JP2007079381A - Toner and manufacturing method of the same, developer, toner charged container, process cartridge, apparatus and method for image forming - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner or the like showing excellent charge rising property of the toner and contamination prevention on an OPC (organic photoconductor), and giving an image of high quality with high image density and less contamination of the base. <P>SOLUTION: The toner comprises toner mother particles containing at least a binder resin and a colorant and fluorocarbon resin fine particles, and is characterized in that average circularity of the toner ranges from 0.88 to 0.96 and that the isolation rate of the fluorocarbon resin fine particles expressed by formula 1:isolation rate (%) of fluorocarbon resin fine particles=(A/B)×100, ranges from 60 to 99%, wherein A represents a fluorine atom concentration on a toner surface measured by X-ray photoelectron spectroscopy on a sample prepared by mixing and agitating 5 g of the, 150 ml of a 15 mass% NaCl aqueous solution, and 1 ml of a surfactant, then dispersing the mixture for 30 minutes in a homogenizer while keeping the temperature at 40°C, and B is a fluorine atom concentration on a toner surface measured before carrying out the dispersion treatment in (A). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, a method for producing the toner, a developer using the toner, a container containing the toner, a process cartridge, and image formation The present invention relates to an apparatus and an image forming method.

As a developing method used in an electrophotographic copying machine or an electrostatic recording apparatus, a developer is transported by a transport member, and an electrostatic latent image carrier (hereinafter referred to as “photoconductor”, “electrophotographic photoreceptor”) is transported by the developer. There are known methods for visualizing the electrostatic latent image formed on the surface. In such a developing method, a one-component developer composed of toner or a two-component developer composed of toner and carrier is generally used.
The toner is usually composed of a binder resin, a colorant, a charge control agent, and other additives.

  Conventionally, various charge control agents have been proposed in order to impart good charging characteristics, stability over time, and environmental stability. In this case, since a colored material cannot be used for the charge control agent for full-color toner, a colorless, white, or light-color charge control agent that does not affect the hue must be used.

Examples of such charge control agents include metal complex salts of salicylic acid derivatives (see Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4), aromatic dicarboxylic acid metal salt compounds (see Patent Document 5). Metal complex salt compounds of anthranilic acid derivatives (see Patent Document 6), organoboron compounds (see Patent Document 7 and Patent Document 8), and the like have been proposed.
However, these charge control agents are chromium-containing compounds that are of concern for environmental safety, and have drawbacks such as insufficient charging effect, insufficient environmental stability, and insufficient charge rise. The charge control agent did not have satisfactory performance.

Further, the charge control agent is difficult to disperse in the binder resin, and it is necessary to add a large amount in order to obtain a desired chargeability, resulting in a high cost.
On the other hand, the adhering of the charge control agent by mechanical mixing has the advantage that only a small amount is required, but due to its structure, the charge control agent tends to fall off from the toner surface, and the charging performance deteriorates with the passage of time in the developing machine. Body (OPC) contamination may be exacerbated. For example, Patent Document 9 proposes using a zirconium organometallic compound as a charge control agent. However, in this proposal, a jet mill pulverizer is used for pulverization, and the average circularity of the toner in each example is as small as 0.83 to 0.85.

  Therefore, by controlling the release rate of the fluororesin fine particles as a charge control agent from the toner surface, it is possible to obtain a high-quality image with excellent toner charge rise and OPC contamination, high image density, and low background contamination. The available toner and related technology have not been provided yet, and it is desired to provide the toner promptly.

Japanese Patent Publication No.55-42752 JP-A-61-69073 JP 61-221756 A JP-A-9-124659 JP-A-57-111541 JP 62-94856 A Japanese Patent Publication No. 7-31421 Japanese Examined Patent Publication No. 7-104620 JP 2001-249500 A

  An object of the present invention is to solve the conventional problems in response to the above-mentioned demands and achieve the following object. That is, according to the present invention, by controlling the liberation rate of the fluororesin fine particles from the toner surface, it is possible to obtain a high-quality image that is excellent in charge rising property of the toner and OPC contamination, has high image density, and has little background stain. It is an object of the present invention to provide a toner to be produced, a method for producing the toner efficiently and inexpensively, and a developer, a toner-containing container, a process cartridge, an image forming apparatus, and an image forming method using the toner.

