toner is used. In the developing device 4, the developer carrying member 4 a carries and conveys the developer, and an alternating electric field is applied at a position facing the photoconductor 1 to develop the latent image on the photoconductor 1. By applying the alternating electric field, the developer is activated, the charge amount distribution of the toner can be narrowed, and the developability can be improved.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. “Part” means part by weight.

As the magnetic carrier used for the two-component developer, the following were used in common with each of the examples.
(Manufacture of magnetic carrier)
・ Core material: Cu—Zn ferrite particles (weight average diameter: 35 μm) 5000 parts ・ Coating material: Toluene 450 parts Silicone resin SR2400
(Toray Dow Corning Silicone, nonvolatile content 50%) 450 parts Aminosilane SH6020
(Toray / Dow Corning / Silicone) 10 parts Carbon black 10 parts The above coating material is dispersed with a stirrer for 10 minutes to prepare a coating liquid, and this coating liquid and core material are placed in a fluidized bed. The coating liquid was applied to the core material by applying the coating liquid while forming a swirling flow with the coating. The obtained coated product was baked in an electric furnace at 250 ° C. for 2 hours to obtain a carrier coated with a silicone resin with an average thickness of 0.5 μm.

(Preparation of two-component developer)
To 100 parts by weight of the carrier, 7 parts by weight of each color toner shown in the following examples was uniformly mixed and charged using a type of tumbler mixer in which the container was rolled and stirred to prepare a developer.

Example 1
(Synthesis of resin fine particle emulsion)
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 11 parts of a sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 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 3800 rpm for 30 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 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 volume average particle size of the [fine particle dispersion 1] measured with a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.) was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The shape of the resin fine particles was spherical. The Tg of the resin was 58 ° C., and the weight average molecular weight was 130,000.

(Adjustment of aqueous phase)
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% 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 as [Aqueous Phase 1].

(Synthesis of low molecular weight polyester)
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were placed, polycondensed at 230 ° C. for 7 hours under normal pressure, and further 10-15 mmHg Was reacted for 5 hours under reduced pressure to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2300, a weight average molecular weight of 6700, a peak molecular weight of 3800, a Tg of 43 ° C., and an acid value of 4.

(Synthesis of intermediate polyester)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 7 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, a peak molecular weight of 3000, a Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
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 pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

(Synthesis of ketimine)
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

(Synthesis of master batch)
1200 parts of water, 540 parts of carbon black (Printex35: manufactured by Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin are added and mixed with a Henschel mixer (manufactured by Mitsui Mining). Was kneaded at 130 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

(Production of oil phase)
378 parts of [Low molecular weight polyester 1], 100 parts of carnauba wax, and 947 parts of ethyl acetate were charged in a container equipped with a stirring bar and a thermometer, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. 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 Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and wax were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and the mixture was subjected to two passes by the bead mill under the above conditions to obtain [Pigment / wax dispersion 1]. The solid content concentration of [Pigment / Wax Dispersion 1] was 50%.

(Emulsification to solvent removal)
[Pigment / Wax Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 7 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 1].

(Washing-drying)
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(i) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(ii) 1% hydrochloric acid was added to the filter cake of (i) so as to have a pH of 3.5 to 4.5, mixed with a TK homomixer (15 minutes at 12,000 rpm), and then filtered. .
(iii) Add 300 parts of ion-exchanged water to the filter cake of (ii), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was.
[Filtration cake 1] was dried at 40 ° C. for 40 hours with a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner Base Particles 1]. Thereafter, 1.5 parts of hydrophobic silica and 0.5 part of hydrophobized titanium oxide are added to 100 parts of [toner base particle 1], mixed with a Henschel mixer, and sieved with a mesh of 35 μm to obtain [Toner 1]. It was. The physical properties of the obtained [Toner 1] are shown in Table 1, and the evaluation results are shown in Table 2.

