JP4815306B2 - Toner, developer and image forming method using the same - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, a developer using the toner, and an image forming method.

  Conventionally, in an electrophotographic image forming apparatus, an electrostatic recording apparatus, or the like, an electric latent image or a magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. This toner image is usually transferred onto a recording medium such as paper and then fixed by a method such as heating. The toner used for electrostatic image development is generally colored particles in which a colorant, a charge control agent, and other additives are contained in a binder resin. And polymerization method.

  In the pulverization method, a toner material such as a colorant, a charge control agent, and an anti-offset agent is melt-mixed and uniformly dispersed in a thermoplastic resin, and the obtained toner composition is pulverized and classified. Toner is manufactured. According to such a pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, a toner composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable apparatus. From this demand, the melt-mixed toner composition must be sufficiently brittle. For this reason, when the toner composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and if an attempt is made to obtain a copy image with good resolution and gradation, for example, A fine powder having a diameter of 5 μm or less and a coarse powder having a diameter of 20 μm or more must be removed by classification, which has a disadvantage that the yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse additives such as a colorant and a charge control agent in the thermoplastic resin. Such non-uniform dispersion of additives adversely affects toner fluidity, developability, durability, image quality, and the like.

  In recent years, in order to overcome problems in the pulverization method, a toner production method using a polymerization method has been proposed and implemented. As a technique for producing a toner for developing an electrostatic latent image by a polymerization method, for example, there is a suspension polymerization method. However, there is a problem that the toner obtained by the suspension polymerization method contaminates a charging roller or the like that contacts and charges the electrostatic latent image carrier (photosensitive member) and cannot exhibit the original charging ability.

For this reason, a method has been proposed in which resin fine particles obtained by an emulsion polymerization method are associated to obtain an amorphous toner (see Patent Document 1). However, in the toner obtained by this emulsion polymerization method, the surfactant remains in a large amount not only on the surface of the toner but also in the toner even after the water washing step, and the environmental stability of charging of the toner is impaired. The charge amount distribution is widened, and the background stain of the obtained image becomes poor. Further, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, etc., and the original charging ability cannot be exhibited.
In addition, in the method of obtaining an irregular shaped toner by associating resin fine particles obtained by emulsion polymerization, in order to improve offset resistance, when releasing agent fine particles are associated, As a result, the offset resistance cannot be sufficiently improved. Resin fine particles, release agent fine particles, colorant fine particles, etc. are randomly fused to form a toner, so that variations in composition (content ratio of constituent components) and molecular weight of constituent resins occur between the obtained toners. . As a result, the surface characteristics differ between the toners, and a stable image cannot be formed over a long period of time. Further, in a low-temperature fixing system that requires low-temperature fixing, there is a problem that fixing temperature range cannot be ensured due to fixing inhibition caused by resin fine particles unevenly distributed on the toner surface.

  Further, a toner production method called a dissolution suspension method has been proposed (see Patent Document 2). This method is a method of granulating from a polymer dissolved in an organic solvent or the like, whereas the suspension polymerization method forms polymer particles from monomers, and it is possible to expand the selection range of resins, control the polarity, etc. There are advantages. In addition, there is an advantage that the structure control of the toner (the preparation of the core / shell structure) is possible, but the shell structure is a resin-only layer intended to reduce the exposure of the pigment and wax to the surface. In particular, the surface condition is not devised, nor is such a structure. Therefore, although it has a core / shell structure, the toner surface is a normal resin and is not particularly devised. When aiming at lower temperature fixing, it is sufficient in terms of heat-resistant storage stability and environmental charge stability. Not a problem.

Moreover, it is common to use a styrene-acrylic acid ester copolymer for any of the above suspension polymerization method, emulsion polymerization method and dissolution suspension method. Distribution and shape control are difficult, and there was a limit to fixability when aiming at lower temperature fixing.
For the purpose of heat-resistant storage stability and low-temperature fixing, it has been proposed to use a polyester resin modified with a urea bond (see Patent Document 3). However, even in this proposal, the surface is not particularly devised, and there is a problem in that it is not sufficient in terms of environmental charge stability which is more severe.

  Recently, in the field of electrophotography, high image quality has been studied from various angles, and among them, the recognition that toner diameter reduction and spheroidization are extremely effective is increasing. However, as the diameter of the toner is reduced, the transferability and the fixing property are lowered, and a tendency to become a poor image is observed. It is also known that transferability is improved by making the toner spherical (see Patent Document 4). Under such circumstances, further speeding up of image formation is desired in the field of color copiers and color printers. In order to achieve such a high speed, the “tandem method” is effective (see Patent Document 5).

  Further, in a fixing process using a contact heating method performed using a heating member such as a heat roller, toner releasability (hereinafter referred to as “offset resistance”) with respect to the heating member is required. Such offset resistance can be improved by the presence of a release agent on the toner surface. Patent Documents 6 and 7 propose not only a method in which the resin fine particles are contained in the toner, but also a method for improving the offset resistance because the resin fine particles are unevenly distributed on the toner surface. . However, in these proposals, the minimum fixing temperature increases, and the low temperature fixing property, that is, the energy saving fixing property is not sufficient.

  As for the charging characteristics of the toner, it has been proposed that the toner contains a fluorine-based compound as a means for increasing the charging ability of the negatively charged toner, for example, as a charge control agent (Patent Document 8 and Patent Document 9). reference). However, these proposals do not have a sufficient effect of improving the charging start-up property, cause toner background contamination (fogging) and toner scattering, and have problems in terms of environmental charging stability.

As a charge control agent, there are many polar compounds, and when the charge control agent is internally added in the toner granulation method using aqueous emulsification using an aqueous phase and an oil phase, the affinity and solubility for the oil phase and the aqueous phase are added. In many cases, it is eluted into the aqueous phase, and it is substantially difficult to internally add a charge control agent to the aqueous granulated toner (see Patent Document 10).
Further, Patent Document 11 proposes a toner having a high charging ability, a sharp charge amount distribution, a weakly charged, and a low amount of reversely charged toner by adding a fluorine compound to the toner surface by wet external addition. However, in this proposal, there is a problem that a charge amount aging decrease due to long-time stirring with the carrier. In Patent Document 11, a toner is proposed in which a fluorine-based compound is dispersed in an aqueous medium to be contained in the toner. However, even in this proposal, a decrease in charge amount with time occurs, and the cause of such a decrease in charge amount is not known and difficult to solve.

  As described above, as a means for increasing the charging ability of toner (particularly negatively charged toner), it is not possible to obtain a sufficient charging effect by simply adding a fluorine-based compound in the toner production process. The current situation is that further improvement and development of conditions are desired.

Japanese Patent No. 2537503 Japanese Patent No. 3141784 Japanese Patent Laid-Open No. 11-133667 JP 9-258474 A JP-A-5-341617 JP 2000-292773 A JP 2000-292978 A Japanese Patent No. 2942588 Japanese Patent No. 3102797 Japanese Patent No. 3069936 JP 2005-115213 A

  An object of the present invention is to solve the conventional problems in response to the above-mentioned demands and achieve the following object. That is, the present invention can form a visible image with a long initial charge buildup, a sharp charge distribution, and a sharp sharpness while maintaining a stable charge with little change in charge over time. An object of the present invention is to provide a toner for developing an electrostatic image corresponding to a low-temperature fixing system, a developer using the toner, and an image forming method.

  In order to solve the above problems, the present inventors have conducted intensive studies. As a result, N, N, N-trimethyl- [3- (4-perfluorononenyloxy) is used as a charge control agent for the binder resin contained in the toner base. Benzamide) propyl] ammonium iodide and other fluorine-containing quaternary ammonium salt compounds are ionically bonded so that the fluorine-containing quaternary ammonium salt compound is uniformly present inside the toner, thereby reducing the change in toner charge over time. It has been found that stable chargeability can be realized.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> Obtained by removing an organic solvent from a dispersion in which a toner material containing at least a binder resin and a charge control agent is dissolved or dispersed in an organic solvent and dispersed in an aqueous medium. Toner,
In the toner, the binder resin has at least a functional group capable of ion binding, and the charge control agent is ionically bonded to the binder resin inside the toner.
<2> The aqueous medium contains at least resin fine particles, the resin fine particles have a functional group capable of ion bonding, and at least one of the resin fine particles and the binder resin is ionically bonded to the charge control agent inside the toner. The toner according to <1>.
<3> The toner according to any one of <1> to <2>, wherein the charge control agent is a fluorine-containing quaternary ammonium salt compound.
<4> The toner according to <3>, wherein the fluorine-containing quaternary ammonium salt compound is a compound represented by the following structural formula (1).
However, in the structural formula (1), R ¹ represents any ^one of a hydrogen atom, a fluorine atom, and a hydrocarbon group. R ^{2 to} R ⁴ may be the same as or different from each other, and each represents a hydrogen atom, a fluorine atom, or a hydrocarbon group. X represents a divalent organic group. Y represents a counter ion. n and m each represents a positive integer.
<5> The above <4>, wherein the fluorine-containing quaternary ammonium salt compound is N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide represented by the following structural formula. The toner described in 1.
<6> The toner according to any one of <1> to <5>, wherein a content of the fluorine-containing quaternary ammonium salt compound in the toner is 0.05 to 10% by mass.
<7> The toner according to any one of <1> to <6>, wherein the binder resin has a carboxyl group at a terminal.
<8> The toner according to any one of <1> to <7>, wherein the binder resin contains a polyester resin.
<9> The toner according to any one of <1> to <8>, wherein the acid value of the binder resin is 1 to 30 mgKOH / g.
<10> The toner according to any one of <1> to <9>, wherein the binder resin has a glass transition temperature (Tg) of 40 to 90 ° C.
<11> The above-mentioned <1>, which contains resin fine particles on at least one of the toner surface and inside, and the resin fine particles contain at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins. To <10>.
<12> The toner according to <11>, wherein the resin fine particles have a mass average molecular weight of 5,000 to 200,000.
<13> The volume average particle diameter (Dv) of the toner is 4 to 8 μm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.25 or less. The toner according to any one of <1> to <12>.
<14> A developer comprising the toner according to any one of <1> to <13>.
<15> The developer according to <14>, which is one of a one-component developer and a two-component developer.
<16> A toner-containing container filled with the toner according to any one of <1> to <13>.
<17> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to <13> to be a visible image And a developing means for forming the process cartridge.
<18> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and using the toner according to any one of <1> to <13>, A developing step for developing to form a visible image; a transferring step for transferring the visible image to a recording medium; a fixing step for fixing the transferred image transferred to the recording medium; and the electrostatic latent image carrier. An image forming method comprising at least a cleaning step of removing toner remaining on the top.
<19> The image forming method according to <18>, further including a recycling step in which the toner removed by the cleaning step is recycled to the development step.
<20> An electrostatic latent image carrier, an electrostatic latent image forming unit for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of <1> to <13> Developing means for developing a visible image by developing using any of the toners, Transfer means for transferring the visible image to a recording medium, and Fixing means for fixing the transferred image transferred to the recording medium And at least a cleaning unit for removing toner remaining on the electrostatic latent image carrier.
<21> The image forming apparatus according to <20>, further including a recycling unit that recycles the toner removed by the cleaning unit to the developing unit.

The toner of the present invention removes an organic solvent from a dispersion in which a solution or dispersion in which a toner material containing at least a binder resin and a charge control agent is dissolved or dispersed in an organic solvent is dispersed in an aqueous medium. Obtained by
The binder resin has at least a functional group capable of ion binding, and the charge control agent is ionically bonded to the binder resin inside the toner.
In the toner of the present invention, it is possible to form a visible image with a long initial charge buildup, sharp charge distribution and good sharpness over a long period of time while maintaining a stable charge amount with little change in charge amount over time. it can.

