JP2008225419A - Toner for electrostatic charge image development, developer and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development which exhibits fast rising of the initial charge amount and a sharp distribution of charges, while keeping a stable charge amount with less changes in the charge amount with the lapse of time, can form a visible image with high sharpness for a long period of time, and has high durability, and to provide a toner for electrostatic charge image development which is adaptable to a low-temperature fixing system. <P>SOLUTION: The toner is obtained by dispersing a dissolved material or a dispersed material containing a toner composition containing at least a binder resin, resin fine particles and a charge control agent in an aqueous medium, and the removing the solvent. The resin fine particles have a functional group that can form an ionic bond, and the charge control agent forms an ionic bond with the resin fine particles within the toner. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner for developing an electrostatic charge image formed on the surface of a photoreceptor in electrophotography, electrostatic recording, and the like, a developer containing the toner, and an image forming method using the toner The present invention relates to a container containing the toner and an image forming apparatus loaded with the toner.

  Conventionally, in an electrophotographic apparatus, an electrostatic recording apparatus, or the like, an electric or 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. The toner image is usually transferred onto a transfer material such as paper and then fixed by a method such as heating.

  Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a suspension polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventing agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. According to the 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, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. For this reason, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, The fine powder of 5 μm or less and the coarse powder of 20 μm or more must be removed by classification, and there is a disadvantage that the yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. The uneven dispersion of the compounding agent adversely affects the fluidity, developability, durability, image quality and the like of the toner.

In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented. A technique for producing a toner for developing an electrostatic latent image by a polymerization method is known. For example, toner particles are obtained by a suspension polymerization method. However, the toner particles obtained by the suspension polymerization method contaminate the charging roller that contacts and charges the photosensitive member, and the original charging ability cannot be exhibited. For this reason, a method for obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method is disclosed (see Patent Document 1).
However, in the toner particles obtained by the emulsion polymerization method, a large amount of the surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of the toner charging is impaired. The 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, the following problems occur in the method of obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method.
When releasing agent fine particles are associated with each other in order to improve offset resistance, the releasing agent fine particles are taken into the toner particles, and 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 constitute toner particles, so there is a variation in composition (content ratio of constituent components) and molecular weight of constituent resins among the obtained toner particles. As a result, the toner particles have different surface characteristics, and a stable image cannot be formed over a long period of time. Further, in a low-temperature fixing system requiring low-temperature fixing, fixing inhibition occurs due to resin fine particles unevenly distributed on the toner surface, and a fixing temperature range cannot be secured.

  On the other hand, a toner manufacturing 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. Has an advantage. In addition, although the advantage that the structure control of the toner (the preparation of the core / shell structure) is possible, the shell structure is a resin-only layer intended to reduce the exposure to the surface of the pigment or wax, In particular, the surface state is not devised, nor is such a structure. Therefore, although it has a shell structure, the toner surface is an ordinary resin, and there is no particular ingenuity. When aiming at lower temperature fixing, it is not sufficient in terms of heat-resistant storage stability and environmental charge stability. Met.

  In addition, in any of the suspension polymerization method, emulsion polymerization method and dissolution suspension method, it is common to use a styrene-acrylic acid ester copolymer. Distribution and shape control were difficult. In addition, there was a limit to fixability when aiming at lower temperature fixing.

  On the other hand, it is also known to use a polyester modified with a urea bond for the purpose of heat-resistant storage stability and low-temperature fixing (see, for example, Patent Document 3). However, it was a problem because it was not sufficient in terms of environmental charge stability.

  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. On the other hand, it is 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. The “tandem method” is effective for speeding up (see, for example, Patent Document 5).

  On the other hand, in a fixing process using a contact heating method performed using a heating member such as a heat roller, the toner particles are required to release from the heating member (hereinafter referred to as “offset resistance”). Here, the offset resistance can be improved by the presence of a release agent on the toner particle surface. On the other hand, Patent Documents 6 and 7 disclose a method for improving the offset resistance not only by containing resin fine particles in the toner particles but also by unevenly distributing the resin fine particles on the surface of the toner particles. Has been. However, the minimum fixing temperature is increased, and the low temperature fixing property, that is, the energy saving fixing property is not sufficient.

  On the other hand, with regard to the charging characteristics of the toner, it is also known that a fluorine compound is contained in the toner as a means for increasing the charging ability of the negatively charged toner in the role of a charge control agent or the like (Patent Document 8, Patent Document 8). (See Patent Document 9). However, this method does not have a sufficient effect of improving the charge rising property, and there is a problem in that toner ground stain (fogging) and toner scattering occur. It was also a problem in terms of environmental charge stability.

  Many charge control agents are polar compounds, and when using an aqueous emulsion and granulation by aqueous emulsification, if the charge control agent is added and used, the affinity to the oil and water phases In many cases, it is eluted into the aqueous phase due to the effect of solubility, 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 discloses a toner having a constitution in which a fluorine compound is added to the toner surface by wet external addition, whereby the charging ability is high, the charge amount distribution is sharp, weakly charged, and there are few reversely charged toners. However, this method has a problem in that the charge amount is reduced with time due to long-time stirring with the carrier. Patent Document 11 discloses a toner having a configuration in which a fluorine-based compound is dispersed in an aqueous medium to be contained in the toner. However, even with this technique, a decrease in charge amount with time occurs. Conventionally, the cause of these reductions in the amount of charge has not been known and has been difficult to solve.

  That is, as described above, as a means for increasing the charging ability of the toner (particularly negatively charged toner) with respect to the charging property, a sufficient charging effect can be obtained only by containing the fluorine-based compound as a charge control agent. Inability to obtain was a problem. That is, if a fluorine compound is simply contained in the toner manufacturing process, there may be a case where a sufficient charging improvement effect cannot be obtained, and examination of the method and conditions during the fluorine treatment has been required.