Means for solving the problems are as follows. That is,
<1> A toner containing toner base particles containing at least a binder resin and a colorant, and fluororesin fine particles,
The toner has an average circularity of 0.88 to 0.96, and a release rate of fluororesin fine particles represented by the following formula 1 in the toner is 60 to 99%. .
<Formula 1>
Fluorine resin fine particle release rate (%) = (A / B) × 100
In Formula 1, A represents X-rays after mixing 5 g of toner, 150 ml of 15 mass% NaCl aqueous solution, and 1 ml of surfactant, stirring, and then dispersing with a homogenizer for 30 minutes while maintaining at 40 ° C. This represents the fluorine atom concentration (atomic number%) on the toner surface measured by photoelectron spectroscopy. B represents the fluorine atom concentration (number of atoms%) on the toner surface before the dispersion treatment in A is performed.
<2> The toner according to <1>, wherein the fluororesin fine particles are a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer represented by the following general formula (1).
However, in said general formula (1), Rf represents a perfluoro group. m and n represent a positive integer.
<3> The toner according to <2>, wherein the fluororesin fine particles have a number average particle size of primary particles of 5 to 2,000 nm.
<4> The toner according to any one of <1> to <3>, wherein the binder resin is a polyester resin.
<5> The toner according to any one of <1> to <4>, wherein the toner is a negatively chargeable toner.
<6> The toner according to any one of <1> to <5>, wherein the toner has a volume average particle diameter of 5 to 10 μm and a toner having a particle diameter of 4 μm or less is 20% by number or less.
<7> a melt-kneading step of melting and kneading a toner material containing at least a binder resin and a colorant;
A toner base particle manufacturing step of pulverizing and classifying the obtained melt-kneaded product to manufacture toner base particles;
And a mechanical mixing step of adding fluorine resin fine particles to the obtained toner base particles and mechanically mixing them.
<8> The method for producing a toner according to <7>, wherein 0.1 to 10 parts by mass of fluororesin fine particles are added to 100 parts by mass of the toner base particles and mechanically mixed.
<9> A developer comprising the toner according to any one of <1> to <6>.
<10> A toner-containing container filled with the toner according to any one of <1> to <6>.
<11> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to <6> to be a visible image And a developing means for forming the process cartridge.
<12> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <1> to <6> An image comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is a forming method.
<13> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of <1> to <6> Development means for forming a visible image by developing using any of the toners, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium The image forming apparatus is characterized by having at least.

The toner of the present invention contains toner base particles containing at least a binder resin and a colorant, and fluororesin fine particles, and the toner has an average circularity of 0.88 to 0.96, and The liberation rate of the fluororesin fine particles represented by the following formula 1 in the toner is 60 to 99%.
<Formula 1>
Fluorine resin fine particle release rate (%) = (A / B) × 100
In Formula 1, A represents X-ray photoelectrons after mixing 5 g of toner, 150 ml of a 15% by weight NaCl aqueous solution, and 1 ml of a surfactant, and after stirring and dispersing for 30 minutes with a homogenizer while maintaining the temperature at 40 ° C. This represents the fluorine atom concentration (number of atoms%) on the toner surface measured by spectroscopy. B represents the fluorine atom concentration (number of atoms%) on the toner surface before the processing in A.
In the toner of the present invention, by using fluorine resin fine particles as a charge control agent, and controlling the liberation rate of the fluorine resin fine particles within a predetermined range, the charge rise is sufficient without contaminating OPC. Thus, a developer suitable as a developer having a high charge level and less occurrence of a reversely charged developer can be obtained. In addition, a high-quality image with high image density and little background stain can be obtained. Furthermore, the fluorine-based resin fine particles have a strong interaction with the binder resin, are uniformly dispersed in the developer particles, and do not easily shift to the fixing roller at a high temperature during fixing, that is, do not cause so-called offset. As a result, the life of the fixing roller is dramatically increased, and the amount of the release agent applied to the fixing roller can be extremely reduced, or it may not be necessary. In particular, when the charge control agent is adhered to the toner surface by mechanical stirring, there is almost no cost merit by adding a small amount, and the fluororesin fine particles are not detached from the toner surface. Contamination is no problem.
The reason for this is not clear, but if it is within the range of the average circularity of a specific toner, the release of the fluororesin fine particles due to the stirring of the developer in the developing machine is alleviated, and the fluororesin fine particles become the final resin. This is presumably due to the strong adhesion.

  The developer of the present invention contains the toner of the present invention. When an image is formed by electrophotography using the developer of the present invention, a high-quality image having excellent toner charge rise and OPC contamination, high image density, and low background contamination can be obtained.

  The toner-containing container of the present invention contains the toner of the present invention in a container. When an image is formed by electrophotography using the toner contained in the toner-containing container of the present invention, a high-quality image having excellent toner charge rising property and OPC contamination, high image density, and low background contamination is obtained. can get.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge of the present invention can be attached to and detached from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that it is excellent in toner charge start-up property and OPC contamination, has high image density, and has a background. A high-quality image with little dirt can be obtained.

  The image forming apparatus of the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. The image forming apparatus includes at least a developing unit that forms a visible image by developing with toner, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium. According to the image forming apparatus of the present invention, since the toner of the present invention is used, it is possible to form a high-quality image that is excellent in toner charge rising property and OPC contamination, has high image density, and has little background stain. Can do.

  The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and the electrostatic latent image is developed using the toner of the present invention to be visible. It includes at least a developing step for forming an image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming method of the present invention, since the toner of the present invention is used, it is possible to form a high-quality image having excellent toner charge rise and OPC contamination, high image density, and low background contamination. it can.

  According to the present invention, conventional problems can be solved, and by controlling the liberation rate of the fluororesin fine particles from the toner surface, the toner has excellent charge start-up property and OPC contamination, high image density, Provided are a toner capable of obtaining a high-quality image with little dirt, a method for producing the toner efficiently and inexpensively, a developer using the toner, a container containing the toner, a process cartridge, an image forming apparatus, and an image forming method. can do.

