JP2006065195A - Image forming method, toner for electrostatic image development, developer and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method in which good offset resistance is achieved, a fixing device and an image are not stained and excellent charging characteristics are ensured, and by which an image with few surface stains is formed, and also to provide a toner for electrostatic image development, a developer, and a process cartridge. <P>SOLUTION: In the image forming method, a fixing device is used which has a heating roller 1 heated by electromagnetic induction, a fixing roller 2, a toner heating medium 3 and a pressure roller 4 forming a fixing nip part N, and a toner is used which is obtained by dissolving or dispersing a toner composition in an organic solvent, dispersing the resulting solution or dispersion in an aqueous medium containing fine resin particles, reacting it with a crosslinking agent, removing the solvent from the resulting dispersion to form particles, and treating the surfaces of the particles with a fluorine-containing compound, wherein a content of F in the toner detected by the XPS method is 2-30% by the number of atoms, and a content of fine resin particles is 0.5-5.0 mass%. The toner for electrostatic image development, the developer, and the process cartridge are also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an image forming method, an electrostatic charge image developing toner, a developer, and a process cartridge for visualizing an electrostatic charge image formed on an image carrier in electrophotography and electrostatic recording.

In recent years, market demands for energy saving and high speed have been increasing for image forming apparatuses such as printers, copiers, and facsimiles. In order to achieve these required performances, it is important to improve the thermal efficiency of the fixing device used in the image forming apparatus.
In an image forming apparatus, an unfixed toner image is transferred to a recording material sheet, printing paper, photosensitive paper, electrostatic recording paper, or the like by an image transfer method or a direct method by an image forming process such as electrophotographic recording, electrostatic recording, or magnetic recording. It is formed on a recording material (image support). As a fixing device for fixing an unfixed toner image, a contact heating method fixing device such as a heat roller method, a film heating method, and an electromagnetic induction heating method is widely used.
The heat roller type fixing device has a rotation roller pair of a fixing roller having a heat source such as a halogen lamp inside and adjusted to a predetermined temperature, and a pressure roller in pressure contact with the fixing roller. A recording material is introduced into a contact portion of the rotating roller pair, that is, a fixing nip portion, and conveyed, and an unfixed toner image is melted and fixed by heat and pressure from the fixing roller and the pressure roller.
A film heating type fixing device is proposed in, for example, Patent Documents 1 and 2. In this apparatus, a recording material is brought into close contact with a heating body fixedly supported by a support member through a thin fixing film having heat resistance, and the heat of the heating body is transferred while the fixing film is slid relative to the heating body. The recording material is supplied to the recording material. In this fixing device, for example, a ceramic heater including a resistance layer on a ceramic substrate such as alumina or aluminum nitride having characteristics such as heat resistance, insulation, and good thermal conductivity is used as a heating body. Since this fixing device can use a thin film with a low heat capacity as the fixing film, the heat transfer efficiency is higher than that of a heat roller type fixing device, the warm-up time can be shortened, quick start and energy saving can be achieved. It becomes possible.
As an electromagnetic induction heating type fixing device, Patent Document 3 proposes a technique in which Joule heat is generated by an eddy current generated in a magnetic metal member by an alternating magnetic field, and a heating body including the metal member is heated by electromagnetic induction.

The configuration of the electromagnetic induction heating type fixing device will be described below.
FIG. 5 is a schematic diagram showing a conventional fixing device using an electromagnetic induction heating method.
As shown in FIG. 5, in the conventional fixing device, a film inner surface guide 21 on which a heating body 20 including an exciting coil unit 18 and a magnetic metal member 19 as a heating unit is mounted, and the magnetic metal member 19 are applied to the inner wall. A fixing nip portion N is formed between the heat-resistant cylindrical film 17 wrapping the film inner surface guide 21 in contact with the film 17 at the position of the magnetic metal member 19 and the film 17. The pressure roller 22 rotates the film 17.
Film 17 has a film thickness of 100 μm or less, preferably 50 μm or less and a heat resistance of 20 μm or more. A composite layer film coated with PTFE, PFA, FEP or the like is used.
The film inner surface guide 21 is made of a member having rigidity and heat resistance formed of a resin such as PEEK or PPS, and the heating body 20 is fitted in the substantially central portion of the film inner surface guide 21 in the longitudinal direction. .
The pressure roller 22 is composed of a core 22a and a heat-resistant rubber layer 22b having good releasability, such as silicon rubber, provided around the core 22a. The film 17 is held so as to be in pressure contact with the magnetic metal member 19 of the heating body 20. The pressure roller 22 is driven to rotate counterclockwise by a driving means (not shown).
By the rotational driving of the pressure roller 22, a frictional force is generated between the pressure roller 22 and the film 17, and the rotational force acts on the film 17, while the film 17 is in close contact with the magnetic metal member 19 of the heating body 20. Slide and rotate.
A recording having an unfixed toner image T formed by an image forming unit (not shown) between the film 17 and the pressure roller 22 in the fixing nip N in a state where the heating body 20 has reached a predetermined temperature. The material 11 is introduced. The recording material 11 is sandwiched between the pressure roller 22 and the film 17 and conveyed through the fixing nip N, whereby the heat of the magnetic metal member 19 is applied to the recording material 11 through the film 17 and the unfixed toner image T Is melt-fixed on the recording material 11. At the exit of the fixing nip N, the recording material 11 that has passed is separated from the surface of the film 17 and conveyed to a paper discharge tray (not shown).
As described above, in the electromagnetic induction heating type fixing device, the magnetic metal member 19 as the induction heating means is disposed close to the toner image T of the recording material 11 through the film 17 by utilizing the generation of eddy current. Therefore, the heating efficiency is further improved as compared with the fixing device of the film heating type.

However, among image forming apparatuses, a fixing device in a full-color image forming apparatus is required to have a capability of sufficiently heating and melting a toner particle layer having a thickness of four or more layers. In order to achieve this requirement, the electromagnetic induction heating type fixing device requires a rubber elastic layer of a certain thickness on the surface of the film in order to sufficiently enclose the toner image and uniformly heat and melt it. Become. In order to solve these problems, when an elastic layer such as silicon rubber is coated on the surface of the film to some extent, the thermal responsiveness deteriorates due to the low thermal conductivity of the elastic layer, and the inner surface of the film heated from the heating body and the toner When the amount of toner is very large due to a very large temperature difference with the outer surface in contact with the belt, the belt surface temperature decreases rapidly, so that sufficient fixing performance cannot be secured, and so-called cold offset occurs. I was doing it.
That is, in the electromagnetic induction heating type fixing device, the above-mentioned fixing property is particularly a problem as compared with a conventional heat roller type fixing device.

On the other hand, in an image forming method, an electrical 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 charge 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 particle size There is a disadvantage that the fine powder of 5 μm or less and the coarse powder of 20 μm or more must be removed by classification, resulting in a very low yield. 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 are spherical and have the disadvantage of poor cleaning properties. Development and transfer with a low image area ratio results in a small amount of residual toner, and poor cleaning does not become a problem. Toner may be generated on the photosensitive member as untransferred toner, and accumulation will cause image smudges. Further, since it has a spherical shape, the contact area between the toners is reduced and the adhesion is reduced, so that the margin for fixing tends to be lowered, and the stability at the lower limit of fixing cannot be obtained.
For this reason, a method of obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method is disclosed (Patent Document 4). However, the toner particles obtained by the emulsion polymerization method have a large amount of surfactant remaining not only on the surface but also inside the particles even after the water washing step, impairing the environmental stability of the toner charge, and the charge amount distribution. The background of the obtained image becomes poor. Further, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, and the like, so that the original charging ability cannot be exhibited.

Further, in the fixing step, the release property of the toner particles with respect to the heating member (hereinafter referred to as “offset resistance”) is required. 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 5 and 6 disclose methods for improving offset resistance not only by containing resin fine particles in toner particles but also by unevenly distributing the resin fine particles on the surface of the toner particles. Yes. However, the minimum fixing temperature is increased, and the low temperature fixing property, that is, the energy saving fixing property is not sufficient.
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. That is, 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, offset resistance can be sufficiently improved. I can't. 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 that requires 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.

  In both the suspension polymerization method and the emulsion polymerization method, a styrene-acrylic acid ester copolymer is generally used, but there is a limit to fixability when aiming at low-temperature fixing. On the other hand, it is also known to use a polyester modified with a urea bond for the purpose of lower temperature fixing and heat resistant storage stability (Patent Document 7). These are not particularly surface-developed, and the charging characteristics of the toner are problematic due to insufficient environmental charge stability, which is more severe, and because it uses a polyester resin, it is difficult to form particles. There are also problems that particle size distribution and shape control are difficult. In these toner particle forming steps, it is known as a known technique to promote control of toner particle size and shape by adding resin fine particles present in the toner particles. However, in a system that requires low-temperature fixing at the same time, if the amount of resin fine particles unevenly distributed on the toner surface increases more than appropriate, fixing inhibition occurs, and there is a problem that the fixing temperature range cannot be secured.