  In the developer of the present invention, since the toner of the present invention is used, the initial charge rise is fast, the charge amount distribution is sharp and sharp, while maintaining a stable charge amount with little change in charge amount over time. Can be formed over a long period of time.

  The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, a fixing step, and a cleaning step. In the image forming method, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. In the cleaning step, the toner remaining on the electrostatic latent image carrier is removed. As a result, in the image forming method of the present invention, a visible image with good sharpness can be formed over a long period of time.

  According to the present invention, conventional problems can be solved, and the initial charge rise is fast, the charge amount distribution is sharp, and the sharpness is excellent while maintaining a stable charge amount with little change in charge amount with time. An image can be formed over a long period of time, and a toner for developing an electrostatic image corresponding to a low-temperature fixing system, a developer using the toner, and an image forming method can be provided.

(toner)
The toner of the present invention removes an organic solvent from a dispersion in which a solution or dispersion in which a toner material containing at least a binder resin and a charge control agent is dissolved or dispersed in an organic solvent is dispersed in an aqueous medium. Is obtained.
The binder resin has at least a functional group capable of ion binding, and the charge control agent is ionically bonded to the binder resin inside the toner.
The aqueous medium contains at least resin fine particles, the resin fine particles have a functional group capable of ion bonding, and at least one of the resin fine particles and the binder resin is ionically bonded to the charge control agent inside the toner. Is preferred.

  Here, when the toner contains a fluorine-containing quaternary ammonium salt compound as a charge control agent, the reason why the toner charge amount decreases with time can be considered as follows. That is, when a toner material containing resin fine particles that are likely to be unevenly distributed on the toner surface or in the vicinity of the toner surface is used for the purpose of preventing aggregation between particles during toner emulsification, a fluorine-containing quaternary ammonium salt compound as a charge control agent is used for the resin fine particles. Are bonded preferentially, and the fluorine-containing quaternary ammonium salt compound is unevenly distributed on the toner surface, and the fluorine-containing quaternary ammonium salt compound may disappear from the toner due to toner surface abrasion or toner surface cracking caused by stirring with a carrier. This is presumed to be the main cause of the decrease in toner charge amount with time.

This is clear from SEM image observation, X-ray photoelectron spectroscopy measurement, NMR measurement, and charge amount measurement results.
That is, using a toner material containing a binder resin and resin fine particles, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamide as a fluorine-containing quaternary ammonium salt compound as a charge control agent )] Propyl] ammonium iodide (hereinafter referred to as fluorine-containing quaternary ammonium salt compound (1)) was added in the same manner as in Japanese Patent Application Laid-Open No. 2005-115213. Results were obtained.

(1) When an SEM image of the toner after mixing and stirring with the carrier is observed, a change in the toner surface is observed, and a state in which peeling occurs in the toner outer skin portion is observed.
For the measurement, JSM-7400F manufactured by JEOL Ltd. was used. FIG. 1 is a diagram showing a toner with a part of the surface shaved, and FIG. 2 is a diagram showing a toner with the surface almost shaved and only a part of the outer skin remaining.

(2) When an EDS element mapping method is used to examine the location of fluorine atoms, a large amount of fluorine atoms are present in the toner coat. On the other hand, the result that there were almost no fluorine atoms inside the toner was obtained.
JSM-7400 made by JEOL Ltd. was used for the measurement. FIG. 3 is a diagram showing the location of fluorine atoms in FIG. 1, and FIG. 4 is a diagram showing the location of fluorine atoms in FIG. The black part in the figure is the part where the detected amount of fluorine atoms is large. The result of FIG. 3 shows that a lot of fluorine atoms exist in the surface shaved portion, and almost no fluorine atoms are detected on the outermost surface. From the results shown in FIG. 4, it can be seen that fluorine atoms are present in the slightly remaining outer skin-like portion, but almost no fluorine atoms are detected in the toner whose outer skin has been completely removed. From this, it can be seen that fluorine atoms are mainly present in the outer skin-like portion near the toner surface and hardly exist inside.

(3) When the presence state of the fluorine-containing quaternary ammonium salt compound in the toner was examined using X-ray photoelectron spectroscopy, the fluorine-containing quaternary ammonium salt compound was a carboxyl group of at least one of the binder resin and the resin fine particles. The result of ionic bonding with was obtained.
The measurement used Shimadzu Corporation AXIS-ULTRA. N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide is N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamide) in the raw material powder. ) Propyl] ammonium ion and iodine are ion-bonded, but in the analyzed toner, iodine is not present, and is present in the same state (ion-bonded state) as in the raw material powder except that iodine is not present. The results were obtained from FIGS.
FIG. 5 is a plot showing that the main peak of iodine does not exist in the toner for analysis obtained by X-ray photoelectron spectroscopy.
FIG. 6 is a plot showing the main peak of fluorine of the toner for analysis obtained by X-ray photoelectron spectroscopy.
FIG. 7 is a plot diagram showing the main peak of nitrogen of the toner for analysis obtained by X-ray photoelectron spectroscopy.
FIG. 8 is a plot showing the main peak of iodine of the fluorine-containing quaternary ammonium salt compound (1) obtained by X-ray photoelectron spectroscopy.
FIG. 9 is a plot showing the main peak of fluorine of the fluorine-containing quaternary ammonium salt compound (1) obtained by X-ray photoelectron spectroscopy.
FIG. 10 is a plot showing the nitrogen main peak of the fluorine-containing quaternary ammonium salt compound (1) obtained by X-ray photoelectron spectroscopy.
Therefore, the portion in which the fluorine-containing quaternary ammonium salt compound can stably ion-bond with at least one of the binder resin and the resin fine particles is only a carboxyl group, and therefore, the fluorine-containing quaternary ammonium salt compound It is presumed that it is ionically bonded to at least one of the carboxyl groups of the binder resin and resin fine particles.

(4) From the NMR measurement results, it is recognized that the fluorine-containing quaternary ammonium salt compound is mainly added to the resin fine particles on the toner surface.
For NMR measurement, JNM-A400 manufactured by JEOL Ltd. was used. The fluorine determination result was obtained as the ratio of the number of fluorine-containing quaternary ammonium salt compounds to the number of bisphenol A-based molecules in the binder resin. Quantitative analysis of the fluorine-containing quaternary ammonium salt compound in the toner using ¹⁹ F-NMR was conducted to examine the change over time in the amount of the fluorine-containing quaternary ammonium salt compound. The result that the detection amount of a quaternary ammonium salt compound increased was obtained (refer FIG. 11). This indicates that the fluorine-containing quaternary ammonium salt compound is attached to a substance that does not dissolve in THF-d8 used as a solvent for NMR measurement, and resin fine particles correspond to the toner material used. The fact that the resin fine particles are not dissolved in THF-d8 in this way is that the ¹ H-NMR measurement result (see FIG. 12) of the toner prepared from the binder resin without using the resin fine particles, and the resin fine particles were prepared from the binder resin and the resin fine particles. This can be confirmed by comparing the results of ¹ H-NMR measurement of the toner (see FIG. 13), and that no different peaks are observed in both.

The resin fine particles are used to control the toner shape (particle size distribution, circularity, etc.) during toner granulation, and adhere to the toner surface and inside (mainly near the surface) during emulsification. Thus, the resin fine particles adhering to the toner surface suppress aggregation between the toners during emulsification. The methacrylic acid constituting the resin fine particles has a carboxyl group, and a large amount of carboxyl groups are present in the resin fine particles. On the other hand, in the polyester-based resin, the carboxyl group exists only at the terminal, and the toner surface where the resin fine particles are mainly present has more carboxyl groups than in the toner.
Thus, the fact that methacrylic acid, which is one of the monomers constituting the resin fine particles, contains carboxyl groups, and the fact that the carboxyl groups present in the toner are present more in the resin fine particles than in the binder resin is the SEM. The results of image, XPS measurement, and NMR measurement can be explained without contradiction.

(5) When the change in the charge amount over time was examined, the charge amount of the toner containing the fluorine-containing quaternary ammonium salt compound was influenced by the amount of the fluorine-containing quaternary ammonium salt compound present compared with the NMR quantitative analysis results. The result that was large was obtained.
The charge amount was measured by using a blow-off method with a developer composed of toner and an iron powder carrier TEFV200 / 300 (manufactured by Powdertech Co., Ltd.) at a toner concentration of 7% by mass. When the time-dependent change of the charge amount was examined, a correlation with the quantitative analysis result of the fluorine-containing quaternary ammonium salt compound by NMR was observed (see FIG. 14). Thus, it can be seen that the charge amount of the toner containing the fluorine-containing quaternary ammonium salt compound as the charge control agent is greatly influenced by the amount of the fluorine-containing quaternary ammonium salt compound.

  From the above results, the charge control agent is reduced when the surface of the toner is scraped by preferential ion binding of the fluorine-containing quaternary ammonium salt compound to the resin fine particles unevenly distributed in the vicinity of the toner surface. The main reason is thought to be a decrease in the amount.

  The toner material contains at least a binder resin and a charge control agent, and further contains a release agent and, if necessary, other components.

-Charge control agent-
The charge control agent is preferably a fluorine-containing quaternary ammonium salt compound, and more preferably a fluorine-containing quaternary ammonium salt compound represented by the following structural formula (1).
However, in the structural formula (1), R ¹ represents any ^one of a hydrogen atom, a fluorine atom, and a hydrocarbon group. R ^{2 to} R ⁴ may be the same as or different from each other, and each represents a hydrogen atom, a fluorine atom, or a hydrocarbon group. X represents a divalent organic group. Y represents a counter ion. n and m each represents a positive integer.

In _C 3n _{F 6n-1} of the structural formula (1), n 1 to 20, preferably an integer of 1 to 10. _{Specifically, CF 3 (CF 2) 5} -, CF 3 (CF 2) 6 -, CF 3 (CF 2) 7 -, CF 3 (CF 2) 8 -, CF 3 (CF 2) 9 -, _{CF 3 (CF 2) 10 -} , CF 3 (CF 2) 11 -, CF 3 (CF 2) 12 -, CF 3 (CF 2) 13 -, CF 3 (CF 2) 14 -, CF 3 (CF 2 ) _15- , CF ₃ (CF ₂ ) _16- , CF ₃ (CF ₂ ) _17- , (CF ₃ ) ₂ CF (CF ₂ ) _6- , and the like.

  In the structural formula (1), Y represents a counter ion. Examples of the counter ion include halogen ions, sulfate ions, nitrate ions, phosphate ions, thiocyanate ions, organic acid ions, and the like. Among these, halogen ions such as fluorine, chlorine, bromine and iodine are particularly preferable.

In the structural formula (1), X represents a divalent organic group. Examples of the divalent organic group, for _{example, -SO 2 -, - CO -} , - (CH 2) x -, - SO 2 N (R 5) - (CH 2) x -, - (CH 2) x- _{CH (OH) - (CH 2} ) x-, and the like. Here, x represents an integer of 1 to 6. R ⁵ represents an alkyl group having 1 to 10 carbon atoms. Among _{these, -SO 2 -, - CO -} , - (CH 2) 2 -, - SO 2 N (C 2 H 5) - (CH 2) 2 -, or _{-CH 2 CH (OH) CH 2} - Are preferred, and —SO ₂ — or —CO— is particularly preferred.
In the structural formula (1), m represents an integer of 1 or more, preferably 1 to 20, and more preferably 1 to 10.