(toner)
The toner of the present invention contains toner base particles containing at least a binder resin and a colorant, and fluorine resin fine particles, and further contains other components as necessary.

  In the present invention, the release rate of the fluororesin fine particles represented by the following formula 1 in the toner is 60 to 99%, preferably 80 to 95%. When the liberation rate of the fluororesin fine particles is less than 60%, OPC contamination by the desorbing fluororesin fine particles and charging stability over time may be inferior. In many cases, the toner is buried in the toner surface, and the toner fluidity is likely to be lowered.

Here, the liberation rate of the fluororesin fine particles is specifically determined by mixing 5 g of toner, 150 ml of an electrolytic solution adjusted to a 15% concentration of NaCl, and 1 ml of a surfactant, and then stirring well. Disperse with a homogenizer for 30 minutes while maintaining the temperature. The homogenizer conditions are arbitrarily adjusted according to the type of toner.
The obtained dispersion is vacuum filtered, dried at an appropriate temperature, and then the fluorine atom concentration on the toner surface is measured by X-ray photoelectron spectroscopy under the following conditions. Then, the fluorine atom concentration is obtained from the toner before and after the treatment, and the liberation rate of the fluorine resin fine particles is calculated by the following formula 1.

-Measurement of fluorine atom concentration-
The fluorine atom concentration was measured by X-ray photoelectron spectroscopy (XPS) under the following conditions. The result obtained is atomic% (number of atoms%). Note that the region of the extreme surface is about several nm from the toner surface.
Apparatus: 1600S type X-ray photoelectron spectrometer manufactured by PHI X-ray source: MgKα (400 W)
Analysis area: 0.8mm x 2.0mm
Pretreatment: The sample was packed in an aluminum pan and measured by adhering to a sample holder with a carbon sheet.
Surface atom concentration calculation: Relative sensitivity factor provided by PHI was used.

<Formula 1>
Fluorine resin fine particle release rate (%) = (A / B) × 100
In Formula 1, A represents X-rays after mixing 5 g of toner, 150 ml of 15 mass% NaCl aqueous solution, and 1 ml of surfactant, stirring, and then dispersing with a homogenizer for 30 minutes while maintaining at 40 ° C. This represents the fluorine atom concentration (atomic number%) on the toner surface measured by photoelectron spectroscopy. B represents the fluorine atom concentration (number of atoms%) on the toner surface before the dispersion treatment in A is performed.

-Fluorine resin fine particles-
The fluororesin in the fluororesin fine particles is not particularly limited and can be selected according to the purpose. For example, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl ether copolymer, tetrafluoro Ethylene-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene, chlorotrifluoroethylene-ethylene copolymer, Examples thereof include polyvinylidene fluoride, polyvinyl fluoride, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer represented by the following general formula (1), and a mixture thereof. These may be used alone or in combination of two or more.
However, in said general formula (1), Rf represents a perfluoro group. m and n represent a positive integer.
Among these, the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer represented by the general formula (1) is particularly preferable.

As the fluororesin fine particles, for example, the thermal properties, physical properties, electrical properties, molecular weight, molecular weight distribution, crystallinity, melting point, particle size, etc. of the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer are not particularly limited. However, the volume specific resistance according to ASTM test method D257 (50% RH.235) is 1.0 × 10 ¹⁸ (Ω · cm) or more. In view of the charge imparting function, those are preferred.
The number average particle size of primary particles of the fluororesin fine particles is preferably 5 to 2,000 nm, more preferably 20 to 200 nm. When the number average particle size is less than 5 nm, the electrification distribution expected for the fluororesin fine particles tends to be broad and background fogging may occur. When the number average particle size exceeds 2,000 nm, the fluororesin fine particles become a toner base. It may be easily detached from the particles, and the photoreceptor may be contaminated.
Here, the number average particle diameter of the primary particle of the fluororesin fine particles can be measured by, for example, a nanotrack particle size analyzer manufactured by Nikkiso Co., Ltd.

  The addition amount of the fluororesin fine particles is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the toner base particles. When the addition amount of the fluororesin fine particles is less than 0.05 parts by mass, the charge holding function may not be sufficiently exhibited, and when it exceeds 10 parts by mass, problems such as fixing problems may occur.