Regarding the charging characteristics of the toner, even if the charging ability as the toner base is relatively good, the good characteristics of the toner base may be covered by the type and characteristics of the fluidizing agent added to the toner base. It has been difficult to maintain the start-up property and the environmental charging stability and to suppress the toner background contamination (fogging) and toner scattering over time in the image forming apparatus.
On the other hand, it is also known that a toner contains a fluorine-based compound as a charge control agent or the like as means for increasing the charging ability of the negatively charged toner (Patent Documents 8 and 9, etc.). However, in a system in which a fluorine-based compound is added as a means for improving the charging ability, it is a problem that a sufficient charging effect cannot be obtained simply by containing a fluorine-based compound in the toner particles in the toner manufacturing process. It was. In addition, as a result of the study by the present inventors, there is a correlation between the content of the fluorine compound and the charging performance, and when the amount of the fluorine compound is increased with the aim of improving the charging property, the fixing property is inhibited accordingly. It has been found. In particular, as described above, in a fixing system with a low margin that requires low-temperature fixing as compared with the conventional method, an image forming method that realizes both fixing property and charging property is required more than before. Therefore, it has been a problem to optimize the conditions during the fluorine treatment in the toner production process and the fluorine content contained in the toner base particles.

JP-A-63-313182 Japanese Patent Laid-Open No. 1-263679 JP-A-8-22206 Japanese Patent No. 2537503 JP 2000-292773 A JP 2000-292978 A Japanese Patent Laid-Open No. 11-133667 Japanese Patent No. 2942588 Japanese Patent No. 3102797

An object of the present invention is to solve the above problems. That is, the object of the present invention is to provide the following.
1) Corresponding to an image forming method requiring low-temperature fixing by an electromagnetic induction heating method, an image forming method that has good offset resistance and does not contaminate an image, a toner for developing an electrostatic image, a developer And providing a process cartridge.
2) In addition to 1) above, the charging ability of the toner is sufficiently high, there are few weakly charged and reversely charged toners, and the charging stability is excellent in high temperature, high humidity, low temperature and low humidity environments. Even if tens of thousands of images are output Provided are an image forming method, an electrostatic charge image developing toner, a developer, and a process cartridge capable of forming an image with less background stain (fogging), less scattering of toner into the machine, and obtaining a sufficient image density. To do.

  As a result of intensive studies, the inventors of the present invention have good low-temperature fixability and offset resistance even in an image forming method equipped with the above-described electromagnetic induction heating type fixing device in which low-temperature fixing is a particular problem. In order to ensure sufficient chargeability for a long period of time, the toner for developing an electrostatic charge image used therefor contains a toner binder resin containing a polyester resin in at least one part, and granulated in an aqueous medium containing resin fine particles. And a toner composition containing a toner binder resin composed of a modified polyester resin capable of reacting with active hydrogen, preferably dissolved or dispersed. The dispersion obtained by dispersing the solution or dispersion in an aqueous medium containing resin fine particles and reacting with a crosslinking agent and / or an extender The toner is formed by removing the solvent to form particles, and the surface of the particles is treated with a fluorine-containing compound, and the toner particles contain 2 to 30 atomic% of fluorine atoms contained in the toner particles. In addition, the resin fine particles added to the toner particles for the purpose of controlling the particle diameter and shape have a property of easily adsorbing fluorine selectively. By controlling the rate within the range of 0.5 to 5.0% by mass, it has been found that stable chargeability is exhibited over a long period of time (and if it is up to 5.0% by mass, it will not interfere with low-temperature fixing). The invention has been completed.

According to the first aspect of the present invention, the electrostatic latent image formed on the image carrier is developed using toner, the toner image formed on the image carrier is transferred to an image support, and the transferred toner image is transferred. In an image forming method including a step of fixing the image by a fixing device,
The fixing device includes a fixing unit having a rotary heating body heated by electromagnetic induction, and a pressure unit that rotates in a forward direction with respect to the rotary heating body to form the fixing unit and a fixing nip portion. ,
The toner includes at least a toner binder resin and a colorant, and the toner binder resin includes a polyester-based resin in at least one part and is granulated in an aqueous medium including resin fine particles, and the surface of the particle is a fluorine-containing compound. An image forming method, wherein the toner is an electrostatic charge image developing toner processed by using the toner, and the toner satisfies the following conditions (1) and (2).
(1) The content of fluorine atoms detected by XPS (X-ray photoelectron spectroscopy) of the toner is 2 to 30 atomic percent.
(2) The content of the resin fine particles contained in the toner with respect to the toner is 0.5 to 5.0 mass%.

  According to a second aspect of the present invention, a toner composition containing a toner binder resin composed of a modified polyester resin capable of reacting with active hydrogen is dissolved or dispersed in an organic solvent. Disperse in an aqueous medium containing fine particles and react with a crosslinking agent and / or extender to remove the solvent from the resulting dispersion to form particles, and treat the surface of the particles with a fluorine-containing compound 2. The image forming method according to claim 1, wherein the toner is an electrostatic charge image developing toner.

According to a third aspect of the present invention, a toner composition containing a toner binder resin made of a modified polyester resin capable of reacting with active hydrogen is dissolved or dispersed in an organic solvent, and the solution or dispersion is dissolved in an aqueous system containing resin fine particles. An electrostatic image obtained by dispersing in a medium and reacting with a crosslinking agent and / or an extender, removing the solvent from the obtained dispersion to form particles, and treating the surface of the particles with a fluorine-containing compound A developing toner, wherein the toner satisfies the following conditions (1) and (2).
(1) The content of fluorine atoms detected by XPS (X-ray photoelectron spectroscopy) of the toner is 2 to 30 atomic percent.
(2) The content of the resin fine particles contained in the toner with respect to the toner is 0.5 to 5.0 mass%.

  In the invention of claim 4, the fluorine-containing compound is represented by the following general formula (1):

(Wherein X is —SO ₂ — or —CO—, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and aryl. A group selected from the group, Y is an iodine atom, bromine atom or chlorine atom, m is an integer of 1 to 10, and n is an integer of 1 to 10)
The toner for developing an electrostatic charge image according to claim 3, which is represented by:

  In the invention of claim 5, non-reactive polyester is further dissolved in the organic solvent together with the modified polyester resin, and the mass ratio of the modified polyester resin to the non-reactive polyester is 5 / 5. The electrostatic image developing toner according to claim 3, wherein the toner is 95 to 75/25.

  The invention of claim 6 is the electrostatic image developing toner according to any one of claims 3 to 5, wherein the toner has a volume average particle diameter (Dv) of 3 to 8 μm.

  7. The electrostatic charge image development according to claim 3, wherein the toner has a volume average particle diameter (Dv) / number average particle diameter (Dn) of 1.25 or less. Toner.

  The invention according to claim 8 is the electrostatic image developing toner according to any one of claims 3 to 7, wherein the toner has an average circularity of 0.900 to 0.980.

  The invention according to claim 9 is characterized in that the resin fine particles are vinyl resin, polyurethane resin, epoxy resin, polyester resin, or a combination of at least two of them. This is a toner for developing an electrostatic image.

  The invention of claim 10 is the electrostatic image developing toner according to any one of claims 3 to 9, wherein the resin fine particles have a glass transition point (Tg) of 40 to 100 ° C.

  The invention of claim 11 is the electrostatic image developing toner according to any one of claims 3 to 10, wherein the resin fine particles have an average particle diameter of 5 to 500 nm.

  A twelfth aspect of the present invention is a dry two-component developer comprising the electrostatic image developing toner according to any one of the third to eleventh aspects.

  According to a thirteenth aspect of the present invention, an image carrier and an electrostatic image formed on the image carrier are developed using the electrostatic image developing toner according to any one of the third to twelfth aspects to produce a visible image. A process cartridge having at least developing means for forming and detachable from a main body of the image forming apparatus.

  According to the present invention, the offset resistance is good, the fixing device and the image are not contaminated, the toner charging capability is sufficiently high, the weakly charged toner and the reversely charged toner are few, high temperature and high humidity, and low temperature and low humidity environment. Is excellent in charging stability, and even if tens of thousands of images are output, an image with little background stain (fogging) is formed, toner is less scattered in the machine, and an image quality with sufficient image density can be obtained. An image forming method, an electrostatic charge image developing toner, a developer, and a process cartridge are provided.