Example 2
In Example 1, a toner was obtained in the same manner as in Example 1 except that the conditions were changed as follows. The physical properties of the obtained [Toner 2] are shown in Table 1, and the evaluation results are shown in Table 2.
(Synthesis of resin fine particle emulsion)
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 11 parts of a sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 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 3800 rpm for 30 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 1 hour. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and then 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 2] was obtained. The volume average particle diameter of [fine particle dispersion 2] measured with a particle size distribution analyzer (LA-920: manufactured by Sysmex Corporation) was 40 nm. A portion of [Fine Particle Dispersion 2] was dried to isolate the resin component. The shape of the resin fine particles was spherical. The Tg of the resin was 56 ° C., and the weight average molecular weight was 120,000.

Example 3
In Example 1, a toner was obtained in the same manner as in Example 1 except that the conditions were changed as follows. The physical properties of the obtained [Toner 3] are shown in Table 1, and the evaluation results are shown in Table 2.
(Emulsification to solvent removal)
[Pigment / Wax Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at 13,000 rpm for 10 minutes to obtain [Emulsified Slurry 2].
[Emulsion slurry 2] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 6 hours, aging was carried out at 45 ° C. for 5 hours to obtain [Dispersed slurry 2].

Example 4
A toner was obtained in the same manner as in Example 1 except that the steps from emulsification to solvent removal were changed to the following conditions. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
A toner was obtained in the same manner as in Example 1 except that the steps from emulsification to solvent removal were changed to the following conditions. The physical properties of the obtained [Toner 4] are shown in Table 1, and the evaluation results are shown in Table 2.
(Emulsification to solvent removal)
[Pigment / Wax Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at 13,000 rpm for 40 minutes to obtain [Emulsified Slurry 3].
[Emulsion slurry 3] 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 5 hours to obtain [Dispersion slurry 3].

Example 5
In Example 1, a toner was obtained in the same manner as in Example 1 except that the conditions were changed as follows. Table 1 shows the physical properties of [Toner 5] and Table 2 shows the evaluation results.
(Production of oil phase)
In a container in which a stir bar and a thermometer are set, 378 parts of [low molecular weight polyester 1], 130 parts of carnauba / rice wax (weight ratio 5: 5) and 947 parts of ethyl acetate are charged, and the temperature is raised to 80 ° C. with stirring. After maintaining at 80 ° C. for 4 hours, it was 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 2 hours to obtain [Raw material solution 2].
[Raw material solution 2] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. Carbon black and wax were dispersed under conditions of filling and 10 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and the mixture was subjected to 5 passes with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 2]. The solid content concentration of [Pigment / Wax Dispersion 2] was 50%.

Example 6
In Example 1, a toner was obtained in the same manner as in Example 1 except that the conditions were changed as follows. The physical properties of the obtained [Toner 6] are shown in Table 1, and the evaluation results are shown in Table 2.
(Production of oil phase)
A container equipped with a stir bar and a thermometer was charged with 378 parts of [low molecular weight polyester 1], 100 parts of carnauba / rice wax (weight ratio 3: 7), and 947 parts of ethyl acetate, and the temperature was raised to 80 ° C. with stirring. , Kept at 80 ° C. for 4 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 0.8 hour to obtain [Raw material solution 3].
[Raw Material Solution 3] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. Carbon black and wax were dispersed under conditions of filling and 5 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and the mixture was passed through a bead mill under the above conditions for 3 passes to obtain [Pigment / Wax Dispersion 3]. The solid content concentration of [Pigment / Wax Dispersion 3] was 50%.