As the charge control agent, in addition to the fluororesin fine particles, other charge control agents may be included in the kneading step (including the raw material mixing step before kneading) as necessary, and the photosensitive member is charged. Depending on whether the charge is positive or negative, a positive or negative charge control agent can be appropriately selected and used.
As the negative charge control agent, for example, a resin or compound having an electron donating functional group, an azo dye, a metal complex of an organic acid, or the like can be used. Specifically, Bontron (product numbers: S-31, S-32, S-34, S-36, S-37, S-39, S-40, S-44, E-81, E-82, E -84, E-86, E-88, A, 1-A, 2-A, 3-A) (above, manufactured by Orient Chemical Industry Co., Ltd.)), Kaya Charge (part numbers: N-1, N-2), Kaya Set Black (Part No .: T-2, 004) (Nippon Kayaku Co., Ltd.), Eisenspiron Black (T-37, T-77, T-95, TRH, TNS-2) FCA-1001-N, FCA-1001-NB, FCA-1001-NZ (manufactured by Fujikura Kasei Co., Ltd.), and the like.
As the positive charge control agent, for example, a basic compound such as a nigrosine dye, a cationic compound such as a quaternary ammonium salt, a metal salt of a higher fatty acid, or the like can be used. Specifically, Bontron (part numbers: N-01, N-02, N-03, N-04, N-05, N-07, N-09, N-10, N-11, N-13, P -51, P-52, AFP-B) (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415, TP-4040 (above, manufactured by Hodogaya Chemical Co., Ltd.), Copy Blue PR, Copy Charge ( Product number: PX-VP-435, NX-VP-434) (manufactured by Hoechst), FCA (Product number: 201, 201-B-1, 201-B-2, 201-B-3, 201-PB, 201-PZ, 301) (above, manufactured by Fujikura Kasei Co., Ltd.), PLZ (product numbers: 1001, 2001, 6001, 7001) (above, manufactured by Shikoku Kasei Kogyo Co., Ltd.), and the like.
These may be used alone or in combination of two or more.

-Average circularity of toner-
The toner has an average circularity of 0.88 to 0.96, preferably 0.90 to 0.95. When the average circularity is less than 0.88, it may be difficult to obtain a desired charge control agent liberation rate. When the average circularity exceeds 0.96, the toner is substantially heated to realize the pulverized toner. However, in this case, a material with low thermal characteristics is likely to be exposed on the toner surface and the charge control agent attached to the toner surface is difficult to adhere. Problems may occur.
The jet mill pulverization conventionally used has a large pulverization energy due to its structure, and therefore the toner circularity does not substantially exceed 0.88 regardless of the equipment conditions.

Here, the average circularity of the toner can be measured by, for example, a flow type particle image analyzer FPIA-2000 manufactured by Sysmex Corporation.
The toner having a low average circularity, that is, a so-called sharp-angled toner having a rugged toner shape, is easily and selectively attached to the toner at a sharp-angled portion in the stirring and mixing step, and the toner does not uniformly adhere to the toner surface. Therefore, the charge control agent is easily detached. This is considered to be because the sharper portion is more susceptible to mixing energy.
As described above, the method for forming the toner in an obtuse angle can be achieved by, for example, selecting a pulverizer at the time of toner production and appropriately setting the conditions.
Specifically, it is also called a so-called mechanical pulverizer or fluidized bed pulverizer, and the toner particles are pulverized many times with a small pulverization energy, so that a desired average circularity is easily obtained. Examples include a turbo counter jet mill pulverizer manufactured by Turbo Industry Co., Ltd. and a counter jet mill pulverizer manufactured by Hosokawa Micron Corporation.

-Volume average particle size and particle size distribution-
The volume average particle diameter (Dv) of the toner is preferably, for example, 5 to 10 μm, and more preferably 5 to 9 μm.
If the volume average particle size is less than 5 μm, poor cleaning may occur. If the volume average particle size exceeds 10 μm, the reproducibility of the latent image may be inferior, and the image quality may deteriorate.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is, for example, preferably 1.25 or less, more preferably 1.00 to 1.20. .10 to 1.20 is more preferable.
The toner having a particle size of 4 μm or less is preferably 20% by number or less, more preferably 10% by number or less, and further preferably 2 to 8% by number. If the toner having a particle size of 4 μm or less exceeds 20% by number, the toner particle size distribution becomes too wide and charging failure may occur.

  Here, the volume average particle size and the particle size distribution can be measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter.

-Binder resin-
The binder resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and a single substitution product thereof. Polymer: Styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-di Chloromethyl methacrylate copolymer, starene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene -Isoprene copolymer, styrene-acrylonitrile Styrene copolymers such as ru-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic resin, acrylic resin, methacrylic resin, polyacetic acid Vinyl, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, rosin, modified rosin, terpene resin, coumaroindene resin, aliphatic or aliphatic hydrocarbon resin, aromatic petroleum resin Chlorinated paraffin, paraffin wax, and the like. These may be used alone or in combination of two or more.
Among these, polyester resins are particularly preferable from the viewpoints of low-temperature fixability and hot offset properties.

The polyester resin is usually obtained by a polycondensation reaction between a polyhydric alcohol compound and a polycarboxylic acid compound.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO), trihydric or higher polyhydric alcohol (TO), and among these, (DIO) alone or (DIO) and a small amount. A mixture with (TO) of is preferred.

Examples of the dihydric alcohol (DIO) include alkylene glycol (eg, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); Alkylene ether glycol (eg, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol (eg, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.) Bisphenols (eg, bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxides of the above alicyclic diols (eg, ethylene oxide, propylene oxide) Side, butylene oxide, etc.) adducts; alkylene oxide (ethylene oxide of the bisphenols, propylene oxide, and the like butylene oxide, etc.) adducts.
Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferred. Combinations of alkylene oxide adducts of bisphenols and alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Is particularly preferred.