In the structural formula (1), R ¹ represents a hydrogen atom, a fluorine atom, or a hydrocarbon group. R ^{2 to} R ⁴ may be the same as or different from each other, and each represents a hydrogen atom, a fluorine atom, or a hydrocarbon group. There is no restriction | limiting in particular as this hydrocarbon group, Although it can select suitably according to the objective, For example, an alkyl group, an alkenyl group, an aryl group, etc. are mentioned. These may be further substituted with a substituent.
As the alkyl group, those having 1 to 10 carbon atoms are preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, n-hexyl group, Examples include isohexyl group, n-heptyl group, n-octyl group, isooctyl group, n-decyl group, isodecyl group, and the like, which may be further substituted with a substituent. As the alkenyl group, those having 2 to 10 carbon atoms are more preferable, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, and an octenyl group. And may be further substituted. As said aryl group, a C6-C24 thing is more preferable, For example, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a styryl group, a mesityl group, a cinnamyl group, a phenethyl group, a benzhydryl group etc. are mentioned. These may be further substituted with a substituent.

  Preferable examples of the fluorine-containing quaternary ammonium salt compound represented by the structural formula (1) include compounds represented by the following structural formula.

In the present invention, in the structural formulas (2) to (55), iodine ion (I ⁻ ) or bromine ion (Br ⁻ ) is replaced with chlorine ion (Cl ⁻ ), fluorine ion (F ⁻ ), etc. A compound in place of the halogen atom ion can also be used.

  Among the structural formulas (2) to (55), N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide (the above structural formula) (3)) is particularly preferred.

  The content of the fluorine-containing quaternary ammonium salt compound in the toner is preferably 0.05 to 10% by mass, and more preferably 0.1 to 8% by mass. Within this range, the toner base can be contained by ionic bonding. When the content of the fluorine-containing quaternary ammonium salt compound is less than 0.05% by mass, a sufficient charge amount may not be obtained, and the effects of the present invention may not be sufficiently obtained, and the content exceeds 10% by mass. Then, fixing failure of the developer may occur.

-Binder resin-
The binder resin is not particularly limited as long as it has an ion-bondable functional group, and can be appropriately selected according to the purpose. For example, polystyrene resin, poly-α-still styrene resin, styrene -Acrylonitrile copolymer, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer Styrene resins (styrene or styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloroacrylic acid methyl copolymer, styrene-acrylonitrile-acrylic acid ester copolymer) Monopolymer or copolymer containing styrene substitution product), polyester Resin, epoxy resin, vinyl chloride resin, rosin-modified maleic acid resin, phenol resin, polyethylene resin, polypropylene resin, petroleum resin, polyurethane resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyrate resin, etc. Is mentioned. Among these, polyester resins have a low softening temperature and a high glass transition temperature, so they are excellent in low-temperature fixability and storage stability, and have good affinity between the ester bonds of polyester resins and paper. Therefore, polyester resins are particularly preferable from the viewpoint of excellent offset resistance.

The binder resin preferably has a functional group capable of ionic bonding. The functional group capable of ion binding is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a carboxyl group, a hydroxyl group, a CN group, and SO ₃ ⁻ . Among these, a resin having a carboxyl group at the terminal is more preferable, and an unmodified polyester resin having a carboxyl group at the terminal is particularly preferable.

-Unmodified polyester resin-
In the present invention, by including an unmodified polyester resin as a binder resin, low-temperature fixability and gloss when used in a full-color image forming apparatus are improved. Examples of such an unmodified polyester resin include polycondensates of polyol (1) and polycarboxylic acid (2).

Examples of the polyol (1) include a diol (1-1) or a tri- or higher valent polyol (1-2), (1-1) alone, or (1-1) and a small amount of (1-2). Is preferred.
Examples of the diol (1-1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (Diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Bisphenols (bisphenol A) Bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol Alkylene oxide of the bisphenols (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among these, alkylene glycol adducts having 2 to 12 carbon atoms or alkylene oxide adducts of bisphenols, particularly preferred are alkylene oxide adducts of bisphenols, or combinations thereof with alkylene glycols having 2 to 12 carbon atoms. is there.
Examples of the trivalent or higher polyol (1-2) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); Phenols (trisphenol PA, phenol novolac, cresol novolac, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols and the like.

Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) or trivalent or higher polycarboxylic acid (2-2), (2-1) alone, and (2-1) and a small amount. The mixture of (2-2) is preferable.
Examples of the dicarboxylic acid (2-1) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, Terephthalic acid, naphthalenedicarboxylic acid, etc.). Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms.
Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  As for the ratio of the polyol (1) and the polycarboxylic acid (2), the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH] is preferably 2/1 to 1/1. 5/1 to 1/1 is more preferable, and 1.3 / 1 to 1.02 / 1 is still more preferable.

The peak molecular weight of the unmodified polyester resin is preferably 1,000 to 30,000, more preferably 1,500 to 10,000, and still more preferably 2,000 to 8,000. When the peak molecular weight is less than 1,000, the heat-resistant storage stability may be deteriorated, and when it exceeds 10,000, the low-temperature fixability may be deteriorated.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g or more, more preferably 10 to 120 mgKOH / g, still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1 to 30 mgKOH / g, and more preferably 5 to 20 mgKOH / g. Thus, it tends to be negatively charged by giving an acid value.
The glass transition temperature (Tg) of the unmodified polyester resin is preferably 40 to 90 ° C, and more preferably 55 to 65 ° C. When the glass transition temperature is less than 50 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
As for the storage elastic modulus of the unmodified polyester resin, the temperature (TG ′) at which a measurement frequency of 20 Hz is 10,000 dyne / cm ² is preferably 100 ° C. or more, and more preferably 110 to 200 ° C. When the TG ′ is less than 100 ° C., the hot offset resistance may be deteriorated.
As the viscosity of the unmodified polyester resin, the temperature (Tη) at which a poise of 1,000 at a measurement frequency of 20 Hz is preferably 180 ° C. or less, and more preferably 90 to 160 ° C. When Tη exceeds 180 ° C., the low-temperature fixability may be deteriorated. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and still more preferably 20 ° C. or higher. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and still more preferably 20 to 80 ° C.

In the present invention, not only the unmodified polyester resin but also a modified polyester resin (modified polyester resin) may be contained as a binder resin.
There is no restriction | limiting in particular as said modified polyester resin, Although it can select suitably according to the objective, The isocyanate group containing polyester prepolymer A) is suitable.
There is no restriction | limiting in particular as said isocyanate group containing polyester prepolymer (A), According to the objective, it can select suitably, For example, the said acid component, at least 1 selected from aliphatic diol and alicyclic diol Examples thereof include those obtained by reacting a polyester resin obtained by condensation polymerization of a seed diol compound in the presence of a catalyst with polyisocyanate (PIC).

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

  As a mixing ratio when the polyisocyanate (PIC) is reacted with the polyester resin, a mixing equivalent ratio of an isocyanate group [NCO] in the polyisocyanate (PIC) and a hydroxyl group [OH] in the polyester resin ( [NCO] / [OH]) is usually preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, and still more preferably 3/1 to 1.5 / 1. When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

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

The mixing mass ratio of the modified polyester resin and the unmodified polyester resin (modified polyester resin / unmodified polyester resin) is preferably 5/95 to 25/75, and more preferably 10/90 to 25/75.
When the mixing mass ratio of the unmodified polyester resin exceeds 95, the hot offset resistance deteriorates, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When it is less than 25, the glossiness deteriorates. There are things to do.

The isocyanate group content based on JIS K1603 in the modified polyester resin is preferably 2.0% by mass or less, and more preferably 1.0 to 2.0% by mass. When the isocyanate group content exceeds 2.0% by mass, the low-temperature fixing performance may not be exhibited.
Here, the said isocyanate group content rate (NCO%) can be measured by the method based on JISK1603, for example.

  The modified polyester resin has a mass average molecular weight of preferably 10,000 to 100,000, and more preferably 10,000 to 50,000. If the mass average molecular weight is less than 10,000, low-temperature fixability may not be exhibited, and if it exceeds 100,000, the viscosity becomes too high and granulation may be difficult.

10-50 degreeC is preferable and, as for the glass transition temperature (Tg) of the said modified polyester resin, 30-50 degreeC is more preferable.
The hydroxyl value of the modified polyester resin is preferably 30 mgKOH / g or less, and more preferably 10 to 25 mgKOH / g.
The acid value of the modified polyester resin is preferably 0 to 10 mgKOH / g, and more preferably 0 to 5 mgKOH / g.
Here, the acid value and the hydroxyl value can be measured by a method defined in JIS K0070.

  Here, the modified polyester resin is, for example, put a diol compound, an acid component, and a titanium-based catalyst in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and at normal pressure at 230 ° C. for 8 hours. It is obtained by reacting, then reacting at a reduced pressure of 10 to 15 mmHg for 5 hours, and further reacting with an isocyanate group-containing compound.

  Next, the toner material used in the present invention contains at least an unmodified polyester resin, a release agent, a colorant, and, if necessary, other components.

  The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include degreen lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon. These may be used individually by 1 type and may use 2 or more types together.

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

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

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

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

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

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

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

<Toner production method>
As the method for producing the toner, for example, a solution or dispersion in which a toner material containing at least a binder resin and a charge control agent is dissolved or dispersed in an organic solvent, and a dispersion liquid in which an aqueous medium is dispersed is used as an organic solvent. Is included, and further includes other steps as necessary.

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

-Dispersion-
The dispersion is prepared by dispersing the dissolved or dispersed material in an aqueous medium.
When the dissolution or dispersion is dispersed in the aqueous medium, a dispersion (oil droplets) composed of the dissolution or dispersion is formed in the aqueous medium.

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

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

  The resin fine particles are not particularly limited and can be obtained by polymerization according to a known method appropriately selected according to the purpose, but it is preferable to obtain the resin fine particles as an aqueous dispersion. As a method for preparing the aqueous dispersion of the resin fine particles, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material, and is selected from a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, and a dispersion polymerization method. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, (Oligomer etc.) or a solvent solution thereof in the presence of a suitable dispersant, and then dispersed in an aqueous medium, followed by heating or adding a curing agent and curing to produce an aqueous dispersion of resin fine particles. 3) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it must be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). A method in which a suitable emulsifier is dissolved in a solution (which may be liquefied by heating), and then water is added to perform phase inversion emulsification. The resin prepared by any polymerization reaction mode such as condensation polymerization) is pulverized using a fine pulverizer such as a mechanical rotary type or a jet type, and then classified to obtain resin fine particles, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization). A method in which resin fine particles are obtained by spraying a resin solution in which a resin is dissolved in a solvent in a mist, and then the resin fine particles are dispersed in water in the presence of a suitable dispersant. (6) A polymerization reaction (addition polymerization, Ring-opening polymerization, polyaddition, addition The resin prepared by adding a poor solvent to a resin solution prepared by dissolving a resin prepared in a solvent in a solvent, or by cooling a resin solution previously heated and dissolved in a solvent. After the fine particles are precipitated and then the solvent is removed to obtain resin particles, the resin particles are dispersed in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, (Any polymerization reaction mode such as polyaddition, addition condensation, condensation polymerization, etc. may be used) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated. Or a method of removing the solvent by reducing pressure, etc., (8) a resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) In resin solution dissolved in A suitable emulsifier is dissolved in water and then water is added to carry out phase inversion emulsification.