Example 7
In Example 1, a toner was obtained in the same manner as in Example 1 except that the steps of solvent removal from low molecular weight polyester and emulsification were changed to the following conditions. The physical properties of [Toner 7] obtained are shown in Table 1, and the evaluation results are shown in Table 2.
(Synthesis of low molecular weight polyester)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react for 7 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, and then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C. under normal pressure. By reacting for 3 hours, [low molecular weight polyester 2] was obtained. [Low molecular polyester 2] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, a peak molecular weight of 3,100, a Tg of 43 ° C., and an acid value of 25.
(Production of oil phase)
378 parts of [Low molecular weight polyester 2], 100 parts of carnauba wax, and 947 parts of ethyl acetate were charged in a container equipped with a stirring bar and a thermometer, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. 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 4].
[Raw material solution 4] Transfer 1324 parts to a container and use a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.) to feed a liquid at a rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5% zirconia beads at 80% by volume. Carbon black and wax were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 2] was added, and the mixture was subjected to 3 passes with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 4]. The solid content concentration of [Pigment / Wax Dispersion 4] was 50%.
(Emulsification to solvent removal)
[Pigment / Wax Dispersion 4] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) for 2 minutes at 5,000 rpm After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 40 minutes to obtain [Emulsion slurry 4].
[Emulsion slurry 4] 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 5 hours to obtain [Dispersed slurry 4].

Example 8
In Example 1, a toner was obtained in the same manner as in Example 1 except that the conditions were changed as follows. The physical properties of the obtained [Toner 8] are shown in Table 1, and the evaluation results are shown in Table 2.
(Production of oil phase)
378 parts of [Low molecular polyester 1], 380 parts of carnauba wax wax, and 947 parts of ethyl acetate were charged in a container equipped with a stir bar and a thermometer, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 4 hours. Thereafter, it was 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 2 hours to obtain [Raw material solution 5].
[Raw material solution 5] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.), liquid feeding speed is 1 kg / hr, disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and wax were dispersed under conditions of filling and 7 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and the mixture was subjected to 4 passes with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 5]. The solid content concentration of [Pigment / Wax Dispersion 5] was 50%.

Comparative Example 1
In Example 1, a toner was obtained in the same manner as in Example 1 except that the conditions were changed as follows. Table 1 shows the physical properties of [Toner 9] obtained, and Table 2 shows the evaluation results.
An alkali (sodium hydroxide) treatment (pH = 11) step was inserted between the emulsification and solvent removal steps to dissolve and remove resin fine particles on the toner surface.

Comparative Example 2
In Example 1, a toner was obtained in the same manner as in Example 1 except that the conditions were changed as follows. The physical properties of [Toner 10] obtained are shown in Table 1, and the evaluation results are shown in Table 2.
(Synthesis of low molecular weight polyester)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react for 7 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, and then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C. under normal pressure. By reacting for 3 hours, [low molecular weight polyester 2] was obtained. [Low molecular polyester 2] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, a peak molecular weight of 3,100, a Tg of 43 ° C., and an acid value of 25.
(Production of oil phase)
378 parts of [Low molecular weight polyester 2], 100 parts of carnauba wax, and 947 parts of ethyl acetate were charged in a container equipped with a stirring bar and a thermometer, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. 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 4].
[Raw material solution 4] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. Carbon black and wax were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 2] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 4]. The solid content concentration of [Pigment / Wax Dispersion 4] was 50%.
(Emulsification to solvent removal)
[Pigment / Wax Dispersion 4] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) for 2 minutes at 5,000 rpm After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and allowed to stand for 1 hour to obtain [Emulsified Slurry 5].
[Emulsion slurry 5] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Dispersion slurry 5].

Comparative Example 3
<First step>
(Preparation of dispersion (1))
Styrene 370g
30g of n-butyl acrylate
Acrylic acid 8g
24g dodecanethiol
Carbon tetrabromide 4g
6 g of nonionic surfactant (Nonipol 400: manufactured by Sanyo Kasei) and 10 g of anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku) were dissolved in 550 g of ion-exchanged water. The mixture was dispersed in a flask, emulsified, and slowly mixed for 10 minutes. To this, 50 g of ion-exchanged water in which 4 g of ammonium persulfate was dissolved was added, and after nitrogen substitution, the inside of the flask was stirred. The contents were heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a dispersion liquid (1) was prepared by dispersing resin particles having an average particle diameter of 155 nm, Tg of 59 ° C., and a weight average molecular weight of 12,000.