  Examples of the trihydric or higher polyhydric alcohol (TO) include 3 to 8 or higher polyhydric aliphatic alcohols (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); 3 And higher phenols (for example, trisphenol PA, phenol novolac, cresol novolak, etc.); alkylene oxide adducts of the above trivalent polyphenols and the like.

Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC), trivalent or higher polyvalent carboxylic acid (TC), (DIC) alone, and (DIC) and a small amount of (TC). And mixtures thereof are preferred.
Examples of the divalent carboxylic acid (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid). , Terephthalic acid, naphthalenedicarboxylic acid, etc.).
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polyvalent carboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid, pyromellitic acid, etc.). The polyvalent carboxylic acid (PC) may be reacted with polyhydric alcohol (PO) using the above acid anhydrides or lower alkyl esters (eg, methyl ester, ethyl ester, isopropyl ester, etc.). Good.

  The ratio of the polyhydric alcohol (PO) to the polyvalent carboxylic acid (PC) is preferably an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH] of 2/1 to 1/1. 1.5 / 1 to 1/1 are more preferable, and 1.3 / 1 to 1.02 / 1 are particularly preferable.

  The polycondensation reaction between the polyhydric alcohol (PO) and the polycarboxylic acid (PC) is heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the pressure is reduced as necessary. The produced water is distilled off to obtain a polyester resin having a hydroxyl group. The hydroxyl value of the polyester resin is preferably 5 or more. The acid value of the polyester resin is usually preferably from 1 to 30, and more preferably from 5 to 20. By giving an acid value as described above, it becomes easy to be negatively charged, and furthermore, at the time of fixing onto a recording paper, the affinity between the recording paper and the toner is good and the low-temperature fixability is improved. However, when the acid value exceeds 30, there is a tendency to deteriorate with respect to the stability of charging, particularly the environmental fluctuation.

The weight average molecular weight (Mw) of the polyester resin is preferably 10,000 to 400,000, and more preferably 20,000 to 200,000. When the weight average molecular weight is less than 10,000, the offset resistance may be deteriorated, and when it exceeds 400,000, the low-temperature fixability may be deteriorated.
Here, the weight average molecular weight of the polyester resin is measured by, for example, gel permeation chromatography (GPC).

  The binder resin preferably has an acid value of 1 to 35 mgKOH / g, and the glass transition temperature (Tg) of the binder resin is preferably 50 to 70 ° C.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used alone or in combination of two or more.
The content of the colorant in the toner is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.

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

-Release agent-
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
The waxes are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include animal and plant waxes such as rice wax, candelilla wax, carnauba wax, lanolin; paraffin wax, microcrystalline wax, Petroleum and other petroleum wax; low density polyethylene, high density polyethylene, polyethylene copolymer, polypropylene, polypropylene copolymer, acid value-modified polyethylene, acid-modified polyethylene, graft-modified polyethylene with aromatic monomers, pyrolysis-type low Examples thereof include polyolefin waxes such as density polyethylene, pyrolytic polypropylene, and low molecular weight polyethylene. These may be used alone or in combination of two or more. Among these, a polyolefin wax having a softening point of 70 to 150 ° C. by the ring and ball method is preferable, and a polyolefin wax having a softening point of 120 to 150 ° C. is more preferable.

  Moreover, as said wax, a commercial item can be used, for example, HNP (product number: 1, 3, 9, 10, 11, 12), SP (product number: 0145, 1035, 3040, 3035, 0110), Hi. -Mic (part number: 2095, 1080, 3080, 1070, 2065, 1045, 2045), POLYCOAT (part number: 1025, 1455, 2255, 3030, 3155), NEOPALAX (part number: 2545, 3240), PALVAX (part number: 1230, 1335, 1430), CARTOWAX-3025, BONTEX (part numbers: 0011, 2266), S-0750, OX (part numbers: 261BN, 0550, 2251, 1949), NSP-8070, NPS (part numbers: L-70, 6010, 9210) ), HAD (Part No .: 5080, 670), WEISSEN-0453, JP-1500, LUVAX (part number: 1266, 2191, 1151, 0321), EMUSTAR (part number: 0001, 042X, 0135, 0136, 0164, 358) (manufactured by Nippon Wax Co., Ltd.), High wax (Part No .: 800P, 400P, 200p, 100P, 720P, 410P, 420P, 320P, 210P, 220P, 110P, 405MP, 310MP, 320MP, 210MP, 220MP, 4051E, 4052E, 4202E, 1105A, 2203A, 1120H, 1140H 1160H, NL100, NL200, NL500, NL800, NP055, NP105, NP505, NP805) (manufactured by Mitsui Petrochemical Co., Ltd.) and the like can be used.

  The melting point of the wax is preferably 40 to 120 ° C, more preferably 50 to 110 ° C. When the melting point of the wax is higher than 120 ° C., the fixability at a low temperature may be insufficient, and when it is lower than 40 ° C., the offset resistance and durability may be lowered. The melting point of the wax can be determined by differential scanning calorimetry (DSC). For example, the melting peak value when a sample of several mg is ripened at a constant heating rate, for example, (10 ° C./min) is obtained. The melting point.