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

The present invention has been made based on the above situation.
That is, the first object of the present invention is to maintain a stable charge amount with little change in charge amount with time, to quickly produce a visible image with a fast initial charge amount rise, a sharp charge amount distribution and good sharpness over a long period of time. An object of the present invention is to provide a toner for developing an electrostatic charge image that can be formed and has high durability.
A second object of the present invention is to provide a toner for developing an electrostatic image corresponding to a low-temperature fixing system.
A third object of the present invention is to provide a developer containing the toner for developing an electrostatic image, an image forming method using the toner, a container containing the toner, and an image forming apparatus loaded with the toner. It is in.

As a result of extensive studies by the present inventors, it was concluded that the cause of a decrease in charge amount with time of a conventional toner containing a fluorine-based compound as a charge control agent was as follows.
That is, when organic resin fine particles are used as a toner material for the purpose of suppressing aggregation between particles during toner emulsification and the surface of the toner is treated with a fluorine compound, the fluorine compound is preferential to the organic resin fine particles in the vicinity of the surface. This is because the fluorine compound itself is unevenly distributed on the toner surface, and when the toner surface is abraded or cracked by stirring with the carrier, it acts as a charge control agent. This is because the fluorine-based compound that is present disappears from the toner.

The evidence will be described as follows from the results of SEM image observation, X-ray photoelectron spectroscopy measurement, NMR measurement, and charge amount measurement.
N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide (hereinafter referred to as fluorine compound (1)) using only a binder resin and organic fine particles When the toner prepared by adding the toner in the same manner as in JP-A-2005-115213 was analyzed, the following results were obtained.
1: When the SEM image of the toner after mixing and stirring with the carrier was observed, there was a change in the toner surface, and it was observed that the toner skin-like part was peeled off.
JSM-made JSM-7400F was used for the measurement. FIG. 1 is a diagram showing toner with a part of the surface shaved, and FIG. 2 is a diagram showing toner with the surface almost shaved and only a part of the outer skin portion remaining.

2: The presence of fluorine was examined using the EDS element mapping method. As a result, a large amount of fluorine was present in the toner outer skin portion, while almost no fluorine was present in the toner.
The measurement used JSM-7400. The results are shown in FIGS. The black part in the figure is a part with a large amount of detected fluorine. FIG. 3 is a diagram showing the fluorine existing position in FIG. 1, and FIG. 4 is a diagram showing the fluorine existing position in FIG. FIG. 3 shows that a large amount of fluorine is present in the surface scraped portion, and almost no fluorine is detected on the outermost surface. When FIG. 4 is seen, although it turns out that the fluorine exists in the skin-like part slightly left, the fluorine is hardly detected in the inside where the skin has been shaved. From this, it can be seen that fluorine is mainly present in the outer skin portion near the toner surface and hardly present in the inside.

3: When the existence state of the fluorine compound in the toner was examined using X-ray photoelectron spectroscopy, the fluorine compound was ionically bonded to the carboxyl group present in the binder resin or the organic resin fine particles. Results were 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 there is no iodine in the analyzed toner, and the result is that it exists in the same state as in the raw material powder except that no iodine is present. 5-obtained from FIG. The only part of the binder resin or organic fine particles that can be stably ion-bonded is the carboxyl group, and this led to the conclusion that it was ion-bonded to the carboxyl group in the binder resin or organic fine particle. .

4: From the NMR measurement result, it was obtained that the fluorine compound was mainly added to the organic 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 compounds to the number of bisphenol A molecules in the binder resin. Quantitative analysis of the fluorine compound in the toner using 19F-NMR was performed, and the time-dependent change in the amount of the fluorine compound was examined. As a result, the detected amount of the fluorine compound was increased at the initial stage of stirring with the carrier (see FIG. 11). This indicates that a fluorine compound is added to a substance that does not dissolve in THF-d8 used as a solvent for NMR measurement, and organic fine particles correspond to the material used. The fact that the organic fine particles do not dissolve in THF-d8 is confirmed from the comparison of the 1H-NMR measurement of the binder resin and the 1H-NMR measurement results of the toner made of the binder resin and the organic fine particles because no different peak is observed. (See FIGS. 12 and 13).

Organic fine particles are used to control the toner shape (particle size distribution, circularity, etc.) at the time of toner granulation, and adhere to the toner surface and inside (mainly near the surface) during emulsification. Suppresses aggregation between toner particles during emulsification. The methacrylic acid constituting the organic fine particles has a carboxyl group, and a large amount of carboxyl groups are present in the organic fine particles. On the other hand, in the polyester-based binder resin, the carboxyl group exists only at the resin terminal, and the toner surface where organic fine particles mainly exist has more carboxyl groups than in the toner.

  The fact that methacrylic acid, which is one of the monomers that make up organic fine particles that are high molecular compounds, contains carboxyl groups, and the carboxyl groups present in the toner are more present in the organic fine particles than in the binder resin. Can explain NMR measurement without contradiction as a result of SEM image and XPS measurement.

5: The change with time of the charge amount was examined. As a result, it was found that the charge amount of the toner containing the fluorine-based compound is greatly affected by the amount of the fluorine-containing compound contained compared with the NMR quantitative analysis result.
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 weight. When the time-dependent change in the charge amount was examined, a correlation with the result of quantitative analysis of the fluorine compound by NMR was observed (see FIG. 14). From this, it was concluded that the charge amount of the toner containing the fluorine compound as a charge control agent is greatly influenced by the amount of the fluorine compound present.

From the above results, the charge reduction is preferentially added to the organic fine particles unevenly distributed in the vicinity of the toner surface, so that when the toner surface is scraped, the amount of charge control agent in the toner is reduced. It was concluded that this was the cause.
As a result of repeated investigations by the present inventors, N, N, N-trimethyl- [3- (4-perfluorononenyloxy) is added to the organic fine particles in order to reduce the change with time in the toner charge amount and realize stable chargeability. A fluorinated compound such as benzamido) propyl] ammonium iodide is added by ionic bonding, and a toner is prepared using the organic fine particles to which the fluorinated compound is added, and the fluorinated compound is present inside the toner, to the vicinity of the toner surface. It has been found that this can be achieved by suppressing the uneven distribution of the fluorine-based compound. The present invention has been completed.