The resin fine particles have a mass average molecular weight of preferably 5,000 to 200,000, and more preferably 50,000 to 150,000. If the mass average molecular weight is less than 5,000, the storage stability of the toner deteriorates, and blocking may occur during storage and in the developing unit. If it exceeds 200,000, resin fine particles are recorded. Adhesiveness with the medium may be hindered, and the minimum fixing temperature may increase.
Here, the mass average molecular weight can be determined as follows by molecular weight distribution measurement by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF).
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or the molecular weights made by Toyo Soda Industry Co., Ltd. are 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8. It is preferable to use 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

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

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The toner solution is prepared by dissolving or dispersing toner materials such as the unmodified polyester resin, the modified polyester resin, the colorant, the release agent, and the charge control agent in the organic solvent. be able to.
The toner material may be mixed when forming a dispersion in an aqueous medium, but it is more preferable that the toner material is mixed in advance and then the mixture is added and dispersed in the aqueous medium. In the present invention, other toner materials such as a colorant and a release agent are not necessarily mixed when particles are formed in an aqueous medium, and are added after particles are formed. Also good. For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method.

The dispersion can be prepared by emulsifying or dispersing the previously prepared toner solution in the previously prepared aqueous medium phase.
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. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited and can be appropriately selected according to the purpose, but is preferably 1,000 to 30,000 rpm, more preferably 5,000 to 20,000 rpm. . The dispersion time is not particularly limited and can be appropriately selected according to the purpose. However, in the case of a batch method, 0.1 to 5 minutes is preferable. As temperature at the time of dispersion | distribution, 0-150 degreeC (under pressurization) is preferable, and 40-98 degreeC is more preferable. A higher temperature is preferable in that the dispersion of the toner material has a low viscosity and is easily dispersed.

The amount of the aqueous medium used with respect to 100 parts by mass of the toner material is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass. If the amount used is less than 50 parts by mass, the dispersion state of the toner material is deteriorated, and toner particles having a predetermined particle size may not be obtained. If the amount exceeds 2,000 parts by mass, it is not economical.
Further, in the step of synthesizing the urea-modified polyester (i) from the prepolymer (A), the amine (B) may be added and reacted before the toner material is dispersed in the aqueous medium, or may be dispersed in the aqueous medium. Then, amines (B) may be added to cause a reaction from the particle interface. In this case, urea-modified polyester is preferentially produced on the surface of the manufactured toner, and a concentration gradient can be provided inside the particles.

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

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

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

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

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

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

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

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

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

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

  The toner preferably has the following volume average particle diameter (Dv), volume average particle diameter (Dv) / number average particle diameter (Dn), and the like.

The volume average particle diameter (Dv) of the toner is preferably 4 to 8 μm, for example, and more preferably 4 to 7 μm. Here, the volume average particle diameter is defined as Dv = [Σ (nD ³ ) / Σn] ^1/3 (where n is the number of particles and D is the particle diameter).
When the volume average particle size is less than 4 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In the case of the agent, toner filming on the developing roller and toner thinning are likely to cause toner fusion to a member such as a blade. On the other hand, when the volume average particle size exceeds 8 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the particle size of the toner is large. May be.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is preferably 1.25 or less, more preferably 1.05 to 1.25.
In general, it is said that the smaller the toner particle size, 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. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, leading to a decrease in the charging ability of the carrier, When used as a 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. Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention. 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. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.
On the other hand, when the volume average particle size / number average particle size is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount, but the toner is not sufficiently charged. It has become clear that there is a case where the cleaning property is deteriorated.

  The volume average particle diameter (Dv) and the ratio (Dv / Dn) of the volume average particle diameter to the number average particle diameter (Dv / Dn) are, for example, a particle size measuring device (“Coulter Counter TAII”, manufactured by Coulter Electronics). It can be measured by measuring with an aperture diameter of 100 μm and analyzing with analysis software (Beckman Coulter Multisizer 3 Version 3.51).

  There is no restriction | limiting in particular as coloring of the said toner, According to the objective, it can select suitably, It can be made into at least 1 sort (s) selected from a black toner, a cyan toner, a magenta toner, and a yellow toner. The toner of each color can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

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

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

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

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 to 200 μm, and more preferably 40 to 100 μm. When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

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

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

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

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

  The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount is less than 0.01% by mass, it may not be possible to form the uniform resin layer on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes too thick. As a result, granulation of carriers occurs, and uniform carrier particles may not be obtained.

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

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

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

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

  Here, for example, as shown in FIG. 26, the process cartridge includes an electrostatic latent image carrier (photosensitive drum) 101, a charging device 102, a developing unit 104, and a cleaning unit 107. Furthermore, it has other means as needed. Reference numeral 103 denotes exposure by an exposure apparatus, 105 denotes a recording medium, and 108 denotes a transfer unit.

  Next, an image forming process using the process cartridge shown in FIG. 26 will be described. The photosensitive drum 101 as an electrostatic latent image carrier is rotated in the direction of the arrow while being charged by the charging device 102 and exposed to light 103 by an exposure device (not shown). Is formed. The electrostatic latent image is developed by the developing unit 104, and the obtained visible image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photosensitive drum after the transfer is cleaned by the cleaning means 107, further neutralized by the neutralizing means (not shown), and the above operation is repeated again.

  As an image forming apparatus used in the present invention, the electrostatic latent image carrier and components such as a developing device and a cleaning device are integrally combined as a process cartridge, and this unit is attached to and detached from the apparatus main body. You may comprise. Further, at least one selected from a charging device, a developing device, a transfer device, a separation device, and a cleaning device is integrally supported together with an electrostatic latent image carrier to form a process cartridge, and is detachably attached to the apparatus main body. One unit may be configured to be detachable using guide means such as a rail of the apparatus main body.

(Image forming apparatus and image forming method)
The image forming apparatus used in the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, a fixing unit, and a cleaning unit. Other means appropriately selected according to the above, for example, static elimination means, recycling means, control means, and the like are provided.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, a fixing step, and a cleaning step, and further other steps appropriately selected as necessary, for example, static elimination. Includes processes, recycling processes, control processes, etc.

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

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The material, shape, structure, size and the like of the electrostatic latent image carrier are not particularly limited and can be appropriately selected according to the purpose. Examples of the shape include a drum shape and a sheet. And endless belts. The structure may be a single-layer structure or a laminated structure, and the size may be appropriately selected according to the size and specifications of the image forming apparatus. Examples of the material include inorganic photoreceptors such as amorphous silicon, selenium, CdS, and ZnO; organic photoreceptors (OPC) such as polysilane and phthalopolymethine, and the like.

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

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

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. Can do.
The electrostatic latent image forming means includes at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. .

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

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

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

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

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

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

Examples of the material of the developing roller that is used when the toner of the present invention is used as a one-component developer include metals such as aluminum, iron, and SUS. Moreover, the surface is processed by a processing method such as sandblasting. As the material having an elastic layer, known materials such as natural rubber, silicone rubber, urethane rubber, butadiene rubber, chloroprene rubber, neoprene rubber, isoprene rubber and NBR can be used. The form of the elastic layer is not particularly limited and may be appropriately selected according to the purpose. For example, these elastic layers are effective when used in the form of rubber, foam, sponge, or the like. It is also effective to change the material of the material depending on the part of the developing roller.
The developing roller may be provided with a magnetic field generating layer, and the magnetic field strength may be changed depending on the portion of the developing roller. Further, a toner supply roller for supplying toner to the developing roller may be provided, and contact or non-contact between these two rollers can be appropriately selected. Further, an AC, DC, or AC + DC electric field may be applied between the two rollers. By providing the toner supply roller, the toner can be charged smoothly, and variations in the toner layer on the developing roller can be eliminated.
The material of the toner supply roller is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include sponge, rubber, SUS, or a material coated with these. In some cases, in addition to the supply roller, it is possible to provide a peeling roller having a function of temporarily removing toner that has not been used for development from the developing roller. Moreover, you may provide the coating layer which contains a mold release component. There is no restriction | limiting in particular as coating resin in the said coating layer, According to the objective, it can select suitably from well-known resin.

Further, it is possible to provide blades upstream and downstream of the rotation of the developing roller with respect to the developing position, and it is also possible to apply a voltage to these members. The supply roller can also serve as a stripping and supplying function. It is also preferable to provide a toner layer regulating member upstream of the developing unit. The toner layer regulating member may be a plate-like member, or a rotating roller may be used. Charge may be injected into the toner by the toner layer regulating member.
Further, the development method used in the present invention is not particularly limited and can be appropriately selected according to the purpose. A non-contact developing method may be used.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.

There is no restriction | limiting in particular as said intermediate transfer body, According to the objective, it can select suitably from well-known transfer bodies, For example, a transfer belt, a transfer roller, etc. are mentioned suitably.
The static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably several Ωcm or more and 10 ³ Ωcm or less. Thus, by setting the volume resistance of the intermediate transfer member to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means hardly remains on the intermediate transfer member. Therefore, transfer unevenness during secondary transfer can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

There is no restriction | limiting in particular as a material of the said intermediate transfer body, Although it can select suitably according to the objective from well-known materials, the following are suitable.
(1) A material having a high Young's modulus (tensile modulus) is used as a single layer belt. For example, PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) and PAT Blend materials, ETFE (ethylene tetrafluoroethylene copolymer) and PC blend materials, ETFE and PAT blend materials, PC and PAT blend materials, carbon black dispersed thermosetting polyimide, etc. . These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and rib displacement is unlikely to occur particularly during color image formation.
(2) A belt having a two- to three-layer structure in which a belt having a high Young's modulus (1) is used as a base layer and a surface layer or an intermediate layer is formed on the outer periphery thereof. It has a performance capable of preventing the line image from being lost due to the hardness of the single layer belt.
(3) An elastic belt having a relatively low Young's modulus using resin, rubber, or elastomer, and such an elastic belt has an advantage that almost no void in a line image occurs due to its softness. In addition, the elastic belt is wider than the drive roll and tension roll, and the elasticity of the belt ears protruding from the roll can be used to prevent meandering, thus reducing costs without requiring ribs or meandering prevention devices. it can. Among these, the elastic belt (3) is particularly preferable.
The elastic belt is deformed corresponding to a toner layer and a recording medium having poor smoothness in the transfer portion. In other words, since the elastic belt deforms following the local unevenness, good adhesion can be obtained without excessively increasing the transfer pressure with respect to the toner layer, there is no void in characters, and flatness is poor. A transfer image with excellent uniformity can be obtained even on a recording medium.

  There is no restriction | limiting in particular as resin used for the said elastic belt, Although it can select suitably according to the objective, For example, polycarbonate resin, fluororesin (ETFE, PVDF), polystyrene resin, chloropolystyrene resin, poly-alpha -Methylstyrene resin, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-acrylic) Acid methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer Polymer (eg, styrene-methyl methacrylate copolymer) Styrene resins such as styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylate copolymer, etc. Or a styrene-substituted monopolymer or copolymer), methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (for example, silicone-modified acrylic resin, vinyl chloride resin-modified) Acrylic resin, acrylic-urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyethylene resin, polypropylene Resin, polybutadiene Emissions, polyvinylidene chloride resins, ionomer resins, polyurethane resins, silicone resins, ketone resins, ethylene - ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, polyamide resin and modified polyphenylene oxide resins. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as rubber | gum used for the said elastic belt, According to the objective, it can select suitably, For example, natural rubber, butyl rubber, fluorine-type rubber, acrylic rubber, EPDM rubber, NBR rubber, acrylonitrile-butadiene-styrene rubber , Isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydride Examples thereof include phosphorus rubber, silicone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, and hydrogenated nitrile rubber. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as an elastomer used for the said elastic belt, According to the objective, it can select suitably, For example, a polystyrene-type thermoplastic elastomer, a polyolefin-type thermoplastic elastomer, a polyvinyl chloride-type thermoplastic elastomer, a polyurethane-type thermoplasticity Examples thereof include elastomers, polyamide-based thermoplastic elastomers, polyurea thermoplastic elastomers, polyester-based thermoplastic elastomers, and fluorine-based thermoplastic elastomers. These may be used individually by 1 type and may use 2 or more types together.