  The present invention is described in detail below. As described above, the toner used in the present invention contains at least a toner binder resin and a colorant, and the toner binder resin is granulated in an aqueous medium containing at least one part of a polyester resin and containing resin fine particles. Any toner may be used as long as it is an electrostatic image developing toner whose surface is treated with a fluorine-containing compound. In a preferred embodiment, the toner used in the present invention is obtained by dissolving or dispersing a toner composition containing a toner binder resin composed of a modified polyester resin capable of reacting with active hydrogen in an organic solvent. , Dispersed in an aqueous medium containing fine resin particles, and reacted with a crosslinking agent and / or an extender to remove the solvent from the resulting dispersion to form particles, and the surface of the particles is made of a fluorine-containing compound The toner for developing an electrostatic charge image processed in this manner. Hereinafter, the toner of such a preferable aspect will be described.

[Organic solvent phase]
<Organic solvent>
In the present invention, the organic solvent is not particularly limited as long as it is a solvent that can dissolve and / or disperse the toner composition. As a preferable thing, it is preferable from the point that removal is easy that the boiling point of this solvent is less than 150 degreeC. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, methyl acetate, ethyl acetate, methyl ethyl ketone, acetone. , Tetrahydrofuran and the like can be used alone or in combination of two or more. Of these, methyl acetate and ethyl acetate are preferred because they are particularly volatile to toner. The amount of the solvent used relative to 100 parts by mass of the toner solid component is usually 40 to 300 parts by mass, preferably 60 to 140 parts by mass, and more preferably 80 to 120 parts by mass.

<Modified polyester resin>
In the present invention, a polyester prepolymer having an isocyanate group can be used as the modified polyester resin. Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group, which is further reacted with a polyisocyanate (3). Can be mentioned. 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 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; And alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, 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.
In order to adjust the polyester having an alcoholic hydroxyl group at the terminal by a polycondensation reaction, the ratio of the polyol (1) to the polycarboxylic acid (2) is equivalent to the equivalent ratio [OH] / [ COOH] is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1.

Examples of the polyisocyanate (3) used for preparing the polyester prepolymer by reacting with the alcoholic hydroxyl group of the polyester include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl carbonate). Proate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); Xylylene diisocyanate); isocyanurates; the polyisocyanate blocked with a phenol derivative, oxime, caprolactam, etc .; and These two or more types can be used in combination.
The use ratio of the polyisocyanate is usually 5/1 to 1/1, preferably 4/1 to 1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 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 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. When the number is less than 1 per molecule, the molecular weight of the modified polyester after crosslinking and / or elongation becomes low, and the hot offset resistance deteriorates.

<Combination of non-reactive polyester>
In the present invention, it is preferable that not only (A) is used alone but also non-reactive polyester (C) which is not modified is contained as a toner binder component together with (A). By using (C) in combination, low-temperature fixability and glossiness when used in a full-color device are improved. Examples of (C) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (A), and preferred ones are also the same as (A). (C) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with, for example, a urethane bond. It is preferable that (A) and (C) are at least partially compatible in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (A) and (C) preferably have similar compositions. When (A) is contained, the mass ratio of (A) to (C) is usually 5/95 to 75/25, preferably 10/90 to 25/75, more preferably 12/88 to 25/75, Especially preferably, it is 12 / 88-22 / 78. If the mass ratio of (A) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The peak molecular weight measured by GPC (gel permeation chromatography) of the polyester (C) is usually 1000 to 30000, preferably 1500 to 10000, more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (C) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (C) is usually from 0.5 to 40, preferably from 5 to 35. If the acid value is too high, it tends to be negatively charged, which is not preferable. Those exceeding this range are susceptible to environmental influences under high temperature and high humidity and low temperature and low humidity environments, and are liable to cause image deterioration.

[Active hydrogen-containing compounds]
As will be described later, the above-mentioned polyester prepolymer (A) having an isocyanate group is made to have a higher molecular weight by subjecting the active hydrogen-containing compound to elongation and / or crosslinking reaction.
In the present invention, amines can be used as a crosslinking agent and / or an extender. 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, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine 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 modified polyester after completion of the reaction can be adjusted by using a terminator for crosslinking and / or elongation. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (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. If [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

<Characteristics of toner binder>
In the present invention, as described above, for example, a urea-modified polyester resin obtained by a reaction between a polyester prepolymer (A) and an amine (B) is used as a toner binder resin. Other components (including a resin used in the case of a colorant master batch) are also used in combination. In the present invention, the glass transition point (Tg) of the toner binder resin is usually 40 to 70 ° C., preferably 45 to 55 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the crosslinked and / or elongated polyester resin, the toner for developing an electrostatic charge image of the present invention exhibits good storage stability even when the glass transition point is low as compared with known polyester-based toners. As the storage elastic modulus of the toner, the temperature (TG ′) at which the measurement frequency is 20 Hz becomes 1000 Pa 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, the temperature (Tη) at 100 Pa · s 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.

[Aqueous medium phase]
<Aqueous medium>
In the present invention, the aqueous medium in which the resin fine particles described later are dispersed to form an aqueous medium phase may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones (acetone, methyl ethyl ketone, etc.). These can be used singly or in combination of two or more.

<Resin fine particles>
The resin fine particles in the toner of the present invention are added in the production process in order to control the toner shape (circularity, particle size distribution, etc.) described later. The fine particles are considered to be bonded to the surface portion when an organic solvent phase and an active hydrogen-containing compound (amines) are dispersed in an aqueous medium to form organic dispersed particles, as will be described later. As a result, like the external additive described later, it is considered that the toner particles obtained are unevenly distributed mainly on the surface portion. In the present invention, it is necessary and important that the amount of resin fine particles contained in the obtained toner particles after the external additive treatment is 0.5 to 5.0% by mass. When the content is less than 0.5% by mass, the storage stability of the toner is deteriorated, and blocking is observed during storage and in the developing machine. The exudation of the wax is hindered, the effect of releasability of the wax cannot be obtained, and the occurrence of offset is observed. Further, the glass transition point (Tg) of the resin fine particles is preferably 40 to 100 ° C., and the mass average molecular weight is preferably 9000 to 200,000. When the Tg of the resin fine particles is less than 40 ° C. and / or the weight average molecular weight is less than 9,000, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the temperature exceeds 100 ° C. and / or the mass average molecular weight exceeds 200,000, the resin fine particles inhibit the adhesion to the fixing paper, and an increase in the minimum fixing temperature is observed.
The content of the resin fine particles can be measured by analyzing a substance caused by the resin fine particles, not by the toner particles, with a pyrolysis gas chromatograph mass spectrometer, and calculating from the peak area. The detector is preferably a mass spectrometer, but is not particularly limited. The dispersion / blending amount of the resin fine particles in the aqueous medium may be set so as to satisfy the conditions related to the content, but is usually in the range of about 0.5 to 10% by mass.
The resin fine particles may 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, polyester resins, polyamide resins, polyimides Examples thereof include resins, silicon-based resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. 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 can be 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.
The average particle diameter of the resin fine particles is preferably 5 to 500 nm.

[Other ingredients]
<Colorant>
As the colorant used in 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 Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R , Para red, phisa red, par Chlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, 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 Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, 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 Tog Lean lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by mass, preferably 3 to 10% by mass as the content in the toner of the present invention.
The colorant used in the present invention can also be used as a master batch combined with a resin. Examples of the binder resin kneaded together with the production of the masterbatch or the masterbatch include, for example, the above-mentioned urea-modified polyester resin and non-reactive polyester resin, as well as the weight of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted products thereof. Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene- α-Chlorme Methyl crylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid Styrene copolymers such as copolymers and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane , Polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. Can be used alone or in combination.
This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet cake of a colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Can be used as it is, so that it is not necessary to dry and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used. The colorant or master batch can be dissolved or dispersed in the organic solvent phase, but is not limited thereto.

<Release agent>
Further, a wax can be contained together with the toner binder resin and the colorant. 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. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecandiol diol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine 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 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 amount of the wax (release agent) used is usually 0 to 40% by mass, preferably 3 to 30% by mass as the content in the toner. Further, the wax (release agent) can be dissolved or dispersed in the organic solvent phase, but is not limited thereto.

<Charge control agent>
The toner of the present invention may contain a charge control agent as necessary. Any known charge control agent can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified) Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.
In the present invention, the amount of charge control agent used is determined uniquely by the type of toner binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. Although it is not a thing, Preferably it is used in 0.1-10 mass parts with respect to 100 mass parts of toner binder resin. Preferably, the range of 0.2-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they may be added when directly dissolving and dispersing in an organic solvent. It is preferable.