Thus, according to the present invention, the following (1) to (18) are provided.
(1) A toner obtained by removing a solvent from a dispersion obtained by dispersing a solution or dispersion containing a toner composition containing at least a binder resin, resin fine particles, and a charge control agent in an aqueous solvent. The electrostatic charge image developing toner, wherein the resin fine particles have at least a functional group capable of ion binding, and the charge control agent is ionically bonded to the resin fine particles inside the toner.
(2) The electrostatic charge image developing toner according to (1), wherein the charge control agent is a quaternary ammonium salt.
(3) The electrostatic charge image developing toner according to (1) or (2), wherein the charge control agent is a fluorine-based compound represented by the following general formula (1).
(Wherein R ^{1 to} R ⁴ are a lower alkyl group having 1 to 10 carbon atoms and an aryl group, X is —SO ₂ —, —CO—, Y is I, Br, n, and m are positive integers. )

(4) The electrostatic charge image according to (3), wherein the fluorine compound is N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide. Development toner.
(5) The electrostatic image developing toner according to any one of (1) to (4), wherein the binder resin has a carboxyl group terminal.
(6) The electrostatic image developing toner according to any one of (1) to (5), wherein the binder resin is a polyester resin.
(7) The toner for developing an electrostatic charge image according to any one of (1) to (6), wherein the content of the fluorine compound is 0.05 to 10% by weight with respect to the toner.
(8) The electrostatic charge image developing toner according to any one of (1) to (7), wherein the binder resin has an acid value of 1 to 30 mgKOH.
(9) The toner for developing an electrostatic charge image according to any one of (1) to (8), wherein the toner binder resin has a glass transition point (Tg) of 40 to 90 ° C.

(10) The above-mentioned (1) to (1), wherein resin fine particles are used in combination on the toner surface or inside, and the resin fine particles comprise a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin and / or a mixture thereof. The toner for developing an electrostatic charge image according to any one of 9).
(11) The electrostatic image developing toner according to any one of (1) to (10), wherein the resin fine particles have a weight average molecular weight of 5,000 to 200,000.
(12) The toner for developing an electrostatic charge image according to any one of (1) to (11), wherein the toner particles have a volume average particle diameter of 4 to 8 μm.
(13) The ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner particles is 1.25 or less, and any one of (1) to (12) above The electrostatic image developing toner according to claim 1.
(14) A developer containing 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) An image forming method comprising using the electrostatic image developing toner according to any one of (1) to (13).
(17) An image forming method using the electrostatic image developing toner according to any one of (1) to (13) in an image forming method using a developing device having a toner recycling mechanism.
(18) A container containing the electrostatic image developing toner according to any one of (1) to (13).

Hereinafter, the present invention will be described in further detail.
(Fluorine compounds)
As the fluorine compound used in the toner of the present invention, a fluorine-containing quaternary ammonium salt or the like is used. For example, a compound represented by the following general formula (1) is preferably used.
(Wherein R ^{1 to} R ⁴ are a lower alkyl group having 1 to 10 carbon atoms and an aryl group, X is —SO ₂ —, —CO—, Y is I, Br, n, and m are positive integers. )

  In the present invention, particularly preferable fluorine-based compounds represented by the general formula (1) are N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide, And mixtures with other fluorine-based compounds. The effects of the present invention are not limited to the characteristics of the fine powder such as the purity, pH, and thermal decomposition temperature of the fluorine compound.

  The fluorine-based compound can be contained in the toner base by ionic bonding, preferably in the range of 0.05 to 10% by weight, more preferably in the range of 0.1 to 8% by weight with respect to the toner. When the fluorine compound content is less than 0.05% by weight, a sufficient charge amount cannot be obtained, and the effects of the present invention cannot be obtained sufficiently. On the other hand, when it exceeds 10% by weight, fixing failure of the developer occurs.

A polyester resin is used as the binder resin in the present invention. The polyester resin is roughly classified into a modified polyester and an unmodified polyester resin, both of which can be used.
(Unmodified polyester)
In the present invention, inclusion of unmodified polyester as a toner binder component improves low-temperature fixability and gloss when used in a full-color device. Examples of the unmodified polyester include a polycondensate of polyol (1) and polycarboxylic acid (2).

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes 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 phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). 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.
The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  The acid value of the polyester used as the binder resin is preferably 1-30, more preferably 5-20. By giving an appropriate acid value, it tends to be negatively charged. When the acid value is 5 to 20, it is easy to achieve both heat-resistant storage stability and low-temperature fixing.

In the present invention, the glass transition point (Tg) of the toner binder resin is usually 40 to 90 ° C., preferably 55 to 65 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 90 ° C., the low-temperature fixability becomes insufficient. As the storage elastic modulus of the toner binder, the temperature (TG ′) at which 10000 dyne / cm ² is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner binder resin, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. 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, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. 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, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

(Resin fine particles)
The resin fine particles used in the present invention can be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resins, polyurethane resins, epoxy resins, Examples thereof include polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.
The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.
Examples of functional groups capable of ion bonding include carboxyl groups, hydroxyl groups, nitriles, halogens, sulfides, thiols, organic phosphorus, nitric acid, nitro compounds, and the like.

(Dv / Dn (ratio of volume average particle diameter / number average particle diameter))
In the present invention, the volume average particle diameter (Dv) of the toner is 4 to 8 μm, and the ratio (Dv / Dn) to the number average particle diameter (Dn) is 1.25 or less, preferably 1.10 to 1. The dry toner of No. 25 is excellent in all of heat-resistant storage stability, low-temperature fixability, and hot-offset resistance, particularly excellent in image gloss when used in a full-color copying machine, etc. Even if the toner balance for a long period of time is performed, the fluctuation of the toner particle diameter in the developer is reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Even when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner is filmed on the developing roller and the toner is made thin. The toner was not fused to a member such as a blade, and good and stable developability and images were obtained even when the developing device was used (stirred) for a long time.

In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced, or the one-component development When used as an agent, 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 higher than the above range of the present invention.