(Preparation of dispersion (2))
280 g of styrene
120g of n-butyl acrylate
Acrylic acid 8g
6 g of nonionic surfactant (Nonipol 400: manufactured by Sanyo Kasei) and 12 g of anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku) were dissolved in 550 g of ion-exchanged water. The mixture was dispersed in a flask, emulsified, and slowly mixed for 10 minutes. To this was added 50 g of ion-exchanged water in which 3 g of ammonium persulfate was dissolved, and the atmosphere in the flask was stirred. While heating in an oil bath until the content reaches 70 ° C., the emulsion polymerization is continued for 5 hours to disperse resin particles having an average particle size of 105 nm, Tg of 53 ° C., and a weight average molecular weight of 550,000. A dispersion (2) was prepared.

(Preparation of colorant dispersion (1))
Carbon black (Mogal L: Cabot) 50g
Nonionic surfactant (Nonipol 400: Sanyo Kasei) 5g
200g of ion exchange water
The above is mixed, dissolved, and dispersed for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA) to disperse a colorant (carbon black) having an average particle size of 250 nm (carbon black) 1) was prepared.

(Preparation of release agent dispersion (1))
Paraffin wax (Nippon Seiwa Co., Ltd .: HNP0190, melting point 85 ° C.) 50 g
Cationic surfactant (Sanisol B50: manufactured by Kao) 7g
200g of ion exchange water
The above was heated to 95 ° C. and dispersed using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then dispersed with a pressure discharge homogenizer to disperse a release agent having an average particle size of 550 nm. A release agent dispersion (1) was prepared.

(Preparation of aggregated particles)
Dispersion (1) 120g
Dispersion (2) 80g
Colorant dispersion (1) 30g
Release agent dispersion (1) 40 g
Cationic surfactant (Sanisol B50: manufactured by Kao) 1.5g
The above was mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then heated to 48 ° C. while stirring the inside of the flask in a heating oil bath. After holding for 30 minutes at 48 ° C., it was confirmed that agglomerated particles child average particle size of about 5μm and observed with an optical microscope is formed.

<Second step>
(Preparation of adhered particles)
To this, 60 g of the dispersion liquid (1) as the resin-containing fine particle dispersion liquid was gradually added . Their to, the temperature of the heating oil bath and held for 1 hour raised to 50 ° C..

<Third step>
Then, after adding 3 g of an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku), the stainless steel flask was sealed and heated to 105 ° C. while continuing stirring using a magnetic seal, Hold for 3 hours. Then, after cooling, the reaction product was filtered, thoroughly washed with ion exchange water, and then dried to obtain a toner base. Thereafter, 100 parts of toner base particles were mixed with 1 part of hydrophobic silica and 1 part of hydrophobic titanium oxide using a Henschel mixer to obtain a toner. Table 1 shows the physical properties of [Toner 11] and Table 2 shows the evaluation results.