  The addition amount of the wax as the release agent is preferably 2 to 7 parts by mass with respect to 100 parts by mass of the binder resin. If the addition amount is less than 2 parts by mass, sufficient releasability cannot be exhibited, and hot offset may occur at the time of toner fixing. If the addition amount exceeds 7 parts by mass, too much wax will come out on the toner surface. As a result, the wax content in the toner fine powder increases, and as a result, the variation in glossiness of the visible image (toner image) may increase. Moreover, when there is too much content of wax, hot offset may generate | occur | produce.

  In addition to the above charge control agent, the toner of the present invention may further contain other external additives in order to improve fluidity. The other external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. Examples thereof include inorganic fine particles and organic fine particles, and inorganic fine particles are particularly preferable. .

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, Wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and those hydrophobized. Can be mentioned. Of these, silica, titanium oxide, and hydrophobized titanium oxide are particularly preferable.

Examples of the silica fine particles include HDK H2000, HDK H2000 / 4, HDK H2050EP, HVK21, and HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, and R812 (all Nippon Aerosil Co., Ltd.) Company-made).
Examples of the titanium oxide fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.). MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like.
Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF- 1500T (all manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (all manufactured by Teika Co., Ltd.); IT-S (manufactured by Ishihara Sangyo Co., Ltd.).

The hydrophobized inorganic fine particles are, for example, silica fine particles, titania fine particles, alumina fine particles, etc., and hydrophilic fine particles are treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. Further, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino acid. Modified silicone oil, epoxy modified silicone oil, epoxy / polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, acrylic modified silicone oil, methacryl modified silicone oil, α-methylstyrene modified silicone oil, etc. Can be used.

The volume average particle size of primary particles of the inorganic fine particles is preferably 0.005 to 1.0 μm, and more preferably 0.01 to 0.5 μm. When the volume average particle size is less than 0.005 μm, the inorganic fine particles are easily embedded in the toner base particles, and thus sufficient fluidity and chargeability may not be obtained, which exceeds 1.0 μm. And sufficient fluidity may not be obtained.
The addition amount of the inorganic fine particles is preferably 0.01 to 5% by mass and more preferably 0.01 to 2% by mass with respect to the toner.

  The organic fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, methacrylate ester copolymer, acrylic ester Examples include copolymers, polycondensation systems such as silicone, benzoguanamine, and nylon, and polymer particles made of thermosetting resin.

  Further, the toner of the present invention may contain a cleaning property improving agent in order to remove the transferred developer remaining on the photoreceptor or the primary transfer medium. Examples of such a cleaning improver include fatty acid metal salts such as zinc stearate and calcium stearate, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene 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 production method)
The toner manufacturing method of the present invention includes a melt-kneading step, a toner base particle manufacturing step, and a mechanical mixing step, and further includes other steps as necessary.

The melt-kneading step is a step of melting and kneading a toner material containing at least a binder resin and a colorant.
The toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial continuous kneader, a biaxial continuous kneader, or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay, PCM type twin screw extruder manufactured by Ikegai Iron Works Co., Ltd. Preferably used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature is performed with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

The toner base particle manufacturing step is a step of manufacturing toner base particles by pulverizing and classifying the obtained melt-kneaded product.
In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing in a narrow gap between a rotor and a stator that rotate mechanically is preferably used. For example, a turbo counter jet mill pulverizer (manufactured by Turbo Industry Co., Ltd.), a counter jet mill (manufactured by Hosokawa Micron Co., Ltd.) and the like are suitable.
In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like. For example, an air classification by a swirling flow (DS classifier, manufactured by Nippon Pneumatic Industry Co., Ltd.) is suitable. is there.
After the pulverization and classification are completed, the pulverized product is classified in an air stream by centrifugal force or the like to produce a toner having a predetermined particle size.

The mechanical mixing step is a step of adding fluorine resin fine particles to the obtained toner base particles and mechanically mixing them.
For the mixing, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer.

The toner is preferably a negatively chargeable toner from the viewpoint of combination with a photoreceptor constituting a recent digital copying machine system.
The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

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

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

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

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D50)) of 10 to 200 μm, and more preferably 40 to 100 μm.
When the average particle size (volume average particle size (D50)) is less than 10 μm, in the distribution of carrier particles, there are many fine powder systems, and the magnetization per particle may be lowered, causing carrier scattering, If it exceeds 200 μm, the specific surface area may decrease and toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be particularly poor.

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

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

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

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

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.
In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 1 to 10.0 parts by mass, more preferably 0.5 to 6.0 parts by mass with respect to 100 parts by mass of the carrier.