On the contrary, when the toner particle diameter is larger than the above range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and the toner in the developer is balanced. In many cases, the fluctuation of the particle size of the particles becomes large. It was also clarified that the same is true when the volume average particle diameter / number average particle diameter (Dv / Dn) is larger than 1.25.
Further, when the volume average particle diameter / number average particle diameter (Dv / Dn) is smaller than 1.10, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount. It has become clear that there is a case where the toner cannot be charged or the cleaning property is deteriorated.

(Urea-modified polyester)
In the present invention, not only the unmodified polyester resin alone but also a modified polyester may be contained as a toner binder resin. As a reaction product of a prepolymer made of a modified polyester resin and a compound that extends or crosslinks, a polyester modified with a urea bond is preferable.
Examples of the polyester modified with a urea bond include a reaction product of a polyester prepolymer (A) having an isocyanate group and amines (B). Examples of the polyester prepolymer (A) having an isocyanate group include a product obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3), which is a polycondensate of polyol (1) and polycarboxylic acid (2). Preferred examples of the polyol (1) and the polycarboxylic acid (2) are the same as those of the unmodified polyester. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diamines). Cyclohexane, isophoronediamine, etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of B1 to B5 blocked amino groups (B6) include ketimine compounds and oxazoline compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates. In the present invention, the polyester (i) modified with a urea bond may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The residual monomer amount in the toner shown in the present invention may be adjusted by any method. For example, it can also be controlled by the temperature and time during condensation polymerization of urea-modified polyester and / or unmodified polyester.
The urea-modified polyester of the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester is not particularly limited, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. In the case of urea-modified polyester alone as the binder resin, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

(Coloring agent)
In the present invention, a colorant may be used in combination. As the colorant of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide , Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used.
The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention may be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the above-mentioned modified and unmodified polyester resins, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and substituted polymers thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, 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, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

  The masterbatch can be obtained by mixing and kneading a resin for a masterbatch and a colorant under high shearing force and kneading. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
In the present invention, a wax may be contained. Known waxes can be used as the wax of the present invention, and examples thereof include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long-chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing waxes. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability.
The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Production method)
The unmodified polyester as the toner binder resin can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off if necessary under reduced pressure. Thus, a polyester having a hydroxyl group is obtained.
When urea-modified polyester is used in combination, an unmodified polyester is prepared by the same method as described above, and then reacted with polyisocyanate (3) at 40 to 140 ° C. to give a prepolymer (A ) Further, (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond. When (3) is reacted and (A) and (B) are reacted, a solvent can be used as necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to the isocyanate (3), such as tetrahydrofuran (such as tetrahydrofuran).

The toner for developing an electrostatic charge image of the present invention can be produced by the following method, but is not limited thereto.
(Toner production method in aqueous medium)
As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
In an aqueous medium, a dispersion composed of a non-modified polyester and other toner composition (hereinafter referred to as toner raw material), a colorant, a colorant masterbatch, a release agent, a charge control agent, a modified polyester resin, etc. Examples of the forming method include a method of adding a toner raw material composition and dispersing it by shearing force.
The toner raw material may be mixed when forming the dispersion in the aqueous medium, but it is more preferable that the toner raw material is mixed in advance and then the mixture is added and dispersed in the aqueous medium. In the present invention, other toner raw materials such as a colorant and a release agent do not necessarily have to be mixed when forming particles in an aqueous medium, and are added after the particles are formed. Also good. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

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, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferable in that the dispersion of the toner raw material has a low viscosity and is easily dispersed.
The amount of the aqueous medium used relative to 100 parts by weight of the toner composition is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  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 composition is dispersed in the aqueous medium, or may be dispersed in the aqueous medium. An amine (B) may be added later 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.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphates, alkylamines as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water Amine salts such as salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl N, amphoteric surfactants such as N- dimethyl ammonium betaine and the like.

By using a surfactant having a fluoroalkyl group, the effect can be increased in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned,
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), Mega-Fac F-l0, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

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

Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

  Further, in order to lower the viscosity of the toner composition, a solvent in which the urea-modified polyester or the prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of the solvent with respect to 100 weight part of prepolymers (A) is 0-300 weight part normally, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after elongation and / or crosslinking reaction.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

The obtained dried toner powder is mixed with different kinds of particles such as release agent fine particles, fluidizing agent fine particles and colorant fine particles, or fixed on the surface by applying mechanical impact force to the mixed powder. By fusing, it is possible to prevent detachment of foreign particles from the surface of the resulting composite particles.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) is modified to reduce the grinding air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system (Made by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

(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 according to the present invention, the toner particle diameter hardly fluctuates even if the balance of the toner is performed, and the filming of the toner on the developing roller or the toner is thinned. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developer, Good and stable developability can be obtained.

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

(Development roller)
Examples of the material of the developing roller that can be used when the toner of the present invention is used as a one-component developer include metals such as aluminum, iron, and SUS as those having no elastic layer. In addition, the surface is processed by a processing method such as sandblasting. For example, natural rubber, silicone rubber, urethane rubber, butadiene rubber, chloroprene rubber, neoprene rubber, isoprene rubber, NBR, and the like can be used as those having an elastic layer. It is effective when used in the form of foam, sponge or the like, and changing the material of these elastic layers depending on the part of the developing roller is effective but not necessarily limited.
It is also possible to provide a magnetic field generating layer, and the magnetic field strength may be changed depending on the part of the developing roller. Further, a toner supply roller that supplies toner to the developing roller may be provided, and contact or non-contact can be appropriately selected between the two rollers. 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 the variation of the toner layer on the developing roller can be eliminated. The material of the toner supply roller is not particularly limited, and a known material such as sponge, rubber, SUS, or a material coated with these can be used. Further, 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. As the coating resin, generally known resins can be used.