[Toner particle adjustment]
The toner of the present invention can be produced by the following method, but is not limited thereto.
<Toner production method in aqueous medium>
The aqueous phase used in the present invention is used by adding resin fine particles in advance. As described above, water used in the aqueous phase may be water alone, or 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 (eg, methyl cellosolve), and lower ketones (acetone, methyl ethyl ketone, etc.).

<Dispersion and reaction of organic solvent phase>
As described above, the toner particles are prepared by dispersing the organic solvent phase containing the polyester prepolymer (A) together with the amines (B) in the aqueous medium phase, and extending and / or crosslinking in the aqueous medium phase. It is formed through a process of forming a urea-modified polyester. As a method for stably forming a dispersion comprising the polyester prepolymer (A) in the aqueous phase, a composition of a toner raw material containing the polyester prepolymer (A) dissolved or dispersed in an organic solvent in the aqueous phase is added. And a method of dispersing by shearing force. The polyester prepolymer (A) dissolved or dispersed in an organic solvent and other toner raw materials, such as a colorant, a colorant masterbatch, a release agent, a charge control agent, and an unmodified polyester resin, are in an aqueous phase. Mixing may be performed when forming the dispersion, but it is more preferable that the toner raw materials are mixed in advance and then dissolved or dispersed in an organic solvent, and then the mixture is added and dispersed in the aqueous phase. Further, in the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in the aqueous phase. After the particles are formed, It may be added. 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 rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the polyester prepolymer (A) has a low viscosity and is easily dispersed.
The usage-amount of the aqueous medium with respect to 100 mass parts of solid components contained in the organic solvent phase of a polyester prepolymer (A) is 50-2000 mass parts normally, Preferably it is 100-1000 mass parts. If the amount is less than 50 parts by mass, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle size cannot be obtained. If it exceeds 2000 parts by mass, it is not economical. Moreover, a dispersing agent can also be used as needed. The use of a dispersant is preferable in that the particle size distribution becomes sharp and the dispersion is stable.

Examples of the dispersant for emulsifying and dispersing the organic solvent phase containing the polyester prepolymer (A) include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamines, and the like. Amine salts such as salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, 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-a Kill -N, amphoteric surfactants such as N- dimethyl ammonium betaine.
Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [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, perfluoroalkyl carboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxye B) Perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate Such as esters,
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, 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 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.
Moreover, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, etc. 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, or esters of compounds containing vinyl alcohol and carboxyl groups For example, pinyl acetate, pinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine Homopolymers or copolymers such as those having a nitrogen atom or its heterocyclic ring, 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 can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the 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.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

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 classification 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, but it is preferably performed in a liquid in terms of efficiency. The obtained unnecessary fine particles or coarse particles can be returned to the kneading step and used for forming 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.

In addition, the dried toner powder is mixed with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or mechanical impact force is applied to the mixed powder. By applying, the different particles are fixed and fused on the toner surface, and the detachment of the different particles from the surface of the resulting composite particles can be prevented.
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.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

<Surface treatment with fluorine-containing compound>
In the present invention, the toner base particles obtained through the steps as described above are then treated on the surface with a fluorine-containing compound that is a charge control agent. As the fluorine-based compound used in the toner of the present invention, any organic or inorganic compound can be used as long as it is a compound containing a fluorine atom, and it is not particularly limited except that it contains a fluorine atom. Among these, the compound of the following general formula (1) is more preferable.

In the formula, X is —SO ₂ — or —CO—, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group. Y is an iodine atom, bromine atom or chlorine atom, m is 1 to 10, and n is an integer of 1 to 10.

  As the charge control agent, it is also preferable to use a metal-containing azo dye in combination with the fluorine-containing quaternary ammonium salt represented by the general formula (1).

  Typical specific examples of the compound of the general formula (1) include the following fluorine-based compounds (1) to (27), all showing white or light yellow. Y is more preferably iodine.

Among these, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide is more preferable in terms of charge imparting ability. Moreover, the mixture with the said compound and another fluorine-type compound is also more preferable.
The fluorine-containing compound is used in the toner so that the content of fluorine atoms detected by XPS (X-ray photoelectron spectroscopy) of the toner is in the range of 2 to 30 atomic percent, preferably 4 to 15 atomic percent. Surface treatment can be applied. If the detected amount of fluorine atoms is smaller than this, there is a problem that the charging effect cannot be obtained, and not only the initial charging property but also the charging is likely to decrease over time. This is not preferable because it causes stains on the upper surface and toner scattering. On the other hand, if the detected amount of fluorine atoms exceeds 30 atomic percent, image density failure due to high charge, further poor fixing of the developer, and the like are undesirable.
As a method for treating the fluorine-containing compound with the toner, the toner base particles before the addition of the inorganic fine particles are dispersed in an aqueous solvent in which the fluorine-containing compound is dispersed (water containing a surfactant is also preferable), and the fluorine-containing compound is formed on the toner surface. After the toner is attached, the solvent can be removed and dried to obtain a toner base, but the present invention is not limited to this method.
In addition, it has been clarified by numerous experiments that the fluorine-containing compound is likely to exhibit the effect of improving the chargeability by being processed in a state where the resin fine particles remain properly in the toner. Specifically, the toner surface treatment with a fluorine-containing compound is performed in an existing state where the amount of resin fine particles remaining in the toner particles measured by a pyrolysis gas chromatograph mass spectrometer is 0.5 to 5.0% by mass. Has been found to have an effect on improving the charging property. Although the mechanism is not clear at this stage, the fluorine-containing compound is likely to adhere to the resin fine particles, and it is considered that the fluorine-containing compound does not adhere and does not exert its effect under the condition that this hardly remains, such as less than 0.5% by mass. It is done. For this reason, it is preferable that the resin fine particles remain on the toner surface. On the other hand, if it exceeds 5.0% by mass, the presence of a large amount of the resin fine particles can become a fixing inhibitor for low-temperature fixability, so that the charging effect is remarkable, but it is not preferable as the toner quality.

[Application of external additives]
As the external additive for assisting the fluidity, developability and chargeability of the toner of the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and particularly preferably 0.01 to 2.0% by mass.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
Other polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, and thermosetting resin Examples include polymer particles.
Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
On the other hand, examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor and the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, such as polymethyl methacrylate fine particles, polystyrene. There may be mentioned polymer fine particles produced by soap-free emulsion polymerization of fine particles and the like. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

[Toner shape, etc.]
<Circularity and circularity distribution>
The toner in the present invention preferably has a specific shape and shape distribution, and an irregularly shaped toner having an average circularity of less than 0.900 and too far from a spherical shape has a satisfactory transferability and a high density without dust. A quality image cannot be obtained. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. Toner having an average circularity of 0.980 to 0.900, which is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle, has high reproducibility with an appropriate density reproducibility. It was found to be effective in forming a clear image. More preferably, particles having an average circularity of 0.970 to 0.950 and a circularity of less than 0.94 are 15% or less. When the average circularity exceeds 0.980, in a system that employs blade cleaning or the like, poor cleaning occurs on the photosensitive member and the transfer belt, causing stain on the image. For example, development / transfer with a low image area ratio results in a small amount of residual toner and poor cleaning does not become a problem. The image-formed toner may be generated as a transfer residual toner on the photosensitive member, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. This value was measured as an average circularity by a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). A specific measurement method will be described later.

<Volume average particle diameter, number average particle diameter>
The toner of the present invention preferably has a volume average particle diameter (Dv) of 3 to 8 μm, and more preferably 4 to 7 μm. The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.25 or less, preferably 1.10 to 1.20. Here, the volume average particle diameter (Dv) is defined as Dv = [Σ (nD ³ ) / Σn] ^1/3 (where n is the number of particles and D is the particle diameter). In the present invention, by setting the value of (Dv / Dn) within the above range, it is excellent in all of heat resistant storage stability, low temperature fixing property, and hot offset resistance. Excellent two-component developer, even with long-term toner balance, fluctuations in toner particle diameter in the developer are reduced, and even with long-term agitation in the developing device, it is stable and stable. Developability is obtained. 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 is not fused to a member such as a blade, and good and stable developability and an image can be obtained even in the long-term use (stirring) of the developing device.
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, 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 larger than the range of the present invention.
On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter (Dv / Dn) is too large. Further, if the volume average particle size / number average particle size (Dv / Dn) is too small, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount, but the toner becomes insufficiently charged. In some cases, it was also found that the cleaning property may be deteriorated.
The volume average particle size / number average particle size (Dv / Dn) was measured using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with a volume average particle size (Dv ) And the number average particle diameter (Dn).