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

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

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

Here, for example, as shown in FIG. 1, the process cartridge includes a photoreceptor 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and other units as necessary. It has. In FIG. 1, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.
As the photoreceptor 101, the same one as an image forming apparatus described later can be used. An arbitrary charging member is used for the charging means 102.
Next, the image forming process using the process cartridge shown in FIG. 1 will be described. The photoconductor 101 is charged on the surface by charging by the charging means 102 and exposure 103 by the exposure means (not shown) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the exposure image is formed. The electrostatic latent image is developed with toner by the developing unit 104, and the toner development is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  The image forming apparatus of the present invention is constructed by integrally combining the electrostatic latent image carrier and the components such as a developing device and a cleaning device as a process cartridge, and this unit can be attached to and detached from the apparatus main body. It may be configured. In addition, at least one selected from a charging device, a developing device, a transfer device, and a cleaning device is integrally supported together with an electrostatic latent image carrier to form a process cartridge, which is a single unit that can be attached to and detached from the apparatus main body. Further, it may be configured to be detachable using guide means such as a rail of the apparatus main body.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention comprises at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, a fixing unit, and a cleaning unit, and further if necessary. And other means appropriately selected, for example, static elimination means, recycling means, control means, and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, a fixing step, and a cleaning step, and further other steps appropriately selected as necessary, for example, static elimination. Process, recycling process, control process and so on.

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

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The material, shape, structure, size, etc. of the electrostatic latent image carrier are not particularly limited, and can be appropriately selected from known ones. The shape is preferably a drum shape. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon and the like are preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method, or the like is applied on the support. A photoconductor having a photoconductive layer made of a-Si (hereinafter sometimes referred to as “a-Si-based photoconductor”) can be used. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

The electrostatic latent image can be formed, for example, by charging the surface of the electrostatic latent image carrier and then exposing it like an image, and by the electrostatic latent image forming means. .
The electrostatic latent image forming unit includes, for example, at least a charger that charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise.

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

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

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

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

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

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

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

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

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

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

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

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

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

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

  Next, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) onto a transfer sheet 95 as a final recording medium. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

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

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. A tandem image forming apparatus 100 shown in FIG. 4 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 4. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22.
In the tandem image forming apparatus 100, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

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

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

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image-corresponding image (L in FIG. 5), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. Developing with color toner (black toner, yellow toner, magenta toner and cyan toner) to form a toner image with each color toner, and intermediate transfer of the toner image 50 includes a transfer charger 62 for transferring the toner image on the toner image 50, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

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

  Since the image forming method and the image forming apparatus of the present invention use the toner of the present invention, which is excellent in toner charge rising property and OPC contamination, has a high image density, and can obtain a high-quality image with little background stains. A high-quality image can be efficiently formed over a long period of time.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.

Example 1
-Preparation of black toner (BK1)-
1200 parts of water and 540 parts of carbon black (MA60, manufactured by Mitsubishi Chemical Corporation) were thoroughly stirred with a flasher. To this, 1,200 parts of polyester resin (acid value = 3, hydroxyl value = 25, number average molecular weight (Mn) = 4,500, Mw / Mn = 4.0, glass transition temperature (Tg) = 60 ° C.) In addition, after kneading at 150 ° C. for 30 minutes, 1,000 parts of xylene was added and kneaded for 1 hour. Subsequently, after removing water and xylene, it was rolled and cooled, and pulverized with a pulverizer to prepare a master batch pigment (MB-1).

  Next, 600 parts of water and C.I. I. Pigment Blue 15: 3 water-containing cake (solid content 50%) 1,200 parts was thoroughly stirred with a flasher. To this, 1,200 parts of polyester resin (acid value = 3, hydroxyl value = 25, number average molecular weight (Mn) = 4,500, Mw / Mn = 4.0, glass transition temperature (Tg) = 60 ° C.) In addition, after kneading at 150 ° C. for 30 minutes, 1,000 parts of xylene was added. Next, the mixture was kneaded for 1 hour, water and xylene were removed, rolled and cooled, pulverized with a pulverizer, and further passed twice with a three-roll mill to prepare a master batch pigment (MB-2).

Next, 100 parts of polyester resin (acid value = 3, hydroxyl value = 25, number average molecular weight (Mn) = 4,500, Mw / Mn = 4.0, glass transition temperature (Tg) = 60 ° C.), master 5 parts of the batch (MB-1) and 0.5 part of the master batch (MB-2) were mixed with a mixer, then melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. Next, a turbo counter jet mill crusher (manufactured by Turbo Kogyo Co., Ltd., rotating blade rotation speed = 7,500 rpm, feed amount = 1.2 kg / hr) and wind classifying by swirling flow (DS classifier, Nippon Pneumatic Industrial Co., Ltd.) The toner base particles were prepared by pulverization and classification.
The obtained toner base particles had a volume average particle size of 9.1 μm and 14.5% by number of particles having a particle size of 4 μm or less.

  Next, with respect to 100 parts by mass of the obtained toner base particles, 0.9 parts by mass of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer having a number average particle size of 0.15 μm of primary particles, hydrophobic silica (H2000, Clariant). (Made in Japan) 0.5 parts by weight was added and mixed at 6,000 rpm for 10 minutes while heating at an appropriate temperature using a Q mixer (Mitsui Mining Co., Ltd.). BK1) was produced.