It is also possible to provide blades upstream and downstream of the developing roller rotation with respect to the developing position. Furthermore, it is possible to apply a voltage to these members. The supply roller can also serve as a stripping and supplying function. Furthermore, it is also preferable to provide a toner layer regulating member on the upstream side of the developing unit. The toner layer regulating member may be plate-shaped or a rotating roller may be used. Charge may be injected into the toner by the toner layer regulating member.
Further, as a developing method used in the present invention, a contact developing method in which the developing roller and the electrostatic charge image holding member are in contact with each other or a non-contact developing method in which the developing roller is not in contact may be used.

  The toner for developing an electrostatic charge image of the present invention is a toner having little change in charge amount with time, good charge rising at the beginning of stirring, excellent low-temperature fixability, and high durability. Further, according to the present invention, it is possible to provide a developer containing the toner, an image forming method using the toner, a container containing the toner, and an image forming apparatus loaded with the toner.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to this. Hereinafter, a part shows a weight part.
[Example 1]
~ Synthesis of organic fine particle emulsion ~
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, 110 butyl acrylate Parts and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Furthermore, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and an aqueous dispersion of vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). [Fine particle dispersion 1] was obtained. The volume average particle diameter of the [fine particle dispersion 1] measured by a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corp.) was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 58 ° C., and the weight average molecular weight was 130,000. [Particulate dispersion 1] 10 parts of N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide (hereinafter referred to as fluorine compound (1)) per 10 parts 20 parts of the aqueous solution dispersed at% concentration was mixed and stirred to obtain [fine particle dispersion 1-2].

-Adjustment of aqueous phase-
86 parts of water, 3.5 parts of [fine particle dispersion 1-2], 25 parts of 50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 14 parts of ethyl acetate are mixed. Agitation gave a milky white liquid. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 691 parts of bisphenol A ethylene oxide 2-mole adduct and 309 parts of terephthalic acid were charged and subjected to a condensation reaction at 210 ° C. for 10 hours under a normal pressure nitrogen stream. . 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 polyester resin obtained had a weight-average molecular weight of 3,500, an acid value of 10 KOH mg / g, a hydroxyl value of 50 KOH mg / g, and a glass transition point of 40 ° C.

~ Creation of oil phase ~
In a container equipped with a stirring bar, 1020 parts of [Low molecular weight polyester 1] and 550 parts of ethyl acetate were charged and mixed for 10 hours to obtain [Oil phase 1].
~ Emulsification⇒Desolvation ~
[Aqueous phase 1] 210 parts are put in a container, mixed with TK homomixer (made by Tokushu Kika) at 3,000 rpm for 5 minutes, and then [oil phase 1] 110 parts are added. The mixture was mixed at 000 rpm for 30 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer, and after removing the solvent at 30 ° C. for 10 hours, aging was carried out at 45 ° C. for 10 hours to obtain [Dispersion slurry 1]. [Dispersion Slurry 1] had a volume average particle size of 5.40 μm and a number average particle size of 4.70 μm (measured with Coulter Electronics Co., Ltd. Coulter Multisizer III).

~ Washing⇒Drying ~
[Emulsified slurry 1] After 100 parts were filtered under reduced pressure,
1: 100 parts of ion-exchanged water was added to the filter cake and mixed with a TK homomixer (5 minutes at 15,000 rpm) and then filtered five times.
100 parts of 10% hydrochloric acid was added to a 2: 1 filter cake, mixed with a TK homomixer (rotation speed: 15,000 rpm for 30 minutes), and then filtered.
300 parts of ion-exchanged water was added to the 3: 2 filter cake, mixed with a TK homomixer (rotation speed: 15,000 rpm for 10 minutes), and then filtered five times to obtain [Filter cake 1].
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, sieved with a mesh of 75 μm, volume average particle diameter Dv 5.30 μm, number average particle diameter Dn 4.80 μm, Dv / Dn 1.10 (Coulter [Toner 1] of (measured with counter TAII) was obtained.

FIG. 15 is a plot of the vicinity of the main peak of iodine showing that the main peak (I 3d) of iodine is not present in the toner 1 as measured by X-ray photoelectron spectroscopy.
FIG. 16 is a plot diagram showing the main peak (F 1s) of fluorine detected by X-ray photoelectron spectroscopy in the toner 1.
FIG. 17 is a plot showing the main peak (I 3d) of iodine detected by X-ray photoelectron spectroscopy in the fluorine compound (1).
FIG. 18 is a plot showing the main peak (F 1s) of fluorine detected by X-ray photoelectron spectroscopy in the fluorine compound (1).
FIG. 19 is a plot diagram showing the change in charge amount of toner 1 with time. For the charge amount, 6 g of developer developer composed of toner and iron powder carrier TEFV200 / 300 (manufactured by Powdertech Co., Ltd.) was weighed, charged into a metal cylinder that can be sealed, and blown to obtain the charge amount. The toner concentration was adjusted to 7% by weight.
FIG. 20 is a diagram (right) showing the SEM observation image (left) of toner 1 and the fluorine addition position at the corresponding position in the left photograph obtained by EDS element mapping.
FIG. 21 is a diagram (right) showing a fluorine addition position at a corresponding position in the SEM observation image (left) of the analytical toner with the surface slightly shaved and the left photograph obtained by EDS element mapping.

From the result of the X-ray photoelectron spectroscopy measurement, the toner 1 does not contain iodine. In addition, the fluorine main peak is present in the toner in the same state as the raw material powder. This shows that in the toner 1, the fluorine compound (1) is added to the carboxyl group by ionic bond.
The change in the charge amount of the toner 1 with time has a fast initial charge rise as in the conventional toner using a fluorine compound, but the toner 1 has a small decrease in charge with time.
Further, in the toner 1 after stirring, when the surface scraped particles are observed using the EDS element mapping method, fluorine is unevenly distributed on the toner surface, the outer skin portion of the toner, and the inside of the toner. The situation was not seen. From the results of EDS element mapping, there is no localization of fluorine in the toner, and the result that fluorine is observed by XPS is that the fluorine is uniformly distributed in the toner without being unevenly distributed at a specific site. Represents that
From the SEM observation, 28 out of 100 toners had cracks.