[Two-component carrier]
When the toner of the present invention is used for a dry two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 toners per 100 parts by mass of the carrier. Part by mass is preferable, and a range of 3 to 9 parts by mass is more preferable. 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 resin such as vinyl, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, 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. The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

[Fixing device]
The fixing device used in the present invention includes a fixing unit having a rotary heating body heated by electromagnetic induction, and a pressure that rotates in the forward direction with respect to the rotary heating body to form the fixing unit and the fixing nip portion. Means. Hereinafter, a fixing device suitable for the present invention will be described with reference to the drawings.
FIG. 1 is a diagram for explaining an example of a fixing device suitable for the present invention. The fixing device of FIG. 1 includes an induction heating means side roller 1 having an electromagnetic induction heating means 6 in the vicinity thereof, a fixing roller 2 as a fixing means arranged in parallel to the induction heating means side roller 1, and an induction heating means. An endless belt-like heat-resistant belt 3 serving as a rotary heating body, which is passed over the side roller 1 and the fixing roller 2 and heated by the induction heating means 6 and rotated in the direction of arrow A by at least rotation of any of these rollers. And a pressure roller 4 as pressure means that is pressed against the fixing roller 2 via the belt 3 and rotates in the forward direction with respect to the belt 3.
The induction heating means side roller 1 is made of a hollow cylindrical magnetic metal member such as iron, cobalt, nickel, or an alloy of these metals, and has an outer diameter of, for example, 20 mm and a wall thickness of, for example, 2 mm.
The fixing roller 2 includes a metal core 2a made of, for example, stainless steel, and an elastic member 2b covered with a core metal 2a made of heat-resistant silicon rubber in a solid or foamed form. In order to form a contact portion having a predetermined width between the pressure roller 4 and the fixing roller 2 by the pressing force from the pressure roller 4, the outer diameter is set to about 30 mm and is larger than the heating roller 1. The elastic member 2b has a thickness of about 3 to 8 mm and a hardness of about 15 to 50 ° (Asker hardness).
The belt 3 laid over the induction heating unit side roller 1 and the fixing roller 2 is heated by the induction heating unit 6 at the contact portion W1 with the induction heating unit side roller 1. Then, the belt 3 is continuously heated by the rotation of the rollers 1 and 2, and as a result, the entire belt is heated.

The thickness of the release layer (not shown) provided on the belt 3 is preferably about 100 μm to 300 μm, particularly about 200 μm. By doing so, the toner image T formed on the recording material 11 is sufficiently wrapped by the surface layer portion of the belt 3, so that the toner image T can be uniformly heated and melted. When the thickness of the release layer is less than 100 μm, the heat capacity of the belt 3 becomes small, and the belt surface temperature rapidly decreases in the toner fixing step, so that sufficient fixing performance cannot be ensured. Further, when the thickness of the release layer is larger than 300 μm, the heat capacity of the belt 3 is increased and the time required for warm-up is increased. In addition, in the toner fixing process, the belt surface temperature is difficult to decrease, the agglomeration effect of the melted toner at the fixing portion outlet cannot be obtained, the belt releasability is reduced, and the toner adheres to the belt. Hot offset occurs.
As the base material of the belt 3, a heat-resistant resin layer such as a fluorine resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a PEEK resin, a PES resin, or a PPS resin may be used.
The pressure roller 4 includes a cored bar 4a made of a cylindrical member made of a metal having high thermal conductivity such as copper or aluminum, and an elastic member having high heat resistance and toner releasability provided on the surface of the cored bar 4a. 4b. In addition to the above metal, SUS may be used for the core metal 4a.
The pressure roller 4 presses the fixing roller 2 via the belt 3 to form the fixing nip portion N. In this embodiment, the pressure roller 4 is harder than the fixing roller 2. As a result, the pressure roller 4 bites into the fixing roller 2 (and the belt 3), and this biting causes the recording material 11 to follow the circumferential shape of the surface of the pressure roller 4, so that the recording material 11 is separated from the belt 3 surface. Has the effect of facilitating. The outer diameter of the pressure roller 4 is about 30 mm, which is the same as that of the fixing roller 2, but the wall pressure is about 2 to 5 mm, thinner than the fixing roller 2, and the hardness is about 20 to 60 ° (Asker hardness). As described above, it is harder than the fixing roller 2.

  As shown in FIGS. 1 and 2A, an induction heating means 6 for heating the belt 3 by electromagnetic induction includes an excitation coil 7 as a magnetic field generation means and a coil guide plate 8 around which the excitation coil 7 is wound. And have. The coil guide plate 8 has a semi-cylindrical shape arranged close to the outer peripheral surface of the heating roller 1, and as shown in FIG. 2 (b), the excitation coil 7 is composed of a long excitation coil wire. 8 is alternately wound in the axial direction of the induction heating means side roller 1. The exciting coil 7 is connected to a driving power source (not shown) whose oscillation circuit has a variable frequency. Outside the excitation coil 7, a semi-cylindrical excitation coil core 9 made of a ferromagnetic material such as ferrite is fixed to the excitation coil core support member 10 and is disposed close to the excitation coil 7. In the present embodiment, the exciting coil core 9 has a relative permeability of 2500. A high frequency alternating current of 10 kHz to 1 MHz, preferably a high frequency alternating current of 20 kHz to 800 kHz is supplied to the exciting coil 7 from a driving power source, thereby generating an alternating magnetic field. The alternating magnetic field acts on the heat generation layer of the induction heating unit side roller 1 and the belt 3 in the contact area W1 between the induction heating unit side roller 1 and the heat-resistant belt 3 and the vicinity thereof. Eddy current flows in a direction that prevents change. This eddy current generates Joule heat corresponding to the resistance of the induction heating means side roller 1 and the heat generation layer, and the induction heating means side roller 1 and the contact area between the induction heating means side roller 1 and the belt 3 and the vicinity thereof mainly. The belt 3 having the heat generating layer 3a is heated by electromagnetic induction. The belt 3 heated in this way is detected by a temperature detecting means 5 comprising a thermosensitive element such as a thermistor disposed in contact with the inner surface side of the belt 3 in the vicinity of the entrance side of the fixing nip N. The belt inner surface temperature is detected.

[Image forming equipment]
Hereinafter, an image forming apparatus using the toner of the present invention or a two-component developer comprising the toner and a carrier will be described.
FIG. 3A is a configuration diagram [an enlarged view of an image forming unit] of an image forming apparatus using the image forming method according to the present embodiment. Around a photosensitive drum (hereinafter referred to as a photosensitive member) 10 as an image carrier, a charging roller 20 as a charging device, an exposure device 30, a cleaning device 60 having a cleaning blade, a static elimination lamp 70 as a static elimination device, and development. An apparatus 40 and an intermediate transfer member 50 as an intermediate transfer member are provided. The intermediate transfer member 50 is suspended by a plurality of suspension rollers 51 and is configured to run endlessly in the direction of the arrow by a driving unit such as a motor (not shown). A part of the suspension roller 51 also serves as a transfer bias roller for supplying a transfer bias to the intermediate transfer member, and a predetermined transfer bias voltage is applied from a power source (not shown). A cleaning device 90 having a cleaning blade for the intermediate transfer member 50 is also provided. Further, a transfer roller 80 is provided as a transfer means for transferring the developed image onto the transfer paper 100 as the final transfer material, facing the intermediate transfer body 50, and the transfer roller 80 is transferred by a power supply device (not shown). Supplied. A corona charger 52 is provided around the intermediate transfer member 50 as charge applying means.
The developing device 40 includes a developing belt 41 as a developer carrying member, a black (hereinafter referred to as “Bk”) developing unit 45K, a yellow (hereinafter referred to as “Y”) developing unit 45Y, The developing unit 45M is hereinafter referred to as “M” and the cyan (hereinafter referred to as “C”) developing unit 45C. Reference numeral 42 is a developing tank, 43 is a pumping roller, and 44 is a coating roller. Further, the developing belt 41 is stretched between a plurality of belt rollers, and is configured to run endlessly in a direction indicated by an arrow by a driving unit such as a motor (not shown). Moves at approximately the same speed as 10.
In addition to the apparatus configuration shown in FIG. 3A, the configuration of the image forming apparatus according to the present embodiment includes each color developing unit 45 as shown in FIG. It may be a device configuration provided around.