Comparative Example 4
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 230 ° C. for 8 hours under normal pressure. The reaction was further carried out at a reduced pressure of 10 to 15 mmHg for 5 hours, followed by cooling to 160 ° C., 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Subsequently, it cooled to 80 degreeC and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours, and isocyanate group containing [Prepolymer 2] was obtained. Next, 267 parts of [Prepolymer 2] and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain [Urea-modified polyester 1] having a weight average molecular weight of 64,000.
In the same manner as above, 724 parts of bisphenol A ethylene oxide 2-mole adduct, 138 parts of terephthalic acid and 138 parts of isophthalic acid were polycondensed at 230 ° C. for 6 hours under normal pressure, and then reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. [Unmodified polyester a] having a peak molecular weight of 2,300, a hydroxyl value of 55 and an acid value of 1 was obtained.
200 parts of [Urea-modified polyester 1] and 800 parts of [unmodified polyester a] were dissolved and mixed in 1000 parts of an ethyl acetate / MEK (1/1) mixed solvent to obtain an ethyl acetate / MEK solution of a toner binder. In a reaction vessel equipped with a condenser, a stirrer, and a thermometer, 942 parts of water and 58 parts of a 10% suspension of hydroxyapatite (Superite 10: manufactured by Nippon Chemical Industry Co., Ltd.) were placed. 1000 parts of MEK solution was added and dispersed. The temperature was raised to 98 ° C., the organic solvent was distilled off, and after cooling, filtered from water, washed and dried to obtain [Toner Binder 1]. [Toner binder 1] had a Tg of 52 ° C., a Tη of 123 ° C., and a TG ′ of 132 ° C.
100 parts of [Toner Binder 1], 7 parts of glycerin tribehenate and 4 parts of cyanine blue KRO (manufactured by Sanyo Dye) were converted into a toner by the following method. First, after premixing using a Henschel mixer (FM10B: manufactured by Mitsui Miike Chemical Co., Ltd.), the mixture was kneaded using a biaxial kneader (PCM-30: manufactured by Ikekai). Subsequently, the mixture was finely pulverized using a supersonic jet pulverizer Labo Jet (manufactured by Nippon Pneumatic Industry) and then classified by an airflow classifier (MDS-I: manufactured by Nippon Pneumatic Industry) to obtain toner base particles. Thereafter, 100 parts of toner base particles were mixed with 1 part of hydrophobic silica and 1 part of hydrophobic titanium oxide using a Henschel mixer to obtain a toner. Table 1 shows the physical properties of [Toner 12] obtained, and Table 2 shows the evaluation results.

Comparative Example 5
(Prepolymer production)
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, and reacted at 230 ° C. for 8 hours under normal pressure. The mixture was further reacted for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg, then cooled to 160 ° C., 74 parts of phthalic anhydride was added thereto, and the mixture was reacted for 2 hours. Next, the mixture was cooled to 80 ° C. and reacted with 174 parts of ethylene glycol diglycidyl ether in toluene for 2 hours to obtain an epoxy group-containing [prepolymer 3] having a weight average molecular weight of 13,000.
(Production of ketimine compounds)
In a reaction vessel equipped with a stir bar and a thermometer, 30 parts of isophoronediamine and 70 parts of MEK were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 2].
(Manufacture of dead polymers)
In the same manner as above, 654 parts of bisphenol A ethylene oxide 2-mol adduct and 516 parts of dimethyl terephthalate were polycondensed at 230 ° C. for 6 hours under normal pressure, and then reacted for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg. [Dead polymer 1] having a peak molecular weight of 2,400 and a hydroxyl value of 2 was obtained.

(Manufacture of toner)
In a beaker, 15.4 parts of the above [Prepolymer 3], 64 parts of [Dead polymer 1] and 78.6 parts of ethyl acetate were stirred and dissolved. Next, 20 parts of pentaerythritol tetrabehenate and 4 parts of cyanine blue KRO (manufactured by Sanyo Dye) were added and stirred at 12,000 rpm with a TK homomixer at 60 ° C. to uniformly dissolve and disperse. Finally, 2.7 parts of [ketimine compound 2] was added and dissolved. This is designated as toner material solution (1).
In a beaker, 706 parts of ion-exchanged water, 294 parts of hydroxyapatite 10% suspension (Superite 10: manufactured by Nippon Kagaku Kogyo) and 0.2 part of sodium dodecylbenzenesulfonate were uniformly dissolved. Next, the temperature was raised to 60 ° C., and the toner material solution (1) was added while stirring at 12,000 rpm with a TK homomixer, followed by stirring for 10 minutes. The mixture is then transferred to a Kolben equipped with a stirrer and a thermometer, heated to 98 ° C., the solvent is removed while undergoing a urea reaction, filtered, washed and dried, and then air classified to obtain a toner base. Particles were obtained. Thereafter, 100 parts of toner base particles were mixed with 1 part of hydrophobic silica and 1 part of hydrophobic titanium oxide using a Henschel mixer to obtain a toner. The toner binder component had a weight average molecular weight of 14,000, a number average molecular weight of 2,000, and a Tg of 52 ° C. Table 1 shows the physical properties of [Toner 13] and Table 2 shows the evaluation results.