[Example 2]
Toner 2 was prepared in the same manner except that the fluorine compound (2) represented by the following formula was used instead of the fluorine compound (1) of Example 1.
Example 3
Toner 3 was prepared in the same manner except that the fluorine compound (3) represented by the following formula was used instead of the fluorine compound (1) of Example 1.

Example 4
Toner 4 was prepared in the same manner except that the fluorine compound (4) represented by the following formula was used instead of the fluorine compound (1) of Example 1.
Example 5
~ Synthesis of low molecular weight polyester ~
271 parts of bisphenol A ethylene oxide 2-mole adduct, 354 parts of bisphenol A propylene oxide 2-mole adduct, 285 parts of terephthalic acid and 14 parts of isophthalic acid are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. Then, condensation reaction was carried out at 210 ° C. for 10 hours under a normal pressure nitrogen stream. Subsequently, 76 parts of 4-t-butylbenzoic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under reduced pressure of 0 to 15 mmHg, followed by cooling to obtain [Low Molecular Polyester 2]. The obtained polyester resin had a weight-average molecular weight of 4,000, an acid value of 55 KOH mg / g, a hydroxyl value of 40 KOH mg / g, and a glass transition point of 51 ° C.
Toner 5 was prepared in the same manner except that [Low molecular polyester 2] was used instead of [Low molecular polyester 1] in Example 1.

Example 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 of bisphenol A ethylene oxide 2-mole adduct, 590 parts of bisphenol A propylene oxide 2-mole adduct, 254 parts of terephthalic acid and 46 parts of isophthalic acid are charged. Then, condensation reaction was carried out at 210 ° C. for 10 hours under a normal pressure nitrogen stream. Subsequently, 38 parts of 4-t-butylbenzoic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, 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 polyester resin obtained had a weight-average molecular weight of 4,200, an acid value of 8 KOH mg / g, a hydroxyl value of 48 KOH mg / g, and a glass transition point of 45 ° C.
Toner 6 was prepared in the same manner except that [Low molecular polyester 3] was used instead of [Low molecular polyester 1] in Example 1.

Example 7
~ Synthesis of low molecular weight polyester ~
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 662 parts of bisphenol A propylene oxide 2-mole adduct, 269 parts of terephthalic acid, and 12 parts of trimellitic anhydride were added. The condensation reaction was carried out at 0 ° C. for 10 hours. Subsequently, 57 parts of 4-t-butylbenzoic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, followed by cooling to obtain a polyester [low molecular polyester 4]. The polyester resin obtained had a weight-average molecular weight of 12,500, THF-soluble content, acid value of 25 KOH mg / g, hydroxyl value of 60 KOH mg / g, and glass transition point of 51 ° C.
Toner 7 was prepared in the same manner except that [Low molecular polyester 4] was used instead of [Low molecular polyester 1] in Example 1.

Example 8
~ Synthesis of organic fine particle emulsion ~
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 14 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 137 parts of styrene, 138 parts of methacrylic acid, When 1.2 parts of ammonium persulfate was charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 71 ° C. for 6 hours, and an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-methacrylic acid etherene oxide adduct sulfate sodium salt) [ A fine particle dispersion 2] was obtained. The volume average particle size of the [fine particle dispersion 2] measured by a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corp.) was 0.18 μm. A portion of [Fine Particle Dispersion 2] was dried to isolate the resin component. The resin content Tg was 150 ° C. 1 part of N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide (hereinafter referred to as fluorine compound (1)) per 10 parts of [fine particle dispersion 2] 20 parts of an aqueous solution dispersed at a% concentration was mixed and stirred to obtain [fine particle dispersion 2-2].
Toner 8 was prepared in the same manner except that [Fine particle dispersion 2-2] was used instead of [Fine particle dispersion 1-2] in Example 1.

Example 9
~ Synthesis of organic fine particle emulsion ~
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 80 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate, 12 parts of butyl thioglycolate and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours. A dispersion was obtained. This is designated as [fine particle dispersion 3]. The volume average particle diameter of this [fine particle dispersion 3] measured by a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corp.) was 120 nm. A portion of [Fine Particle Dispersion 3] was dried to isolate the resin component. The Tg of the resin was 42 ° C., and the weight average molecular weight was 30,000. 1 part of N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide (hereinafter referred to as fluorine compound (1)) per 10 parts of [fine particle dispersion 3] 20 parts of the aqueous solution dispersed at% concentration was mixed and stirred to obtain [Fine Particle Dispersion 3-2].
Toner 9 was prepared in the same manner except that [Fine particle dispersion 3-2] was used instead of [Fine particle dispersion 1-2] in Example 1.

Example 10
~ Creation of water phase ~
Mix 86 parts of water, 1.5 parts of [fine particle dispersion 1-2], 25 parts of 50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 14 parts of ethyl acetate. Agitation gave a milky white liquid. This is designated as [Aqueous Phase 2].
Toner 10 was prepared in the same manner except that [aqueous phase 2] was used instead of [aqueous phase 1] in Example 1.
Example 11
~ Creation of water phase ~
86 parts of water, 10.5 parts of [fine particle dispersion 1-2], 25 parts of 50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 14 parts of ethyl acetate are mixed. Agitation gave a milky white liquid. This is designated as [Aqueous Phase 3].
Toner 10 was prepared in the same manner except that [aqueous phase 3] was used instead of [aqueous phase 1] in Example 1.