Next, the operation of the copying machine according to the present embodiment will be described. 3A and 3B, the photosensitive member 10 is uniformly charged by the charging roller 20 while being driven to rotate in the direction of the arrow, and then the reflected light from the document is imaged and projected by the exposure device 30 by an optical system (not shown). Thus, an electrostatic latent image is formed on the photoreceptor 10. The electrostatic latent image is developed by the developing device 40 to form a toner image as a visible image. The developer thin layer on the developing belt 41 is peeled off from the belt 41 in a thin layer state by contact with the photosensitive member in the developing region, and moves to a portion where a latent image is formed on the photosensitive member 10. The toner image developed by the developing device 40 is transferred to the surface of the intermediate transfer member 50 at the contact portion (primary transfer region) between the photosensitive member 10 and the intermediate transfer member 50 moving at a constant speed (primary transfer). Transcription). When transferring three or four colors to be superimposed, this process is repeated for each color to form a color image on the intermediate transfer member 50.
The corona charger 52 for applying an electric charge to the superimposed toner image on the intermediate transfer member is provided at a contact facing portion between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is installed on the downstream side and on the upstream side of the contact facing portion between the intermediate transfer member 50 and the transfer paper 100. The corona charger 52 gives the toner image a true charge having the same polarity as the charge polarity of the toner particles forming the toner image, and is sufficient for good transfer to the transfer paper 100. Charge is applied to the toner image. The toner image is charged by the corona charger 52 and then transferred to the transfer paper 100 conveyed in the direction of the arrow from a paper supply unit (not shown) by a transfer bias from the transfer roller 80 (two). Next transfer). Thereafter, the transfer paper 100 onto which the toner image has been transferred is separated from the photoconductor 10 by a separation device (not shown), and after a fixing process is performed by a fixing device (not shown), the transfer paper 100 is discharged from the device. On the other hand, after the transfer, the untransferred toner is collected and removed by the cleaning device 60, and the residual charge is discharged by the discharging lamp 70 in preparation for the next charging.
Surface layer material of developing belt 41, surface layer prevents contamination of photosensitive member by elastic material, reduces surface friction resistance to transfer belt surface, reduces toner adhesion, and improves cleaning property and secondary transfer property Is required. For example, materials that use one or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and improve lubricity, such as powders of fluororesins, fluorine compounds, fluorocarbons, titanium dioxide, silicon carbide, etc. One body, two or more kinds of particles or particles having different particle diameters can be dispersed and used. Further, it is also possible to use a material such as a fluorine-based rubber material in which a surface is reduced in surface energy by forming a fluorine-rich layer on the surface.

[Process cartridge]
The process cartridge of the present invention is capable of developing an electrostatic image carrier carrying an electrostatic image and the electrostatic image carried on the electrostatic image carrier using a developer containing the toner of the present invention. At least developing means for forming a visual image, and other means appropriately selected as necessary. The developing means includes at least a developer container that contains the toner or developer of the present invention and a developer carrier that carries and transports the toner or developer contained in the developer container. Further, a layer thickness regulating member for regulating the thickness of the toner layer to be carried may be provided. The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably provided detachably in an image forming apparatus main body to be described later.
FIG. 4 is a schematic view for explaining the process cartridge of the present invention.
In FIG. 4, in an image forming apparatus having a process cartridge 450 of the present invention, a photosensitive member 451 as an electrostatic charge image carrier is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member 451 is uniformly charged at a predetermined positive or negative potential on the peripheral surface thereof by the charging unit 452, and then image exposure from an image exposure unit such as slit exposure or laser beam scanning exposure (not shown). The electrostatic image is sequentially formed on the peripheral surface of the photoreceptor in this manner, and the formed electrostatic image is then developed with toner by the developing means 453, and the developed toner image is fed to a paper feeding unit (not shown) To the recording material fed in synchronism with the rotation of the photosensitive member between the photosensitive member and the transfer means, the recording material is sequentially transferred by the transfer means, and the recording material which has received the image transfer is separated from the surface of the photosensitive member and image fixing means Then, the image is fixed and printed out as a copy. The surface of the photoconductor after the image transfer is cleaned by removing the transfer residual toner by the cleaning unit 454, and after being further neutralized, it is repeatedly used for image formation.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, “part” means mass part, and “%” means mass%.
[Example 1]
~ Synthesis of organic fine particle emulsion ~
In a reaction vessel in which a stir bar and a thermometer were set, 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 temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion was obtained. This is designated as [fine particle dispersion 1]. 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 120 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 42 ° C. and the mass average molecular weight was 30,000.

-Adjustment of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred to give milky white A liquid was obtained. This is referred to as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Put 2 parts of tin oxide, react at 230 ° C for 8 hours at normal pressure, and further react for 5 hours under reduced pressure of 10-15mmHg, then put 44 parts of trimellitic anhydride into the reaction vessel, 180 ° C at normal pressure Reaction was performed for 2 hours to obtain a polyester. This is referred to as [low molecular polyester 1]. The [low molecular weight polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25.

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

~ Synthesis of ketimine ~
A reaction vessel equipped with a stir bar and a thermometer was charged with 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone, and reacted at 50 ° C. for 5 hours to obtain a ketimine compound. This is referred to as [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

~ Master batch synthesis ~
Add 1200 parts of water, 540 parts of carbon black (made by Printex35 Dexa) [DBP oil absorption = 42ml / 100mg, pH = 9.5], 1200 parts of polyester resin (RS801 made by Sanyo Kasei) and mix with Henschel mixer (made by Mitsui Mining Co., Ltd.) The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain a master batch. This is designated as [Master batch 1].

~ Creation of oil phase ~
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular weight polyester 1], Carnauba WAX11O part, 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain a mixed solution. This is referred to as [Raw material solution 1].
[Raw material solution 1] Transfer 1324 parts to a container and use a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.). The carbon black and WAX were dispersed under the condition of 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain a dispersion. This is designated as [Pigment / WAX Dispersion 1]. The [pigment / WAX dispersion 1] had a solid concentration (130 ° C.) of 50%.

~ Emulsification, solvent removal ~
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and mixed for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika) Then, 1200 parts of [Aqueous Phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain an emulsion. This is designated as [Emulsified slurry 1].
[Emulsion slurry 1] is put into a container equipped with a stirrer and a thermometer, and after desolvation at 30 ° C for 8 hours, aging is performed at 200 rpm and 45 ° C for 4 hours to obtain [dispersed slurry 1]. It was. [Dispersion Slurry 1] had a volume average particle size of 5.99 μm and a number average particle size of 5.70 μm (measured with Multisizer II).

~ Washing, drying, fluorine treatment ~
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 1OO parts of 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 12,000 rpm) and filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered twice to obtain a cake. This is designated as [Filter cake 1].
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier.
Thereafter, 15 parts of [Filter Cake 1] is added to 90 parts of water, and 0.0005 part of the fluorine-containing compound (Exemplary Compound (2)) is dispersed therein, thereby the fluorine-containing compound (2) on the toner particle surface. Then, it was dried at 45 ° C. for 48 hours in a circulating dryer. Thereafter, the mixture was sieved with a 75 μm mesh to obtain toner base particles. This is designated as [toner base particle 1].

~ External additive treatment ~
To 100 parts of [Toner Base Particle 1] obtained above, 0.7 parts of hydrophobic silica as an external additive and 0.3 parts of hydrophobic titanium oxide were mixed with a Henschel mixer to obtain a toner. It was. This is referred to as [Toner 1]. The physical property values (and the fixing results) of [Toner 1] are listed in Table 1.

-Adjustment of developer-
[Toner base particle 1] A two-component developer consisting of 5% by mass and 95% by mass of a copper-zinc ferrite carrier coated with a silicone resin and having an average particle size of 40 μm was prepared. Using this developer, Ricoh imagio Neo 450, which can print 45 sheets of A4 size paper per minute, was continuously printed and evaluated by the following evaluation method. The evaluation results obtained are shown in Table 2. It was.

[Example 2]
~ 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), 78 parts of styrene, 83 parts of methacrylic acid, When 115 parts of butyl acrylate, 2 parts of butyl thioglycolate and 1 part of ammonium persulfate were charged and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the temperature in the system 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 [fine particle dispersion 2] was obtained. The volume average particle diameter of [fine particle dispersion 2] measured by LA-920 was 115 μm. A portion of [Fine Particle Dispersion 2] was dried to isolate the resin component. The Tg of the resin was 51 ° C., and the mass average molecular weight was 100,000.

~ Creation of [Toner 2] ~
[Filter cake 2] was obtained in the same manner as in Example 1 except that [Fine particle dispersion 2] was used instead of [Fine particle dispersion 1] in Example 1. Thereafter, 15 parts of [Filter Cake 2] is added to 90 parts of water, and 0.001 part of a fluorine-containing compound (Exemplary Compound (2)) is dispersed therein, whereby the fluorine-containing compound (2) is dispersed on the toner particle surface. Then, it was dried at 45 ° C. for 48 hours with a circulating dryer. Thereafter, the mixture was sieved with a 75 μm mesh to obtain toner base particles. This is designated as [toner base particle 2]. This was subjected to the same external additive treatment as in Example 1 to obtain [Toner 2].