  The conductive agent for adjusting the resistance value used in the elastic belt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, metal powder such as carbon black, graphite, aluminum, nickel; tin oxide, titanium oxide And conductive metal oxides such as antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), and indium oxide-tin oxide composite oxide (ITO). The conductive metal oxide may be coated with insulating fine particles such as barium sulfate, magnesium silicate, and calcium carbonate.

  In addition, the surface layer of the elastic belt prevents contamination of the electrostatic latent image carrier by the elastic material, reduces the frictional resistance of the belt surface, reduces the adhesion of the toner, and improves the cleaning property and the secondary transfer property. What can do is preferable. The surface layer is made of, for example, a binder resin such as a polyurethane resin, a polyester resin, or an epoxy resin, and a material capable of increasing the lubricity by reducing the surface energy, such as a fluororesin, a fluorine compound, a fluorocarbon, titanium dioxide, a silicon car It is preferable to contain powder or particles such as bites. Further, it is possible to use a material having a reduced surface energy by forming a fluorine-rich surface layer by heat treatment, such as a fluorine-based rubber material.

  There is no restriction | limiting in particular as a manufacturing method of the said elastic belt, Although it can select suitably according to the objective, For example, (1) Centrifugal molding method which pours material into a rotating cylindrical type | mold and forms a belt, ( 2) Spray coating method to form a film by spraying a liquid paint, (3) Dipping method in which a cylindrical mold is dipped in a solution of the material, and (4) Casting to be injected into an inner mold or an outer mold And (5) a method in which a compound is wound around a cylindrical mold and vulcanized and polished.

The method for preventing the elastic belt from stretching is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) a method of adding a material for preventing elongation to the core layer, 2) A method of forming a rubber layer on a core layer with little elongation, and the like.
There is no restriction | limiting in particular as a material which prevents the said elongation, Although it can select suitably according to the objective, For example, natural fibers, such as cotton and silk; Polyester fiber, nylon fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol Synthetic fibers such as fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers, phenol fibers; inorganic fibers such as carbon fibers, glass fibers, boron fibers; iron fibers, copper fibers, etc. A metal fiber etc. are mentioned, What made these materials into the shape of a woven fabric or a thread form is used suitably.

The method for forming the core layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) a woven fabric woven in a cylindrical shape is covered with a mold or the like and coated thereon (2) A method of providing a coating layer on one or both sides of the core layer by immersing a woven fabric woven in a cylindrical shape into liquid rubber, etc. For example, a method of winding in a spiral shape and providing a coating layer thereon may be used.
The thickness of the coating layer depends on the hardness of the coating layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur on the surface layer. Further, since the amount of expansion / contraction increases and the expansion and contraction of the image increase, it is not preferable that the thickness is too large (about 1 mm or more).

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

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this. There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

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

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

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

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

  Next, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 27 includes a photosensitive drum 10 as the electrostatic latent image carrier, a charging roller 20 as the charging unit, an exposure device 30 as the exposure unit, and a developing unit. A developing device 40, an intermediate transfer member 50, a cleaning device 60 as the cleaning unit having a cleaning blade, and a static elimination lamp 70 as the static elimination unit.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. An intermediate transfer member cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50, and a transfer bias for transferring a transfer image (secondary transfer) to the recording medium 95 can be applied. Further, a transfer roller 80 as the transfer means is disposed so as to face. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is connected to the electrostatic latent image carrier 10 and the intermediate transfer member in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion with the body 50 and the contact portion between the intermediate transfer member 50 and the recording medium 95.

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

  In the image forming apparatus 100 shown in FIG. 27, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the recording medium 95. As a result, a transfer image is formed on the recording medium 95. The residual toner on the electrostatic latent image carrier 10 is removed by the cleaning device 60, and the charge on the electrostatic latent image carrier 10 is once removed by the static elimination lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 28 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 27, and has a black developing unit 45K, a yellow developing unit 45Y, and a magenta around the electrostatic latent image carrier 10. Except that the developing unit 45M and the cyan developing unit 45C are directly opposed to each other, the image forming apparatus 100 has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 28, the same components as those in FIG. 27 are denoted by the same reference numerals.

Next, a tandem type image forming apparatus that performs the image forming method of the present invention using the image forming apparatus of the present invention will be described.
The tandem type image forming apparatus has a plurality of image forming elements including at least an electrostatic latent image carrier, a charging unit, a developing unit, and a transfer unit. In this tandem type image forming apparatus, four image forming elements for yellow, magenta, cyan, and black are mounted, and each visible image is created in parallel with the four image forming elements, and is recorded on a recording medium or an intermediate transfer member. Therefore, a full color image can be formed at a higher speed.

  As the tandem type image forming apparatus, (1) as shown in FIG. 29, the surface moves so as to pass through a transfer position that is a region facing each electrostatic latent image carrier 1 of a plurality of image forming elements. A direct transfer system in which a visible image formed on each electrostatic latent image carrier 1 is sequentially transferred to the recording medium S to be transferred by the transfer means 2, and (2) a plurality of images as shown in FIG. The visible image on each electrostatic latent image carrier 1 of the forming element is once transferred sequentially to the intermediate transfer body 4 by the transfer means (primary transfer means) 2, and then the image on the intermediate transfer body 4 is transferred to the secondary transfer means 5. There is an indirect transfer method in which the image is transferred to the recording medium S at once. In FIG. 30, a transfer conveyance belt is used as the secondary transfer unit, but a roller shape may be used.

Comparing the direct transfer method (1) and the indirect transfer method (2), the direct transfer method (1) is a tandem type image forming unit T in which the electrostatic latent image carriers 1 are arranged. A sheet feeding device 6 must be disposed on the upstream side, and a fixing device 7 as a fixing unit must be disposed on the downstream side, which increases the size of the recording medium in the conveyance direction. On the other hand, in the indirect transfer method (2), the secondary transfer position can be set relatively freely, and the paper feeding device 6 and the fixing device 7 are arranged so as to overlap the tandem type image forming unit T. There is an advantage that downsizing is possible.
In the direct transfer method (1), the fixing device 7 is disposed close to the tandem image forming unit T in order not to increase the size in the recording medium conveyance direction. Therefore, the fixing device 7 cannot be disposed with a sufficient margin that the recording medium S can bend, and an impact when the leading end of the recording medium S enters the fixing device 7 (particularly with a thick recording medium). In addition, the fixing device 7 tends to affect upstream image formation due to the speed difference between the recording medium conveyance speed when passing through the fixing device 7 and the recording medium conveyance speed by the transfer conveyance belt. On the other hand, in the indirect transfer method (2), the fixing device 7 can be arranged with a sufficient margin that the recording medium S can be bent, and therefore the fixing device 7 hardly affects the image formation.
For these reasons, indirect transfer systems have recently attracted attention. In this type of color image forming apparatus, the transfer residual toner remaining on the electrostatic latent image carrier 1 after the primary transfer as shown in FIG. The surface of the carrier 1 is cleaned to prepare for the image formation again. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

Further, the tandem image forming apparatus shown in FIG. 31 is a tandem color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 31. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the recording medium conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22.
In the vicinity of the secondary transfer device 22 and the fixing device 25, a sheet reversing device 28 for reversing the recording medium in order to form an image on both sides of the recording medium is disposed.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300. 400 is closed.

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

  The black, yellow, magenta, and cyan image information is obtained from each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image forming unit) in the tandem developing device 120. Each image forming unit forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is respectively shown in FIG. Electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); Then, the electrostatic latent image carrier is uniformly charged, and the electrostatic latent image carrier is exposed like an image corresponding to each color image based on each color image information (L in FIG. 32). An exposure device (not shown) for forming an electrostatic latent image corresponding to each color image on the photoconductor, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) on the electrostatic latent image. Using A developing device 61 for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer body 50, a cleaning device 63, and a charge eliminating device 64. Each single-color image (black image, yellow image, magenta image, and cyan image) can be formed based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on the body 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording medium from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the sheet feeding roller 142 is rotated to feed out the recording medium on the manual feed tray 54, separated one by one by the separation roller 145, put into the manual sheet feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in time with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and the recording medium is sent between the intermediate transfer member 50 and the secondary transfer device 22. Then, by transferring (secondary transfer) the composite color image (color transfer image) onto the recording medium by the secondary transfer device 22, a color image is transferred and formed on the recording medium. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

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

  In the image forming method and the image forming apparatus of the present invention, it is possible to produce a visible image with a long initial charge buildup, a sharp charge amount distribution, and a sharp sharpness while maintaining a stable charge amount with little change in charge amount over time. Since the toner of the present invention that can be formed over a wide range is used, a high-quality image can be formed efficiently.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples and comparative examples, the volume average particle size (Dv) and particle size distribution (Dv / Dn) of toner, the weight average molecular weight of resin, the glass transition temperature (Tg) of resin, the acid value, and the hydroxyl value are measured. This was done as follows.

<Measurement of Volume Average Particle Diameter (Dv) and [Dv / Dn] Value>
A Coulter Multisizer IIe type (manufactured by Coulter Inc.) is used as a measuring device, and an interface for outputting the number distribution and volume distribution (manufactured by Nikka Kikai Co., Ltd.) and a personal computer are connected. 1 mass% NaCl aqueous solution was prepared. As a measuring method, 0.1 to 5 ml of a surfactant (alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. Dispersion processing for a minute was performed. Next, 100 to 200 ml of an electrolytic aqueous solution is put into another beaker, and the sample dispersion is added to a predetermined concentration therein, and 50,000 particles are used with the Coulter Multisizer IIe as a 100 μm aperture. The average of was measured. Dv / Dn was determined from the obtained volume average particle diameter (Dv) and number average particle shape (Dn).
The channel includes a particle size of 2.00 μm to less than 2.52 μm, a particle size of 2.52 μm to less than 3.17 μm, a particle size of 3.17 μm to less than 4.00 μm, a particle size of 4.00 μm to less than 5.04 μm, 5.04 μm or more and less than 6.35 μm, particle size of 6.35 μm or more and less than 8.00 μm, particle size of 8.00 μm or more and less than 10.08 μm, particle size of 10.08 μm or more and less than 12.70 μm, particle size of 12.70 μm or more and 16. 13 channels of less than 00 μm, particle size of 16.00 μm or more and less than 20.20 μm, particle size of 20.20 μm or more and less than 25.40 μm, particle size of 25.40 μm or more and less than 32.00 μm, particle size of 32.00 μm or more and less than 40.30 μm The target is particles having a particle size of 2.00 μm or more and less than 40.30 μm.

<Measurement of glass transition temperature (Tg) of resin>
A TG-DSC system TAS-100 manufactured by Rigaku Corporation was used as a device for measuring the glass transition temperature (Tg) of the resin. First, 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. Next, after heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, then the sample was cooled to room temperature and allowed to stand for 10 minutes, and again at 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at a heating rate of 10 ° C./min. As for Tg, the glass transition temperature (Tg) was calculated from the intersection of the tangent line of the endothermic curve portion and the baseline using the analysis system in the TAS-100 system.