[Comparative Example 1]
[Aqueous phase 4] was obtained in the same manner as in [Example 1] except that the fluorine compound (1) was not added to [Fine particle dispersion 1-2] in [Example 1].
~ Emulsification⇒Desolvation ~
[Emulsion slurry 2] was obtained in the same manner as in Example 1 except that [Water phase 4] was used instead of [Water phase 1] in [Example 1].
~ Washing⇒Drying ~
[Emulsified slurry 2] After filtering 100 parts under reduced pressure,
1: 100 parts of ion-exchanged water was added to the filter cake and mixed with a TK homomixer (5 minutes at 15,000 rpm) and then filtered five times.
To a 2: 1 filter cake, 100 parts of 10% hydrochloric acid and an aqueous solution in which the fluorine compound (1) is dispersed at a concentration of 1 wt% are mixed so that the fluorine compound is 0.1 wt% with respect to the toner base. After mixing with a mixer (rotation speed: 15,000 rpm for 30 minutes), the mixture was filtered.
300 parts of ion-exchanged water was added to the 3: 2 filter cake, mixed with a TK homomixer (10 minutes at a rotation speed of 15,000 rpm), and then filtered five times to obtain [Filter cake 2].
[Filter cake 2] was dried at 45 ° C. for 24 hours in a circulating drier, sieved with a mesh opening of 75 μm, volume average particle diameter Dv 5.02 μm, number average particle diameter Dn 4.51 μm, Dv / Dn = 1.11. [Toner 12] (measured with Coulter Counter TAII) was obtained.

FIG. 22 is a plot of the vicinity of the main peak of iodine indicating that the main peak (I 3d) of iodine is not present in the toner 12 as measured by X-ray photoelectron spectroscopy.
FIG. 23 is a plot showing the main peak (F 1s) of fluorine detected by X-ray photoelectron spectroscopy in the toner 12.
FIG. 24 is a plot showing the main peak (I 3d) of iodine detected by X-ray photoelectron spectroscopy in the fluorine compound (1).
FIG. 25 is a plot showing the main peak (F 1s) of fluorine detected by X-ray photoelectron spectroscopy in the fluorine compound (1).
FIG. 26 is a plot diagram showing a change with time in the charge amount of the toner 12.
FIG. 27 is a diagram (right) showing the SEM observation image (left) of the toner 12 and the fluorine addition position at the corresponding position in the left photograph obtained by EDS element mapping.
From the result of the X-ray photoelectron spectroscopy measurement, the toner 12 does not contain iodine. The main peaks of fluorine and nitrogen are present in the toner in the same state as the raw material powder. This shows that in the toner 12, the fluorine compound (1) is added to the carboxyl group by ionic bond.
The change in the charging amount of the toner 12 with time is similar to the toner 1 and the conventional toner using the fluorine compound, but the initial charge rising is fast, but unlike the toner 1, the charging decrease with time is seen (see FIG. 24). .
In addition, when the abraded toner 12 was observed for particles with surface abrasion using the EDS element mapping method, uneven distribution of fluorine was observed in the outer skin portion of the toner.
From SEM observation, 47 out of 100 toners had surface cracks.

[Comparative Example 2]
The volume average particle diameter Dv5.01 μm, the number average particle diameter Dn4.50 μm, and Dv / Dn = 1.11 in the same manner as in Comparative Example 1 except that the fluorine compound (1) is not added to the filter cake of [Comparative Example 1]. [Toner 13] (measured with Coulter Counter TAII) was obtained.
The toner 13 having a constitution not containing a fluorine compound has a change in the charge amount with time, unlike the toner 1 and the toner 2, the charge rise is slow, and the time to reach the maximum charge amount is 600 seconds. There is no decrease in the charge amount, which is almost a monotonically increasing function (see FIG. 28).

[Evaluation method]
(1) Measurement of Volume Average Particle Size (Dv) and [Dv / Dn] Value The particle size distribution of the toner can be measured by various methods, but in the present invention, it was performed using a Coulter Multisizer. That is, Coulter Multisizer IIe type (manufactured by Coulter Inc.) is used as a measuring device, and an interface (manufactured by Nikkaki Co., Ltd.) for outputting number distribution and volume distribution is connected to a personal computer. A 1% NaCl aqueous solution was prepared. As a measurement method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. A dispersion treatment of ˜3 minutes was performed. Further, 100 to 200 ml of the electrolytic aqueous solution was put into another beaker, and the sample dispersion was added to a predetermined concentration therein, and 50,000 particles were used with the Coulter Multisizer III 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).
(2) Charging 1: Charge amount 6 g of a two-component developer was weighed and charged in a metal cylinder that could be sealed, stirred at a stirring speed of 640 rpm, and the charge amount was determined by a blow-off method. The toner concentration is adjusted to 7% by weight. As the carrier, TEFV200 / 300 (manufactured by Powdertech Co., Ltd.) was used.
2: Charging speed In the measurement of the charge amount, “good” was given when the charge amount in 60 seconds was 70% or more of the maximum charge amount, and “x” was given when the charge amount did not reach 70%.
3: Charge reduction In the measurement of the charge amount, ◯ was given as good when the charge amount in 3600 seconds was 70% or more of the maximum charge amount, and x was shown to be reduced to 70% or less.

(3) Measurement of glass transition point (Tg, ° C) of resin TG-DSC system TAS-100 manufactured by Rigaku Corporation was used as an apparatus for measuring Tg of resin. First, about 10 mg of a sample is put in an aluminum sample container, 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. 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.
(4) Fixability A solid image of 1.0 ± 0.1 mg / cm ^{2 on} a plain paper and cardboard transfer paper (Ricoh type 6200 and NBS Ricoh copy printing paper) using Ricoh's imgio Neo 450 Adjustment was made so that the toner was developed at a ratio, and adjustment was made so that the temperature of the fixing belt was variable, and the temperature at which no offset occurred on plain paper and the fixing lower limit temperature on thick paper were measured. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.

(5) Measurement of Resin Acid Value The acid value of the resin is measured by a method based on JIS K0070. However, if the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.
(6) Weight average molecular weight of resin (Mw)
The weight average molecular weight of the resin is measured under the following conditions using GPC for the THF-soluble component.
Apparatus: Tosoh HLC-8120
Column: TSKgelGMHXL (2)
TSKgelMultiporeHXL-M (1 pc.)
Measurement temperature: 40 ° C
Sample solution: 0.25% THF solution
Solution injection volume: 100 μl
Detector: Refractive index detector
Reference material: Polystyrene
The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight.
(7) Durability 100 toners were randomly observed by SEM image observation to count how many toners were broken. The number of broken toners was 30 or less out of 100.