Example 3
~ 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 a sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 103 parts of styrene, 83 parts of methacrylic acid, When 90 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 temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 3] was obtained. The volume average particle diameter of [fine particle dispersion 3] measured with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corp.) was 104 nm. A portion of [Fine Particle Dispersion 3] was dried to isolate the resin component. The Tg of the resin was 78 ° C., and the mass average molecular weight was 25,000.

-Adjustment of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 3], 37 parts of 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred to give milky white A liquid was obtained. This is called [Aqueous Phase 3].

~ Emulsification, solvent removal ~
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and mixed for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika) Then, 1200 parts of [Aqueous phase 3] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain an emulsion. This is designated as [Emulsified slurry 3].
[Emulsion slurry 3] is put into a container equipped with a stirrer and a thermometer, and after desolvation at 30 ° C for 8 hours, aging is performed at 200 rpm and 45 ° C for 8 hours to obtain [dispersed slurry 3]. It was. [Dispersion Slurry 3] had a volume average particle size of 5.86 μm and a number average particle size of 5.40 μm (measured with Multisizer II).
~ Creation of [Toner 3] ~
As described above, Example 1 was used except that [Fine particle dispersion 3] was used instead of [Fine particle dispersion 1] in Example 1, and [Dispersion slurry 3] was used instead of [Dispersion slurry 1]. [Filtered cake 3] was obtained using the same process as in the above step. Thereafter, 15 parts of [Filter Cake 3] is added to 90 parts of water, and 0.001 part of a fluorine-containing compound (Exemplary Compound (2)) is dispersed therein, whereby the fluorine-containing compound (2) is dispersed on the toner particle surface. Then, it was dried at 45 ° C. for 48 hours with a circulating dryer. Thereafter, the mixture was sieved with a 75 μm mesh to obtain toner base particles. This is designated as [toner base particle 3]. This was subjected to the same external additive treatment as in Example 1 to obtain [Toner 3].

Example 4
~ 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, Sanyo Chemical Industries), 68 parts of styrene, 93 parts of methacrylic acid, When 115 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 4] was obtained. The volume average particle diameter of [fine particle dispersion 4] measured by LA-920 was 90 nm. A portion of [Fine Particle Dispersion 4] was dried to isolate the resin component. The Tg of the resin was 56 ° C., and the mass average molecular weight was 150,000.

-Adjustment of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 4], 37 parts of 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred to give milky white A liquid was obtained. This is referred to as [Aqueous Phase 4].

~ Emulsification, solvent removal ~
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and mixed for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika) Then, 1200 parts of [Aqueous Phase 4] was added to the container and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain an emulsion. This is designated as [Emulsified slurry 4].
[Emulsion slurry 4] is put into a container equipped with a stirrer and a thermometer, and after desolvation at 30 ° C for 8 hours, aging is performed at 200 rpm and 27 ° C for 2 hours to obtain [dispersed slurry 4]. It was. [Dispersion slurry 4] had a volume average particle size of 5.16 μm and a number average particle size of 4.52 μm (measured with Multisizer II).

~ Creation of [Toner 3] ~
As described above, Example 1 was used except that [Fine particle dispersion 4] was used instead of [Fine particle dispersion 1] in Example 1, and [Dispersion slurry 4] was used instead of [Dispersion slurry 1]. [Filtered cake 4] was obtained as a toner in the same process as in Example 1. Thereafter, 15 parts of [Filter Cake 4] is added to 90 parts of water, and 0.001 part of a fluorine-containing compound (Exemplary Compound (2)) is dispersed therein, whereby the fluorine-containing compound (2) is dispersed on the toner particle surface. Then, it was dried at 45 ° C. for 48 hours in a circulating dryer. Thereafter, the mixture was sieved with a 75 μm mesh to obtain toner base particles. This was designated as [toner base particle 4]. This was subjected to the same external additive treatment as in Example 1 to obtain [Toner 4].

Example 5
~ Synthesis of low molecular weight polyester ~
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Put 2 parts of tin oxide, react at 230 ° C for 8 hours at normal pressure, and react for 5 hours at 10-15mmHg, then add 26 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. Reaction was performed for 2 hours to obtain polyester. This is designated as [Low molecular polyester 2]. The [low molecular weight polyester 2] had a number average molecular weight of 2,400, a weight average molecular weight of 6,200, Tg of 43 ° C., and an acid value of 15.

~ Creation of [Toner 5] ~
[Filter cake 5] was obtained in the same manner as in Example 1 except that [Low molecular polyester 2] was used instead of [Low molecular polyester 1] in Example 1. Thereafter, 15 parts of [Filtration cake 5] is added to 90 parts of water, and 0.0005 part of the fluorine-containing compound (the exemplified compound (2)) is dispersed therein, whereby the fluorine-containing compound (2) is dispersed on the toner particle surface. Then, it was dried at 45 ° C. for 48 hours with a circulating dryer. Thereafter, the mixture was sieved with a 75 μm mesh to obtain toner base particles. This was designated as [toner base particle 5]. This was subjected to the same external additive treatment as in Example 1 to obtain [Toner 5].

Example 6
~ Creation of [Toner 6] ~
In Example 5, 15 parts of [Filtration cake 5] is added to 90 parts of water, and 0.002 part of the fluorine-containing compound (Exemplary Compound (2)) is dispersed therein to thereby add a fluorine-containing compound on the toner particle surface. After adhering (2), it was dried at 45 ° C. for 48 hours with a circulating dryer. Thereafter, the mixture was sieved with a 75 μm mesh to obtain toner base particles. This was designated as [toner base particle 6]. This was subjected to the same external additive treatment as in Example 1 to obtain [Toner 6].

[Comparative Example 1]
After adding 451 g of a 0.1 M Na ₃ PO ₄ aqueous solution to 709 g of ion-exchanged water and heating to 60 ° C., the mixture was stirred at 12,000 rpm using a TK homomixer. To this, 68 g of 1.0 M CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ . 170 g of styrene, 30 g of 2-ethylhexyl acrylate, 10 g of Regal 400R, 60 g of paraffin wax (sp. 70 ° C.), 5 g of metal compound of di-tert-butylsalicylate, styrene-methacrylic acid copolymer (Mw 50,000, acid value) 10 mg of 20 mg KOH / g) was put into a TK homomixer, heated to 60 ° C., and uniformly dissolved and dispersed at 12,000 rpm. In this, 10 g of a polymerization initiator, 2,2′-azobis (2,4-dimethylvaleronitrile), was dissolved to prepare a polymerizable monomer system. The polymerizable monomer system was put into the aqueous medium and stirred at 10,000 rpm for 20 minutes with a TK homomixer at 60 ° C. in an N ₂ atmosphere to granulate the polymerizable monomer system. Then, after making it react with a paddle stirring blade for 3 hours at 60 degreeC, liquid temperature was made 80 degreeC and it was made to react for 10 hours.
That is, without using an organic solvent phase, the polymerization reaction was completed and the mixture was cooled, and hydrochloric acid was added to dissolve calcium phosphate, followed by filtration, washing with water and drying to obtain [Toner 7].

[Comparative Example 2]
In Example 1, [Toner 8] was obtained in the same manner as in Example 1 except that 0.0003 parts of the fluorine-containing compound (Exemplary Compound (2)) was dispersed in the washing, drying, and fluorine treatment steps.

[Comparative Example 3]
In Example 5, [Toner 9] was obtained in the same manner as in Example 1 except that 0.01 parts of the fluorine-containing compound (Exemplary Compound (2)) was dispersed in the washing, drying, and fluorine treatment steps.

[Comparative Example 4]
In [Example 4], [Toner 10] was obtained in the same manner as Example 1 except that the cleaning, drying, and fluorine treatment steps were the same except that the treatment step of the fluorine-containing compound (2) was omitted.