<Method for measuring acid value and hydroxyl value of resin>
Specifically, the acid value (AV) and the hydroxyl value (OHV) were determined by the following procedure. However, when the sample did not dissolve, a solvent such as dioxane or THF was used as the solvent.
・ Measuring device: potentiometric automatic titrator DL-53 Titrator (Metler Toledo)
-Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
・ Analysis software: LabX Light Version1.00.000
-Calibration of apparatus: A mixed solvent of 120 ml of toluene and 30 ml of ethanol was used.
・ Measurement temperature: 23 ℃
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
At maximum volume [mL] 10.0
At potential No
At slope No
After number EQPs Yes
n = 1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

-Method of measuring acid value-
The acid value was measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) was added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Furthermore, 30 ml of ethanol was added to prepare a sample solution.
The measurement can be calculated with the above-described apparatus. Specifically, the measurement was performed as follows.
Titration was carried out in advance using standardized N / 10 caustic potassium to alcohol solution, and the acid value was determined from the consumption amount of the alcohol potassium solution by the following formula.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of (N / 10) KOH)

-Measurement method of hydroxyl value-
The hydroxyl value was measured as follows based on the measurement method described in JIS K0070-1996.
0.5 g of the sample was precisely weighed into a 100 ml volumetric flask, and 5 ml of an acetylating reagent was correctly added thereto. Then, it was heated by being immersed in a bath at 100 ° C. ± 5 ° C. After 1 to 2 hours, the flask was taken out of the bath, allowed to cool, then added with water and shaken to decompose acetic anhydride. Next, in order to complete the decomposition, the flask was again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask was thoroughly washed with an organic solvent. This solution was subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the hydroxyl value.

<Mass average molecular weight of resin>
The mass average molecular weight of the resin was measured using GPC (gel permeation chromatography) for the tetrahydrofuran (THF) soluble component under the following conditions.
・ Apparatus: HLC-8120 manufactured by Tosoh Corporation
・ Column: TSKgelGMHXL (2)
・ TSKgel MultiporeHXL-M (1 pc.)
・ Measurement temperature: 40 ℃
・ Sample solution: 0.25 mass% THF solution ・ Solution injection amount: 100 μl
-Detector: Refractive index detector-Reference material: Polystyrene The molecular weight showing the maximum peak height on the obtained chromatogram was defined as the peak top molecular weight.

Example 1
<Preparation of Toner 1>
-Synthesis of organic fine particle emulsion-
In a reaction vessel in which a stirrer and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 166 methacrylic acid When a mass part, 110 mass parts of butyl acrylate, and 1 mass part of ammonium persulfate were prepared and stirred for 30 minutes at 3,800 rpm, a white emulsion was obtained. The system temperature was raised to 75 ° C. and reacted for 4 hours. Subsequently, 30 parts by mass of a 1% by mass aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 6 hours to obtain an aqueous vinyl resin (a copolymer of methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 1] was obtained. The obtained [Fine Particle Dispersion 1] was measured with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corporation), and the volume average particle diameter was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 58 ° C., and the mass average molecular weight was 130,000.

-Preparation of aqueous phase-
86 parts by weight of water, 3.3 parts by weight of [fine particle dispersion 1], 25 parts by weight of a 50% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries Ltd.), and 14 parts by weight of ethyl acetate Were mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].

-Synthesis of low molecular weight polyester-
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 691 parts by mass of bisphenol A ethylene oxide 2-mole adduct and 309 parts by mass of terephthalic acid were added, and the reaction was carried out at 210 ° C. under normal pressure and nitrogen flow. A time condensation reaction was carried out. Next, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, followed by cooling to obtain [Low Molecular Polyester 1]. The obtained [Low molecular weight polyester 1] had a mass average molecular weight of 3,500 in THF, an acid value of 10 mgKOH / g, a hydroxyl value of 50 mgKOH / g, and a glass transition temperature (Tg) of 40 ° C.

-Preparation of oil phase-
In a container in which a stirring bar was set, 1,020 parts by mass of [Low molecular polyester 1] and 550 parts by mass of ethyl acetate were charged and mixed for 10 hours to obtain [Raw material solution 1].
Next, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide represented by the following structural formula (hereinafter referred to as fluorine-containing quaternary ammonium salt compound (1)). ) Was mixed and stirred so as to be 0.1% by mass with respect to the above [raw material solution 1] to obtain [oil phase 1].

-Emulsification and solvent removal-
[Aqueous phase 1] 190 parts by mass was put in a container, mixed with TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at 3,000 rpm for 5 minutes, and then [oil phase 1] was added with 110 parts by mass. The mixture was mixed for 30 minutes at a rotation speed of 9,000 rpm to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer, and the solvent was removed at 30 ° C. for 10 hours, followed by aging at 45 ° C. for 10 hours to obtain [Dispersion slurry 1]. [Dispersion Slurry 1] had a volume average particle diameter (Dv) of 4.95 μm and a number average particle diameter (Dn) of 4.4 μm.

-Cleaning and drying-
[Dispersion Slurry 1] 100 parts by mass were filtered under reduced pressure, and then washed and dried as follows.
(1) 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at 15,000 rpm), and then filtered five times.
(2) 100 mass parts of 10 mass% hydrochloric acid was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 15,000 rpm) and then filtered.
(3) Add 300 parts by mass of ion-exchanged water to the filter cake of (2), mix with a TK homomixer (10 minutes at 15,000 rpm), and then filter 5 times to obtain [Filter cake 1]. It was.
The obtained [Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, sieved with a mesh of 75 μm, volume average particle size (Dv) 5.1 μm, number average particle size (Dn) 4. [Toner 1] of 6 μm and Dv / Dn = 1.11 was obtained.

FIG. 15 is a plot of the vicinity of the iodine main peak in [Toner 1], indicating that there is no iodine main peak (I 3d) as measured by X-ray photoelectron spectroscopy using AXIS-ULTRA manufactured by Shimadzu Corporation. It is.
FIG. 16 is a plot showing a main peak (F 1s) of fluorine detected by X-ray photoelectron spectroscopy using AXIS-ULTRA manufactured by Shimadzu Corporation in [Toner 1].
FIG. 17 is a plot showing the main peak (I 3d) of iodine detected by X-ray photoelectron spectroscopy using AXIS-ULTRA manufactured by Shimadzu Corporation in the fluorine-containing quaternary ammonium salt compound (1).
FIG. 18 is a plot showing the fluorine main peak (F 1s) detected by X-ray photoelectron spectroscopy using Shimadzu AXIS-ULTRA, which is a fluorine-containing quaternary ammonium salt compound (1).
FIG. 19 is a plot diagram showing the change over time in the charge amount of [Toner 1]. The charge amount was determined by weighing 6 g of developer composed of toner and iron powder carrier TEFV200 / 300 (manufactured by Powdertech Co., Ltd.), charging it into a metal cylinder that can be sealed, and blowing it. The toner concentration was adjusted to 7% by mass.

  From the results of X-ray photoelectron spectroscopy measurement, it was confirmed that [Toner 1] does not contain iodine. Further, the main peak of fluorine was present in the toner in the same state as the raw material powder. Therefore, in [Toner 1], the fluorine-containing quaternary ammonium salt compound (1) is ionically bonded to the carboxyl group of [Low Molecular Polyester 1] as the binder resin and the carboxyl group of the resin fine particles. I understood. In addition, as to the change in the charge amount of [Toner 1] with time, the initial charge rise was fast as in the conventional toner using a fluorine-containing quaternary ammonium salt compound, and no decrease in charge with time was observed.

(Example 2)
-Production of Toner 2-
In Example 1, except that the fluorine-containing quaternary ammonium salt compound (2) represented by the following structural formula was used instead of the fluorine-containing quaternary ammonium salt compound (1), in the same manner as in Example 1, [ Toner 2] was prepared.

  From the result of X-ray photoelectron spectroscopy measured in the same manner as in Example 1 for the obtained [Toner 2], it was confirmed that iodine was not present in [Toner 2]. Further, the main peak of fluorine was present in the toner in the same state as the raw material powder. From this, it is understood that the fluorine-containing quaternary ammonium salt compound (2) is ionically bonded to the carboxyl group of [low molecular polyester 1] as the binder resin and the carboxyl group of the resin fine particles in [Toner 2]. It was. In addition, as to the change in the charge amount of [Toner 2] with time, the initial charge rise was fast as in the conventional toner using a fluorine-containing quaternary ammonium salt compound, and no decrease in charge with time was observed.

(Example 3)
-Production of Toner 3-
In Example 1, except that the fluorine-containing quaternary ammonium salt compound (3) represented by the following structural formula was used instead of the fluorine-containing quaternary ammonium salt compound (1), in the same manner as in Example 1, [ Toner 3] was prepared.

  From the result of X-ray photoelectron spectroscopy measured for the obtained [Toner 3] in the same manner as in Example 1, it was confirmed that iodine was not present in [Toner 3]. There is no iodine present. Further, the main peak of fluorine was present in the toner in the same state as the raw material powder. From this, it can be seen that in [Toner 3], the fluorine-containing quaternary ammonium salt compound (3) is ionically bonded to the carboxyl group of [Low Molecular Polyester 1] as the binder resin and the carboxyl group of the resin fine particles. all right. In addition, as to the change in the charge amount of [Toner 3] with time, the initial charge rise was fast as in the conventional toner using the fluorine-containing quaternary ammonium salt compound, and no decrease in charge with time was observed.

Example 4
-Production of Toner 4-
In Example 1, except that the fluorine-containing quaternary ammonium salt compound (4) represented by the following structural formula was used instead of the fluorine-containing quaternary ammonium salt compound (1), in the same manner as in Example 1, [ Toner 4] was prepared.

  From the result of X-ray photoelectron spectroscopy measured in the same manner as in Example 1 for the obtained [Toner 4], it was confirmed that iodine was not present in [Toner 4]. Further, the main peak of fluorine was present in the toner in the same state as the raw material powder. From this, it can be seen that in [Toner 4], the fluorine-containing quaternary ammonium salt compound (4) is ionically bonded to the carboxyl group of [Low Molecular Polyester 1] as the binder resin and the carboxyl group of the resin fine particles. It was. In addition, as for the change in the charge amount of [Toner 4] with time, the initial charge rise was fast as in the conventional toner using the fluorine-containing quaternary ammonium salt compound, and no decrease in charge with time was observed.

(Example 5)
<Preparation of Toner 5>
-Synthesis of low molecular weight polyester-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 271 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 354 parts by mass of bisphenol A propylene oxide 2-mole adduct, 285 parts by mass of terephthalic acid, and isophthalic acid 14 parts by mass were charged and subjected to a condensation reaction at 210 ° C. for 10 hours under normal pressure and nitrogen flow. Subsequently, 76 parts by mass of 4-t-butylbenzoic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Next, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 0 to 15 mmHg, followed by cooling to obtain [Low Molecular Polyester 2].
The obtained polyester resin had a mass average molecular weight of 4,000, an acid value of 55 mgKOH / g, a hydroxyl value of 40 mgKOH / g, and a glass transition temperature (Tg) of 51 ° C.