Comparative Example 6
(Method for producing polymer A)
A flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 300 g of methanol, 100 g of toluene, 570 g of styrene, 30 g of 2-acrylamido-2-methylpropanesulfonic acid, and 12 g of lauroyl peroxide, and stirred at 65 ° C. while introducing nitrogen. The solution was polymerized for 10 hours, the contents were taken out from the flask, dried under reduced pressure, and then pulverized by a jet mill to produce an A polymer having a weight average molecular weight of 3,000.

(Manufacture of toner)
Styrene 183 parts 2-ethylhexyl acrylate 17 parts A polymer 0.1 part
CI Pigment Yellow 17 7 parts Paraffin wax (melting point 155 ° F: manufactured by Taisei Kosan Co., Ltd.) 32 parts Initiator (V-601: Wako Pure Chemical Industries, Ltd.) 10 parts The above formulation is heated to 65 ° C and dissolved or dispersed uniformly. A monomer composition was obtained.
Separately, 0.3 g of a silane coupling agent (KBE903: manufactured by Shin-Etsu Silicone) was uniformly dispersed in 1200 ml of ion-exchanged water, and 6 g of colloidal silica (Aerosil # 200: manufactured by Nippon Aerosil) was added to further uniformly disperse. This dispersion was adjusted to pH = 6 with hydrochloric acid to prepare a dispersion medium system.
The monomer composition was charged into this dispersion medium, and stirred at 6,500 rpm for 60 minutes at 70 ° C. in a nitrogen atmosphere to granulate the monomer composition. Thereafter, polymerization was performed at 75 ° C. for 8 hours while stirring with a paddle stirring blade.
After completion of the polymerization reaction, the reaction product was cooled, 42 g of a 20% aqueous sodium hydroxide solution was added and the mixture was alkali treated overnight to dissolve the dispersant, filtered, washed with water, and dried to obtain a toner. The physical properties of the obtained [Toner 4] are shown in Table 1, and the evaluation results are shown in Table 2.

The physical properties of the toner were evaluated as follows.
(Surface properties)
A Digital Instruments Nanoscope IIIa controller and D-3100 / P system were used as an atomic force microscope (AFM) apparatus. The surface shape was measured and analyzed using the tapping mode. As the cantilever, a Si single crystal (TESP) having a spring constant of about 50 N / m and a resonance frequency of 270 kHz was used.
(Roundness)
Measurement was carried out using a flow particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 mL of water from which impure solids had been removed in advance was added, 0.1 to 0.5 mL of a surfactant was added as a dispersant, and about 0.1 to 9.5 g of a measurement sample was further added. . The suspension in which the sample was dispersed was subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the dispersion concentration was set to 3,000 to 10,000 / μL, and the shape and distribution of the toner were measured.
(Shape factor)
A toner photograph was taken with a scanning electron microscope (S-800: manufactured by Hitachi, Ltd.), and this was analyzed and calculated using an image analyzer (LUSEX 3: manufactured by Nireco).
(Average particle size and particle size distribution)
A Coulter counter TA-II type (manufactured by Coulter Inc.) was connected to an interface (manufactured by Nikka Giken) and PC9801 personal computer (manufactured by NEC) to output the number distribution and volume distribution.

The toner was evaluated as follows.
(Evaluation item)
1) Cleanability After outputting 1,000 sheets of a 95% image area ratio chart, the transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to white paper with a scotch tape (manufactured by Sumitomo 3M), and this is transferred to a Macbeth reflection densitometer RD514. Measured with a mold, the difference between the blank and less than 0.005 is ◎, 0.005 to 0.010 is ◯, 0.011 to 0.02 is △, and more than 0.02 It evaluated as x.