[Evaluation methods]
(1) Measurement of Volume Average Particle Diameter and (Dv / Dn) The particle diameter of the toner was measured using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle diameter and the number average particle diameter were determined by the particle size measuring instrument. (Dv / Dn) was automatically calculated from the above values.
(2) Average circularity The average circularity can be measured by a flow particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .
(3) Measurement of fluorine content in toner base particles The fluorine content in toner base particles in the present invention can be measured by the following method.
The apparatus used was XPS (X-ray photoelectron spectroscopy). The measurement method, apparatus type, conditions, and the like are not particularly limited as long as similar results can be obtained, but the following conditions are more preferable. Under the following conditions, the content of fluorine atoms in the region of the extreme surface of the toner surface of about several nm is measured.
Equipment: PHI 1600S X-ray photoelectron spectrometer X-ray source: MgKα (400W)
Analysis area: 0.8 × 2.0mm
Pretreatment: Samples were packed in an aluminum dish and the surface was smoothed before measurement.
Surface atomic concentration calculation: RHI-provided relative sensitivity factor was used.
The result obtained is atomic% (number of atoms%).
(4) Measurement method of resin fine particle content The toner is thermally decomposed, and the amount of styrene monomer in the thermal decomposition product is measured using the styrene monomer derived from the styrene-acrylic copolymer resin fine particles as a label. Based on the measurement results, the resin fine particle content in the toner was calculated and determined. That is, using styrene-acrylic copolymer resin fine particles having a known composition as a labeling component, 0.01% by mass, 0.10% by mass, 1.00% by mass, Using each model toner having a known composition obtained by using a mass ratio of 0.000% by mass and 10.0% by mass, thermal decomposition was performed under the conditions of 590 ° C. × 12 seconds, and heat was applied under the following conditions. The decomposition products were analyzed and the peak area of the styrene monomer was determined for each.
Analytical instrument: Pyrolysis gas chromatograph mass spectrometer Configuration body: Shimadzu QR-5000
Accessory pyrolysis furnace: Nippon Analytical Industry JHP-3S
Thermal decomposition temperature: 590 ° C. × 12 seconds Column: DB-1 L = 30 m D = 0.25 mm Film = 0.25 μm
Column temperature: 40 ° C. (holding 2 minutes) to (10 ° C./minute temperature increase) 300 ° C.
Vaporization chamber temperature: 300 ° C
(5) Tg measuring method The measuring method of Tg is demonstrated. As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, the sample was cooled to room temperature and left for 10 minutes, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was calculated from the tangent of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

<Copy image formation performance>
(A) Fixability Using Ricoh's imagio Neo 450, solid images and thick paper transfer paper (Ricoh type 6200 and NBS Ricoh's copy printing paper <135>) are solid images, 1.0 ± 0.1 mg Adjustment was performed so that a toner of / cm ² was developed. As the fixing device, a device as shown in FIGS. 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 minimum fixing 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. In the evaluation, those having a lower fixing limit higher than 160 ° C. were judged as defective.
(B) Charge amount transition The image chart having a 5% image area was continuously run up to 50000 sheets, and then the following evaluation was performed. (The same applies to items (c) to (e) below)
In the initial state (after start-up) and after the passage of 50000 sheets, 6 g of the developer was weighed, charged into a metal cylinder that can be sealed, and blown to determine the transition of the charge amount.
(C) Image density After outputting a solid image, the image density was measured by X-Rite (manufactured by X-Rite). This was measured at five points for each color alone, and the average was obtained for each color.
(D) Background stain The blank image is stopped during development, the developer on the developed photoconductor is transferred to tape, and the difference from the image density of the untransferred tape is measured by 938 Spectrodensitometer (manufactured by X-Rite) ).

Regarding Examples 1 to 6, the evaluation results of the fixing property are good, and the results of the respective qualities such as the stability of the charging performance with time, the maintenance of the image density, and the background stains are good.
In Comparative Examples 1 and 3, the lower fixing minimum temperature is the result, and both the fixing properties are poor. In particular, in Comparative Example 3, since the initial charge amount was too large, the image density was insufficient from the initial value, and continuous printing could not be performed, and the evaluation was stopped midway. In Comparative Example 2 and Comparative Example 4 where the fluorine content is low / not contained, the charging property is poor, and the continuous printing up to 50,000 sheets becomes remarkable due to the deterioration of toner scattering and the deterioration of the background stain due to the reduction of charging. The evaluation was discontinued.

  According to the present invention, the offset resistance is good, the fixing device and the image are not contaminated, the toner charging capability is sufficiently high, the weakly charged toner and the reversely charged toner are few, high temperature and high humidity, and low temperature and low humidity environment. Is excellent in charging stability, and even if tens of thousands of images are output, an image with little background stain (fogging) is formed, toner is less scattered in the machine, and an image quality with sufficient image density can be obtained. An image forming method, an electrostatic charge image developing toner, a developer, and a process cartridge are provided.

It is a figure for demonstrating an example of the fixing device used for this invention. (A) is sectional drawing which shows arrangement | positioning of the excitation coil of the induction heating means in the fixing device of this invention, (b) is a side view which shows arrangement | positioning of the excitation coil of the induction heating means in the fixing device of this invention. 1 is a configuration diagram of an image forming apparatus using an image forming method of the present invention. It is the schematic for demonstrating the process cartridge of this invention. It is a schematic diagram which shows the fixing device by the conventional electromagnetic induction heating system.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Induction heating means side roller 2 Fixing roller 3 Belt 4 Pressure roller 6 Induction heating means 7 Excitation coil 8 Coil guide plate 10 Photoconductor 20 Charging roller 30 Exposure device 40 Developing device 45 Developing unit 50 Intermediate transfer body 60 Cleaning device 70 Static elimination Lamp 80 Transfer roller 90 Cleaning device 450 Process cartridge

Claims (13)

Developing the electrostatic latent image formed on the image carrier using toner, transferring the toner image formed on the image carrier to an image support, and fixing the transferred toner image by a fixing device; In an image forming method including:
The fixing device includes a fixing unit having a rotary heating body heated by electromagnetic induction, and a pressure unit that rotates in a forward direction with respect to the rotary heating body to form the fixing unit and a fixing nip portion. ,
The toner includes at least a toner binder resin and a colorant, and the toner binder resin includes a polyester-based resin in at least one part and is granulated in an aqueous medium including resin fine particles, and the surface of the particle is a fluorine-containing compound. An image forming method, wherein the toner is an electrostatic charge image developing toner processed by using the toner, and the toner satisfies the following conditions (1) and (2).
(1) The content of fluorine atoms detected by XPS (X-ray photoelectron spectroscopy) of the toner is 2 to 30 atomic percent.
(2) The content of the resin fine particles contained in the toner with respect to the toner is 0.5 to 5.0 mass%.   The toner dissolves or disperses a toner composition containing a toner binder resin composed of a modified polyester resin capable of reacting with active hydrogen in an organic solvent, and the dissolved or dispersed solution is dissolved in an aqueous medium containing resin fine particles. An electrostatic charge image developing toner which is dispersed and reacted with a cross-linking agent and / or an extender, and the solvent is removed from the resulting dispersion to form particles, and the surface of the particles is treated with a fluorine-containing compound. The image forming method according to claim 1, wherein: A toner composition containing a toner binder resin composed of a modified polyester resin capable of reacting with active hydrogen is dissolved or dispersed in an organic solvent, the dissolved or dispersed material is dispersed in an aqueous medium containing resin fine particles, and A toner for developing an electrostatic charge image, wherein the toner is reacted with a crosslinking agent and / or an extender, and the solvent is removed from the obtained dispersion to form particles, and the surface of the particles is treated with a fluorine-containing compound. An electrostatic charge image developing toner, wherein the toner satisfies the following conditions (1) and (2).
(1) The content of fluorine atoms detected by XPS (X-ray photoelectron spectroscopy) of the toner is 2 to 30 atomic percent.
(2) The content of the resin fine particles contained in the toner with respect to the toner is 0.5 to 5.0 mass%. The fluorine-containing compound is represented by the following general formula (1):

(Wherein X is —SO ₂ — or —CO—, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and aryl. A group selected from the group, Y is an iodine atom, bromine atom or chlorine atom, m is an integer of 1 to 10, and n is an integer of 1 to 10)
The electrostatic charge image developing toner according to claim 3, wherein   A non-reactive polyester is further dissolved in the organic solvent together with the modified polyester resin, and a mass ratio of the modified polyester resin to the non-reactive polyester is 5/95 to 75/25. 5. The toner for developing an electrostatic charge image according to claim 3, wherein the toner is for developing an electrostatic image.   6. The electrostatic image developing toner according to claim 3, wherein the toner has a volume average particle diameter (Dv) of 3 to 8 [mu] m.   7. The electrostatic image developing toner according to claim 3, wherein the toner has a volume average particle diameter (Dv) / number average particle diameter (Dn) of 1.25 or less.   8. The electrostatic image developing toner according to claim 3, wherein the toner has an average circularity of 0.900 to 0.980.   9. The electrostatic image developing toner according to claim 3, wherein the resin fine particles are vinyl resin, polyurethane resin, epoxy resin, polyester resin, or a combination of at least two of them.   10. The electrostatic charge image developing toner according to claim 3, wherein the resin fine particles have a glass transition point (Tg) of 40 to 100 ° C. 10.   The toner for developing an electrostatic charge image according to any one of claims 3 to 10, wherein the resin fine particles have an average particle diameter of 5 to 500 nm.   A dry two-component developer comprising the electrostatic image developing toner according to claim 3. An image carrier and at least developing means for developing an electrostatic image formed on the image carrier using the electrostatic image developing toner according to claim 3 to form a visible image. And a process cartridge that is detachable from the main body of the image forming apparatus.

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