Next, [Toner 5] was produced in the same manner as in Example 1, except that [Low molecular polyester 2] was used instead of [Low molecular polyester 1].
From the result of X-ray photoelectron spectroscopy measured in the same manner as in Example 1 for the obtained [Toner 5], it was confirmed that iodine was not present in [Toner 5]. Further, the main peak of fluorine was present in the toner in the same state as the raw material powder. From this, it is understood that the fluorine-containing quaternary ammonium salt compound (1) is ionically bonded to the carboxyl group of the [low molecular weight polyester 2] as the binder resin and the carboxyl group of the resin fine particles inside the [toner 5]. all right. In addition, the change in the charge amount of [Toner 5] with time was as fast as the initial charge rise as in the conventional toner using the fluorine-containing quaternary ammonium salt compound, and no decrease in charge with time was observed.

(Example 6)
<Preparation of Toner 6>
-Synthesis of low molecular weight polyester-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 73 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 590 parts by mass of bisphenol A propylene oxide 2 mol adduct, 254 parts by mass of terephthalic acid, and isophthalic acid 46 parts by mass was charged and subjected to a condensation reaction at 210 ° C. for 10 hours under normal pressure and nitrogen flow. Subsequently, 38 parts by mass of 4-t-butylbenzoic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Next, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 0 to 15 mmHg, followed by cooling to obtain [Low Molecular Polyester 3]. The obtained polyester resin had a mass average molecular weight of 4,200, an acid value of 8 mgKOH / g, a hydroxyl value of 48 mgKOH / g, and a glass transition temperature (Tg) of 45 ° C.

Next, [Toner 6] was produced in the same manner as in Example 1, except that [Low molecular polyester 3] was used instead of [Low molecular polyester 1].
From the results of X-ray photoelectron spectroscopy measured for the obtained [Toner 6] in the same manner as in Example 1, it was confirmed that iodine was not present in [Toner 6]. Further, the main peak of fluorine was present in the toner in the same state as the raw material powder. From this, it can be seen that in [Toner 6], the fluorine-containing quaternary ammonium salt compound (1) is ionically bonded to the carboxyl group of [Low Molecular Polyester 3] as the binder resin and the carboxyl group of the resin fine particles. all right. In addition, as to the change in the charge amount of [Toner 6] with time, the initial charge rise was fast as in the conventional toner using the fluorine-containing quaternary ammonium salt compound, and no decrease in charge with time was observed.

(Example 7)
<Preparation of Toner 7>
-Synthesis of low molecular weight polyester-
Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 662 parts by mass of a bisphenol A propylene oxide 2-mole adduct, 269 parts by mass of terephthalic acid, and 12 parts by mass of trimellitic anhydride were added, Under a nitrogen stream, the condensation reaction was performed at 210 ° C. for 10 hours. Subsequently, 57 parts by mass of 4-t-butylbenzoic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Next, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, and then cooled to obtain a polyester [low molecular polyester 4]. The obtained polyester resin had a mass-soluble molecular weight of 1,500, an acid value of 25 mgKOH / g, a hydroxyl value of 60 mgKOH / g, and a glass transition temperature (Tg) of 51 ° C.

  Next, [Toner 7] was produced in the same manner as in Example 1 except that [Low molecular polyester 4] was used instead of [Low molecular polyester 1] in Example 1.

  From the result of X-ray photoelectron spectroscopy measured for the obtained [Toner 7] in the same manner as in Example 1, it was confirmed that iodine was not present in [Toner 7]. Further, the main peak of fluorine was present in the toner in the same state as the raw material powder. From this, it can be seen that inside [Toner 7], the fluorine-containing quaternary ammonium salt compound (1) is ionically bonded to the carboxyl group of [low molecular weight polyester 4] as the binder resin and the carboxyl group of the resin fine particles. It was. In addition, as to the change in the charge amount of [Toner 7] with time, the initial charge rise was fast as in the conventional toner using the fluorine-containing quaternary ammonium salt compound, and no decrease in charge with time was observed.

(Example 8)
<Preparation of Toner 8>
-Synthesis of organic fine particle emulsion-
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 14 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 137 parts by mass of styrene Part, 138 parts by weight of methacrylic acid, and 1.2 parts by weight of ammonium persulfate were stirred for 15 minutes at 400 rpm, and a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Next, 30 parts by mass of a 1% by mass aqueous ammonium persulfate solution was added, and the mixture was aged at 71 ° C. for 6 hours, and an aqueous dispersion of a vinyl resin (styrene salt copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate). [Fine particle dispersion 2] was obtained.
The volume average particle diameter of the obtained [Fine Particle Dispersion 2] measured by a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corporation) was 0.18 μm. A portion of [Fine Particle Dispersion 2] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 150 ° C., and the mass average molecular weight was 150,000.

Next, [Toner 8] was produced in the same manner as in Example 1 except that [Fine particle dispersion 2] was used instead of [Fine particle dispersion 1] in Example 1.
From the result of X-ray photoelectron spectroscopy measured for the obtained [Toner 8] in the same manner as in Example 1, it was confirmed that iodine was not present in [Toner 8]. Further, the main peak of fluorine was present in the toner in the same state as the raw material powder. From this, it is understood that the fluorine-containing quaternary ammonium salt compound (1) is ionically bonded to the carboxyl group of [low molecular weight polyester 1] as the binder resin and the carboxyl group of the resin fine particles inside [Toner 8]. all right. In addition, as to the change in the charge amount of [Toner 8] with time, the initial charge rise was fast as in the conventional toner using the fluorine-containing quaternary ammonium salt compound, and no decrease in charge with time was observed.

Example 9
<Preparation of Toner 9>
-Synthesis of organic fine particle emulsion-
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 80 parts by mass of styrene Parts, 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, 12 parts by weight of butyl thioglycolate, and 1 part by weight of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain a white emulsion. It was. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass aqueous ammonium persulfate solution was added and aged at 75 ° C. for 5 hours to copolymerize a vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). ) Aqueous dispersion was obtained. This is designated as [fine particle dispersion 3]. When this [Fine Particle Dispersion 3] was measured with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corporation), the volume average particle size was 120 nm. A portion of [Fine Particle Dispersion 3] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 42 ° C., and the mass average molecular weight was 30,000.

Next, [Toner 9] was produced in the same manner as in Example 1 except that [Fine particle dispersion 3] was used instead of [Fine particle dispersion 1] in Example 1.
From the result of X-ray photoelectron spectroscopy measured in the same manner as in Example 1 for the obtained [Toner 9], it was confirmed that iodine was not present in [Toner 9]. Further, the main peak of fluorine was present in the toner in the same state as the raw material powder. From this, it is understood that the fluorine-containing quaternary ammonium salt compound (1) is ionically bonded to the carboxyl group of [low molecular weight polyester 1] as the binder resin and the carboxyl group of the resin fine particles inside [toner 9]. all right. In addition, as to the change in the charge amount of [Toner 9] with time, the initial charge rise was fast as in the conventional toner using the fluorine-containing quaternary ammonium salt compound, and no decrease in charge with time was observed.

(Example 10)
<Preparation of Toner 10>
-Preparation of oil phase-
In a container in which a stir bar was set, 1,020 parts by mass of [Low molecular weight polyester 1] and 550 parts by mass of ethyl acetate were charged and mixed for 10 hours to prepare [Raw material solution 1].
N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide (fluorine-containing quaternary ammonium salt represented by the following structural formula was added to the obtained [raw material solution 1]. An aqueous solution in which the compound (1)) was dispersed at a concentration of 1% by mass was mixed and stirred so as to be 0.08% by mass with respect to the [raw material solution 1], thereby obtaining [Oil Phase 2].

Next, [Toner 10] was produced in the same manner as in Example 1 except that [Oil phase 2] was used instead of [Oil phase 1] in Example 1.
From the result of X-ray photoelectron spectroscopy measured for the obtained [Toner 10] in the same manner as in Example 1, it was confirmed that iodine was not present in [Toner 10]. Further, the main peak of fluorine was present in the toner in the same state as the raw material powder. From this, it is understood that the fluorine-containing quaternary ammonium salt compound (1) is ionically bonded to the carboxyl group of [low molecular polyester 1] as the binder resin and the carboxyl group of the resin fine particles inside [toner 10]. all right. In addition, as for the change in the charge amount of [Toner 10] with time, the initial charge rise was fast as in the conventional toner using the fluorine-containing quaternary ammonium salt compound, and no decrease in charge over time was observed.

(Example 11)
<Preparation of Toner 11>
-Preparation of oil phase-
In a container in which a stirring bar was set, 1,020 parts by mass of [Low molecular polyester 1] and 550 parts by mass of ethyl acetate were charged and mixed for 10 hours to obtain [Raw material solution 1].
N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide (fluorine-containing quaternary ammonium salt represented by the following structural formula was added to the obtained [raw material solution 1]. An aqueous solution in which the compound (1)) was dispersed at a concentration of 1% by mass was mixed and stirred so as to be 5% by mass with respect to [Raw Material Solution 1] to obtain [Oil Phase 3].

Next, [Toner 11] was produced in the same manner as in Example 1 except that [Oil phase 3] was used instead of [Oil phase 1] in Example 1.
From the result of X-ray photoelectron spectroscopy measured for the obtained [Toner 11] in the same manner as in Example 1, it was confirmed that iodine was not present in [Toner 11]. Further, the main peak of fluorine was present in the toner in the same state as the raw material powder. From this, it is understood that the fluorine-containing quaternary ammonium salt compound (1) is ionically bonded to the carboxyl group of [low molecular polyester 1] as the binder resin and the carboxyl group of the resin fine particles inside [toner 11]. all right. In addition, as for the change in the charge amount of [Toner 11] with time, the initial charge rise was fast as in the conventional toner using the fluorine-containing quaternary ammonium salt compound, and no decrease in charge with time was observed.

(Comparative Example 1)
<Preparation of Toner 12>
-Preparation of oil phase-
[Oil phase 4] was obtained in the same manner as in Example 1, except that the fluorine-containing quaternary ammonium salt compound (1) was not added to [Oil phase 1].

-Emulsification and solvent removal-
[Emulsified slurry 2] was obtained in the same manner as in Example 1, except that [Oil phase 4] was used instead of [Oil phase 1] in Example 1.

-Cleaning and drying-
[Emulsified slurry 2] After 100 parts by mass of the mixture was filtered under reduced pressure, washing and drying were performed as follows.
(1) 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at 15,000 rpm), and then filtered five times.
(2) An aqueous solution in which 100 mass parts of 10 mass% hydrochloric acid and a fluorine-containing quaternary ammonium salt compound (1) represented by the following structural formula are dispersed at a concentration of 1 mass% in the filter cake of (1) is used as a toner base. Fluorine-containing quaternary ammonium salt compound (1) was mixed so as to be 0.1% by mass, mixed with a TK homomixer (30 minutes at 15,000 rpm) and then filtered.
(3) Add 300 parts by mass of ion-exchanged water to the filter cake of (2), mix with a TK homomixer (rotation speed: 15,000 rpm for 10 minutes), and then filter 5 times to obtain [Filter cake 2]. It was.
The obtained [Filtered cake 2] was dried at 45 ° C. for 24 hours in a circulating drier, sieved with a mesh of 75 μm, volume average particle size (Dv) 5.02 μm, number average particle size (Dn) 4. [Toner 12] having 51 μm and Dv / Dn = 1.11 was obtained.