Table 1 shows the evaluation items.
Table 1

  According to the present invention, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium ion is added to the terminal of the unmodified polyester that is a binder resin, and N is uniformly distributed in the toner. , N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium ion makes it possible to reduce the amount of charge with time even when the toner surface is scraped, and to have high durability. Toner can be provided.

It is a figure which shows the toner for analysis obtained by SEM observation that the surface was slightly shaved. It is a figure which shows the toner for analysis obtained by SEM observation, where the surface is shaved and hardly remains. It is a figure which shows the fluorine addition position of the toner for analysis obtained by EDS element mapping of SEM observation, and the surface was shaved slightly. It is a figure which shows the fluorine addition position of the toner for analysis obtained by the EDS element mapping of SEM observation, and the surface is shaved and hardly remains. FIG. 5 is a plot diagram showing that the main peak of iodine does not exist in the analytical toner obtained by X-ray photoelectron spectroscopy. It is a plot figure which shows the main peak of the fluorine of the toner for analysis obtained by X-ray photoelectron spectroscopy. It is a plot diagram showing the main peak of nitrogen of the toner for analysis obtained by X-ray photoelectron spectroscopy. It is a plot figure which shows the main peak of the iodine of a fluorine compound (1) obtained by X ray photoelectron spectroscopy. It is a plot figure which shows the main peak of the fluorine of a fluorine compound (1) obtained by X-ray photoelectron spectroscopy. It is a plot figure which shows the main peak of nitrogen of the fluorine compound (1) obtained by X-ray photoelectron spectroscopy. It is a figure which shows the peak of the toner for analysis obtained by 1H-NMR measurement. It is a figure which shows the peak of the unmodified polyester used for the toner preparation for analysis obtained by 1H-NMR measurement. It is a plot which shows the time-dependent change of the fluorine 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. 2 is a graph illustrating changes in charge amount of an analysis toner with time. FIG. 6 is a plot diagram showing that the main peak of iodine does not exist in the toner of Example 1 obtained by X-ray photoelectron spectroscopy. FIG. 3 is a plot diagram showing the main peak of fluorine of the toner of Example 1 obtained by X-ray photoelectron spectroscopy. It is a plot figure which shows the main peak of the iodine of a fluorine compound (1) obtained by X ray photoelectron spectroscopy. It is a plot figure which shows the main peak of the fluorine of a fluorine compound (1) obtained by X-ray photoelectron spectroscopy. 3 is a graph showing changes with time in the charge amount of the toner of Example 1. FIG. FIG. 6 is a diagram (right) showing a fluorine addition position at a corresponding position in an SEM observation image (left) of toner 1 and a left photograph obtained by EDS element mapping. It is a figure (right) which shows the SEM observation image (left) of the toner for analysis in which the surface was shaved slightly, and the fluorine addition position in the corresponding position of the left photograph obtained by EDS element mapping. FIG. 6 is a plot diagram showing that the main peak of iodine does not exist in the toner of Comparative Example 1 obtained by X-ray photoelectron spectroscopy. FIG. 6 is a plot diagram showing the main peak of fluorine of the toner of Comparative Example 1 obtained by X-ray photoelectron spectroscopy. It is a plot figure which shows the main peak of the iodine of a fluorine compound (1) obtained by X ray photoelectron spectroscopy. It is a plot figure which shows the main peak of the fluorine of a fluorine compound (1) obtained by X-ray photoelectron spectroscopy. 3 is a graph showing changes with time in the charge amount of the toner of Comparative Example 1. FIG. FIG. 6 is a diagram (right) showing the SEM observation image (left) of toner 12 and the fluorine addition position at the corresponding position in the left photograph obtained by EDS element mapping. 6 is a graph showing changes with time in the charge amount of the toner of Comparative Example 2.

Claims (18)

A toner obtained by removing a solvent from a dispersion obtained by dispersing a solution or dispersion containing a toner composition containing at least a binder resin, resin fine particles, and a charge control agent in an aqueous solvent. The toner for developing an electrostatic charge image, wherein the resin fine particles have at least a functional group capable of ion bonding, and the charge control agent is ion-bonded to the resin fine particles inside the toner. The electrostatic charge image developing toner according to claim 1, wherein the charge control agent is a quaternary ammonium salt. The electrostatic charge image developing toner according to claim 1, wherein the charge control agent is a fluorine-based compound represented by the following general formula (1).
(Wherein R ^{1 to} R ⁴ are a lower alkyl group having 1 to 10 carbon atoms and an aryl group, X is —SO ₂ —, —CO—, Y is I, Br, n, and m are positive integers. ) The electrostatic image developing toner according to claim 3, wherein the fluorine compound is N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide. The electrostatic charge image developing toner according to claim 1, wherein the resin fine particles have a carboxyl group terminal. 6. The electrostatic image developing toner according to claim 1, wherein the binder resin is a polyester resin. The toner for developing an electrostatic charge image according to claim 1, wherein the content of the fluorine compound is 0.05 to 10% by weight with respect to the toner. The electrostatic image developing toner according to claim 1, wherein an acid value of the binder resin is 1 to 30 mg KOH. The toner for developing an electrostatic charge image according to claim 1, wherein the binder resin has a glass transition point (Tg) of 40 to 90 ° C. The electrostatic image developing toner according to claim 1, wherein the resin fine particles are made of a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and / or a mixture thereof. The toner for developing an electrostatic charge image according to claim 1, wherein the resin fine particles have a weight average molecular weight of 5,000 to 200,000. The toner for developing an electrostatic charge image according to claim 1, wherein the toner particles have a volume average particle diameter of 4 to 8 μm. The electrostatic charge according to claim 1, wherein a ratio Dv / Dn of the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner particles is 1.25 or less. Toner for image development. A developer comprising the toner according to claim 1. The developer according to claim 14, which is one of a one-component developer and a two-component developer. An image forming method using the electrostatic image developing toner according to claim 1. 14. An image forming method using a developing device having a toner recycling mechanism, wherein the electrostatic image developing toner according to claim 1 is used. A container containing the electrostatic image developing toner according to claim 1.