2) Transferability After transferring the chart with an image area ratio of 20% from the photoconductor to the paper, the transfer residual toner on the photoconductor immediately before the cleaning process is transferred to white paper with Scotch tape (manufactured by Sumitomo 3M), and it is applied to the Macbeth reflection densitometer. Measured with RD514 type, ◎ if the difference from the blank is less than 0.005, ○ if 0.005 to 0.010, Δ if 0.011 to 0.02, and more than 0.02. Was evaluated as x.

3) Charging Stability Using an evaluation machine that was tuned by remodeling Ricoh's IPSiO Color 8100 into an oil-less fixing system, an image area ratio 5% chart continuous 100,000 sheet output durability test was conducted using each toner. The change in the charge amount at that time was evaluated. 1 g of developer was weighed and the change in charge amount was determined by the blow-off method. When the change in the charge amount was 5 μc / g or less, it was evaluated as ◯, when it was 10 μc / g or less, Δ when it exceeded 10 μc / g.

4) Image Density Ricoh's imagio Neo 450 was remodeled as a belt fixing method, and after printing a solid image with an adhesion amount of 0.4 ± 0.1 mg / cm ^{2 on} plain paper transfer paper (Ricoh Type 6200), the image The concentration was measured by X-Rite (manufactured by X-Rite). An image density of 1.4 or higher was evaluated as ◯, and an image density lower than that as X.

5) Image graininess and sharpness Using an evaluation machine that has been tuned by remodeling Ricoh's IPSiO Color 8100 into an oil-less fixing system, output a photographic image in a single color and visually evaluate the degree of graininess and sharpness. did. Evaluations were made from GOOD, ◎, ○, Δ, and ×.並 is equivalent to offset printing, ◯ is slightly worse than offset printing, Δ is much worse than offset printing, and × is very bad compared to conventional electrophotographic images.

6) Fog In an environment with a temperature of 10 ° C and a humidity of 15%, using an evaluation machine that was tuned by remodeling Ricoh's IPSiO Color 8100 into an oil-less fixing system, using each toner, an image area ratio of 5% chart 100, After the 000 sheet output durability test, the degree of toner contamination on the transfer paper upper surface was visually evaluated (loupe). Evaluations were made from GOOD, ◎, ○, Δ, and ×. ◎ indicates a good state in which no toner stains are observed, ○ indicates a state in which slight stains are not observed and does not pose a problem, Δ indicates a state in which slight stains are observed, and × indicates very dirty outside the allowable range Indicates a problem state.

7) Toner scattering In an environment with a temperature of 40 ° C. and a humidity of 90%, using an evaluation machine that has been tuned by modifying the Ricoh IPSiO Color 8100 into an oilless fixing system, an image area ratio of 5% is continuously displayed using each toner. After the 1,000 sheet output durability test, the toner contamination state in the copying machine was visually evaluated. ◎ indicates a good state in which no toner stains are observed, ○ indicates a state in which slight stains are observed and does not pose a problem, Δ indicates a state in which slight stains are observed, and × indicates a state outside the allowable range. This indicates a state that is dirty and causes a problem.

8) Environmental preservation (blocking resistance)
Weigh 10 g of toner, put it in a 20 ml glass container, tap the glass bottle 100 times, leave it in a thermostatic chamber set at 55 ° C. and 80% humidity for 24 hours, and then check the penetration with a penetration meter. It was measured. The toner stored in a low-temperature and low-humidity (10 ° C., 15%) environment was similarly evaluated for penetration, and the value with the lower penetration was employed in a high-temperature and high-humidity and low-temperature and low-humidity environment. From the good one, ◎: 20 mm or more, ◯: 15 mm or more and less than 20 mm, Δ: 10 mm or more to less than 15 mm, x: less than 10 mm.

The physical properties of the toners obtained in the above examples and comparative examples are shown in Table 1 below, and the evaluation results of the toner are shown in Table 2 below.