FIG. 20 is a plot of the vicinity of the iodine main peak in [Toner 12], indicating that there is no iodine main peak (I 3d) as measured by X-ray photoelectron spectroscopy using AXIS-ULTRA manufactured by Shimadzu Corporation. It is.
FIG. 21 is a plot showing a main peak (F 1s) of fluorine detected by X-ray photoelectron spectroscopy using AXIS-ULTRA manufactured by Shimadzu Corporation in [Toner 12].
FIG. 22 is a plot showing the main peak (I 3d) of iodine detected by X-ray photoelectron spectroscopy using AXIS-ULTRA manufactured by Shimadzu Corporation with the fluorine-containing quaternary ammonium salt compound (1).
FIG. 23 is a plot diagram showing the fluorine main peak (F 1s) detected by X-ray photoelectron spectroscopy using Shimadzu AXIS-ULTRA, which is a fluorine-containing quaternary ammonium salt compound (1).
FIG. 24 is a plot diagram showing the change over time in the charge amount of [Toner 12].

From the result of X-ray photoelectron spectroscopy measurement, it was confirmed that [Toner 12] does not contain iodine. Further, the main peaks of fluorine and nitrogen were present in the toner in the same state as the raw material powder. From this, it was found that the fluorine-containing quaternary ammonium salt compound (1) was ionically bonded to the carboxyl groups of the resin fine particles on the [Toner 12] surface.
The change with time in the charge amount of [Toner 12] is as fast as that of [Toner 1] and the conventional toner using a fluorine-containing quaternary ammonium salt compound, but is different from that of [Toner 1]. (See FIG. 24).

(Comparative Example 2)
-Production of Toner 13-
In Example 1, except that [Oil Phase 4] was used instead of [Oil Phase 1], the volume average particle size (Dv) was 5.01 μm and the number average particle size (Dn) in the same manner as in Example 1. [Toner 13] of 4.50 μm and Dv / Dn = 1.11 was obtained.
Next, unlike [Toner 1] and [Toner 12], the change with time in the charge amount of [Toner 13], which does not contain a fluorine-containing quaternary ammonium salt compound, is slow and the charge amount reaches the maximum. The time to complete was 600 seconds. Note that there was no decrease in the charge amount, which was almost a monotonically increasing function (see FIG. 25).

  Next, for the toners 1 to 13 of Examples 1 to 11 and Comparative Examples 1 to 2, the charging property and the fixing property were evaluated as follows. The results are shown in Table 1.

<Chargeability>
-Charge amount-
Using an iron powder carrier (TEFV200 / 300, manufactured by Powdertech Co., Ltd.), 6 g of a two-component developer prepared by a conventional method is weighed, charged into a metal cylinder that can be sealed, stirred at a stirring speed of 640 rpm, and blow-off method. The charge amount was determined. The toner concentration was adjusted to 7% by mass.

−Charging speed−
In the measurement of the charge amount, “◯” was given as good when the charge amount in 60 seconds was 90% or more of the maximum charge amount, and “X” was given when the charge amount did not reach 90%.

−Charging reduction−
In the measurement of the charge amount, “◯” was given as good when the charge amount in 3,600 seconds was 90% or more of the maximum charge amount, and “X” was reduced to 90% or less.

From the results shown in Table 1, the toners of Examples 1 to 11 have fluorine-containing quaternary ammonium salt compounds as charge control agents at the ends of the unmodified polyester resin as the binder resin, as compared with the toners of Comparative Examples 1 and 2. It is recognized that the amount of charge decreases with time even when the surface of the toner is scraped by causing the toner to be ionically bonded so that the fluorine-containing quaternary ammonium salt compound is uniformly present inside the toner.
On the other hand, in Comparative Example 1 having a fluorine-containing quaternary ammonium salt compound as a charge control agent on the toner surface by conventional wet external addition, a reduction in charge amount is recognized when the toner surface is scraped over time.
Further, Comparative Example 2 which does not contain a fluorine-containing quaternary ammonium salt compound as a charge control agent has a low charging speed and a slow charge rise.

  The toner of the present invention has little change over time in the charge amount, good charge rise at the beginning of stirring, and excellent low-temperature fixability. Therefore, a developer, a container containing toner, a process cartridge, an image forming method, and an image Suitable for forming apparatus.

FIG. 1 is a diagram showing an analytical toner obtained by SEM observation with a slightly scraped surface. FIG. 2 is a view showing the toner for analysis obtained by SEM observation, the surface of which is scraped and hardly remains. FIG. 3 is a diagram showing the fluorine addition position of the analysis toner obtained by SEM observation EDS element mapping with the surface slightly shaved. FIG. 4 is a diagram showing the fluorine addition position of the analysis toner obtained by EDS element mapping in SEM observation, with the surface being scraped and hardly remaining. FIG. 5 is a plot showing that the main peak of iodine does not exist in the toner for analysis obtained by X-ray photoelectron spectroscopy. FIG. 6 is a plot diagram showing the main peak of fluorine of the analytical toner obtained by X-ray photoelectron spectroscopy. FIG. 7 is a plot diagram showing the main peak of nitrogen of the toner for analysis obtained by X-ray photoelectron spectroscopy. FIG. 8 is a plot showing the main peak of iodine of the fluorine-containing quaternary ammonium salt compound (1) obtained by X-ray photoelectron spectroscopy. FIG. 9 is a plot showing the main peak of fluorine of the fluorine-containing quaternary ammonium compound (1) obtained by X-ray photoelectron spectroscopy. FIG. 10 is a plot showing the nitrogen main peak of the fluorine-containing quaternary ammonium salt compound (1) obtained by X-ray photoelectron spectroscopy. FIG. 11 is a plot diagram showing the change with time of the fluorine-containing quaternary ammonium salt compound (1) molecular number ratio with respect to the number of bisphenol A derivatives in the binder resin polyester of the toner for analysis obtained by NMR quantitative analysis. FIG. 12 is a diagram showing the peak of the analytical toner obtained by ¹ H-NMR measurement. FIG. 13 is a diagram showing the peak of the unmodified polyester used for preparing the analytical toner, obtained by ¹ H-NMR measurement. FIG. 14 is a graph showing the change over time in the charge amount of the analysis toner. FIG. 15 is a plot showing that the main peak of iodine does not exist in the toner of Example 1 obtained by X-ray photoelectron spectroscopy. FIG. 16 is a plot diagram showing the main peak of fluorine of the toner of Example 1 obtained by X-ray photoelectron spectroscopy. FIG. 17 is a plot showing the main peak of iodine of the fluorine-containing quaternary ammonium salt compound (1) obtained by X-ray photoelectron spectroscopy. FIG. 18 is a plot showing the main peak of fluorine of the fluorine-containing quaternary ammonium salt compound (1) obtained by X-ray photoelectron spectroscopy. FIG. 19 is a graph showing the change over time in the charge amount of the toner of Example 1. FIG. 20 is a plot showing that the main peak of iodine does not exist in the toner of Comparative Example 1 obtained by X-ray photoelectron spectroscopy. FIG. 21 is a plot diagram showing the main peak of fluorine of the toner of Comparative Example 1 obtained by X-ray photoelectron spectroscopy. FIG. 22 is a plot showing the main peak of iodine of the fluorine-containing quaternary ammonium salt compound (1) obtained by X-ray photoelectron spectroscopy. FIG. 23 is a plot showing the main peak of fluorine of the fluorine-containing quaternary ammonium salt compound (1) obtained by X-ray photoelectron spectroscopy. FIG. 24 is a graph showing the change with time of the charge amount of the toner of Comparative Example 1. FIG. 25 is a graph showing the change over time in the charge amount of the toner of Comparative Example 2. FIG. 26 is a schematic configuration diagram showing an example of a process cartridge used in the present invention. FIG. 27 is a schematic configuration diagram showing an example of an image forming apparatus used in the image forming method of the present invention. FIG. 28 is a schematic configuration diagram showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 29 is a schematic configuration diagram showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 30 is a schematic configuration diagram showing another example of an image forming apparatus used in the image forming method of the present invention. FIG. 31 is a schematic configuration diagram showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 32 is a schematic enlarged view of the image forming element portion of FIG.

Explanation of symbols

1 Electrostatic latent image carrier (photosensitive drum)
DESCRIPTION OF SYMBOLS 2 Transfer apparatus 3 Sheet conveyance belt 4 Intermediate transfer body 5 Secondary transfer apparatus 6 Paper feeding apparatus 7 Fixing apparatus 8 Cleaning apparatus 9 Intermediate transfer body cleaning apparatus 10 Electrostatic latent image carrier (photosensitive drum)
10K Electrostatic latent image carrier for black 10Y Electrostatic latent image carrier for yellow 10M Electrostatic latent image carrier for magenta 10C Electrostatic latent image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device DESCRIPTION OF SYMBOLS 18 Image forming means 20 Charging roller 21 Exposure apparatus 22 Secondary transfer apparatus 23 Roller 24 Secondary transfer belt 25 Fixing apparatus 26 Fixing belt 27 Pressure roller 28 Sheet reversing apparatus 30 Exposure apparatus 32 Contact glass 33 1st traveling body 34 2nd Traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Development roller La 44Y Development roller 44M Development roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 switching claw 56 discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 cleaning device 64 discharge device 70 discharge lamp 80 transfer roller 90 cleaning device 95 recording medium 100 image forming device 101 electrostatic latent image Carrier 102 Charging device 103 Exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem developing device 130 Document table 142 Paper feed roller 143 Paper bank 1 44 Paper Feed Cassette 145 Separation Roller 146 Paper Feed Path 147 Transport Roller 148 Paper Feed Path 150 Copier Main Body 160 Charging Device 200 Paper Feed Table 210 Image Fixing Device 220 Heating Roller 230 Pressure Roller 300 Scanner 400 Automatic Document Feeder (ADF)

Claims (13)

A toner obtained by removing an organic solvent from a dispersion in which a solution or dispersion in which a toner material containing at least a binder resin and a charge control agent is dissolved or dispersed in an organic solvent is dispersed in an aqueous medium. And
The toner, wherein the binder resin has at least a functional group capable of ion binding, and the charge control agent is ionically bonded to the binder resin inside the toner. The toner according to claim 1, wherein the charge control agent is a fluorine-containing quaternary ammonium salt compound. The toner according to claim 2, wherein the fluorine-containing quaternary ammonium salt compound is a compound represented by the following structural formula (1).
However, in the structural formula (1), R ¹ Represents any one of a hydrogen atom, a fluorine atom, and a hydrocarbon group. R ² ~ R ⁴ May be the same as or different from each other, and each represents a hydrogen atom, a fluorine atom, or a hydrocarbon group. X represents a divalent organic group. Y represents a counter ion. n and m each represents a positive integer. The toner according to claim 3, wherein the fluorine-containing quaternary ammonium salt compound is N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide represented by the following structural formula. .
The toner according to claim 2, wherein the content of the fluorine-containing quaternary ammonium salt compound in the toner is 0.05 to 10% by mass. The toner according to claim 1, wherein the binder resin has a carboxyl group at a terminal . The toner according to claim 1, wherein the binder resin contains a polyester resin. The toner according to claim 1, wherein the binder resin has an acid value of 1 to 30 mg KOH / g. The toner according to claim 1, wherein the binder resin has a glass transition temperature (Tg) of 40 to 90 ° C. 9. The volume average particle diameter (Dv) of the toner is 4 to 8 μm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.25 or less. The toner according to any one of 1 to 9. A developer containing the toner according to claim 1. The developer according to claim 11, which is one of a one-component developer and a two-component developer. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to claim 1 to produce a visible image A developing step for forming the visible image, a transferring step for transferring the visible image to a recording medium, a fixing step for fixing the transferred image transferred to the recording medium, and a toner remaining on the electrostatic latent image carrier. An image forming method comprising at least a cleaning step of removing.