  As can be seen from the results in Tables 1 and 2, the toner having the specified surface properties of the present invention is a toner having good chargeability, developability and transferability. Further, by controlling the circularity, the shape factor, and the particle size, it is possible to obtain a toner that is free from fogging, toner scattering, etc., has excellent cleaning properties, and has excellent environmental preservation stability.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present invention.

Explanation of symbols

1 Photoconductor (latent image carrier)
2 Charging device 3 Exposure device 4 Developing device 4a Developer carrier 6 Transfer device 7 Fixing device 8 Cleaning device 100 Image forming device

Claims (14)

In a toner comprising at least a binder resin and a colorant,
The toner includes a toner material solution obtained by dissolving or dispersing at least a polyester prepolymer having a functional group containing a nitrogen atom, a polyester, a colorant, and a release agent in an organic solvent. Alternatively, it is allowed to elongate and granulate in a liquid medium containing resin fine particles to adhere the resin fine particles to the toner surface. After the granulation step in the liquid medium, the washing and solvent removal steps are followed by the washing. Either before or after the solvent removal step , inorganic particles are adhered to the toner base particles obtained through the aging step of aging the toner particles in the liquid medium at 25 to 50 ° C. for 10 minutes to 23 hours and having the following surface properties Toner.
(1) The surface roughness Ra is 1 to 30 nm.
(2) The standard deviation RMS of the surface roughness is 10 to 90 nm.
(3) The number of convex portions having a height difference of 10 nm or more from the bottom of the concave portion to the top of the convex portion is 1 to 20 / μm. The toner according to claim 1.
The toner has an average circularity of toner particles of 0.93 to 1.00. The toner according to claim 2,
The toner is characterized in that the ratio of toner particles having a circularity of less than 0.93 is 30% or less. The toner according to any one of claims 1 to 3,
The toner has a volume average particle diameter (Dv) of 2.0 to 6.0 μm and a ratio Dv / Dn to the number average particle diameter (Dn) of 1.00 to 1.40. Toner. In the toner according to any one of claims 1 to 4,
The toner is characterized in that the ratio Ra (nm) / Dv (μm) between the surface roughness (Ra) and the volume average particle diameter (Dv) is 0.2 to 6.0. The toner according to any one of claims 1 to 5,
The toner has a shape factor SF-2 in the range of 100 to 140, and a ratio Ra (nm) / SF-2 of the surface roughness (Ra) to the shape factor SF-2 is 0.007 to 0.30. Toner characterized by being. The toner according to any one of claims 1 to 6,
The toner has a vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin and polycarbonate resin on the surface of the toner base particles. A toner characterized in that at least one of them is present. The toner according to claim 7,
The toner is obtained by granulating in a liquid medium containing resin fine particles having a volume average particle diameter of 20 to 150 nm, and the resin fine particles adhere to the toner surface. The toner according to claim 8.
The toner according to claim 1, wherein the resin fine particles have a spherical shape. The toner according to claim 7, wherein:
The toner includes a release agent. A developer for developing an electrostatic latent image formed on a latent image carrier,
  The developer is a two-component developer comprising the toner according to any one of claims 1 to 10 and a magnetic carrier.
  A developer characterized by that. A developer for developing an electrostatic latent image formed on a latent image carrier,
  The developer is a one-component developer using the toner according to any one of claims 1 to 10.
  A developer characterized by that. A developing device that carries and conveys a developer by a developer carrying member, an alternating electric field is applied at a position facing the latent image carrying member, and develops an electrostatic latent image on the latent image carrying member,
The developer uses the developer according to claim 11 or 12.
A developing device. A latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and the surface of the charged latent image carrier is exposed based on image data, whereby an electrostatic latent image is obtained. An exposure unit for writing, a developing unit for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier and a visible image, and a visible image on the surface of the latent image carrier are transferred to a transfer target In an image forming apparatus comprising: a transfer unit that fixes; and a fixing unit that fixes a visible image on the transfer target.
  The developing device is the developing device according to claim 13.
  An image forming apparatus.

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