(Example 2)
-Production of yellow toner (Y1)-
600 parts of water, and C.I. I. 1,200 parts of Pigment Yellow 17 water-containing cake (solid content 50%) was thoroughly stirred with a flasher. Here, 1,200 parts of polyester resin (acid value = 3, hydroxyl value = 25, number average molecular weight (Mn) = 4,500, Mw / Mn = 4.0, glass transition temperature (Tg) = 60 ° C.) In addition, after kneading at 150 ° C. for 30 minutes, 1,000 parts of xylene was added and kneaded for 1 hour. Next, after removing water and xylene, the product was cooled by rolling, pulverized with a pulverizer, and further passed twice with three rolls to prepare a master batch pigment.

Next, 100 parts of a polyester resin (acid value = 3, hydroxyl value = 25, number average molecular weight (Mn) = 4,500, Mw / Mn = 4.0, glass transition temperature (Tg) = 60 ° C.), and the above After mixing 5 parts of the master batch with a mixer, the mixture was melt-kneaded with a two-roll mill, and the resulting kneaded product was rolled and cooled. Next, the mixture is pulverized by a turbo counter jet mill pulverizer (manufactured by Turbo Kogyo Co., Ltd., rotating blade rotation speed = 7700 rpm, feed amount = 1.3 kg / hr), and air classification of the same apparatus as in Example 1 is performed to obtain a toner base. Particles were made.
The obtained toner base particles had a volume average particle size of 5.5 μm and 8% by number of particles having a particle size of 4 μm or less.

  Next, with respect to 100 parts by mass of the obtained toner base particles, 1.1 parts by mass of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer having a number average particle size of 0.2 μm of primary particles, hydrophobic silica (H2000, Clariant). 0.5 parts by mass (Japan) was added, and the mixture was mixed at 6,000 rpm for 10 minutes while heating at an appropriate temperature using a Q mixer (Mitsui Mining Co., Ltd.). Y1) was prepared.

(Example 3)
-Preparation of magenta toner (M1)-
600 parts of water, and C.I. I. 1,200 parts of Pigment Red 57-1 water-containing cake (solid content 50%) was thoroughly stirred with a flasher. Here, 1,200 parts of polyester resin (acid value = 3, hydroxyl value = 25, number average molecular weight (Mn) = 4500, Mw / Mn = 4.0, glass transition temperature (Tg) = 60 ° C.) was added, After kneading at 150 ° C. for 30 minutes, 1,000 parts of xylene was added. Next, after kneading for 1 hour, water and xylene were removed, the product was cooled by rolling, pulverized with a pulverizer, and further passed twice with a three-roll mill to prepare a master batch pigment.

Next, 100 parts of polyester resin (acid value = 3, hydroxyl value = 25, number average molecular weight (Mn) = 4500, Mw / Mn = 4.0, glass transition temperature (Tg) = 60 ° C.), and the masterbatch After mixing 5 parts with a mixer, it was melt-kneaded with a two-roll mill. The obtained kneaded product was rolled and cooled, pulverized with a counter jet mill (feed amount = 1.3 kg / hr) manufactured by Hosokawa Micron Co., Ltd., and air classification was performed with the same apparatus as in Example 1 to prepare toner base particles. .
The obtained toner base particles had a volume average particle size of 9.1 μm and 16.3% by number of particles having a particle size of 4 μm or less.

  Next, with respect to 100 parts by mass of the obtained toner base particles, 1.2 parts by mass of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer having a number average particle size of 0.15 μm of primary particles, hydrophobic silica (H2000, Clariant). (Made in Japan) 0.2 parts by weight was added and mixed at 6,000 rpm for 10 minutes while heating at an appropriate temperature using a Q mixer (Mitsui Mining Co., Ltd.). M1) was prepared.

Example 4
-Production of cyan toner (C1)-
600 parts of water, and C.I. I. Pigment Blue 15: 3 water-containing cake (solid content 50%) 1,200 parts was thoroughly stirred with a flasher. Here, 1,200 parts of polyester resin (acid value = 3, hydroxyl value = 25, number average molecular weight (Mn) = 4,500, Mw / Mn = 4.0, glass transition temperature (Tg) = 60 ° C.) In addition, after kneading at 150 ° C. for 30 minutes, add 1,000 parts of xylene, knead for another hour, remove water and xylene, cool by rolling, pulverize with a pulverizer, and further pass two times with a three-roll mill. A master batch pigment was prepared.

Next, 100 parts of polyester resin (acid value = 3, hydroxyl value = 25, number average molecular weight (Mn) = 4,500, Mw / Mn = 4.0, glass transition temperature (Tg) = 60 ° C.), master 3 parts of a batch pigment and 0.5 part of a quaternary ammonium salt compound as a secondary charge control agent were mixed with a mixer and then melt-kneaded with a two-roll mill. The obtained kneaded product was rolled and cooled, and pulverized with a turbo counter jet mill pulverizer (manufactured by Turbo Kogyo Co., Ltd., rotating blade rotation speed = 8500 rpm, feed amount = 2.0 kg / hr), and the same apparatus as in Example 1 Was used to classify the air to produce toner base particles.
The obtained toner base particles had a volume average particle size of 9.0 μm and 15.5% by number of particles having a particle size of 4 μm or less.

  Next, with respect to 100 parts by mass of the obtained toner base particles, 1.0 part by mass of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer having a number average particle size of 0.15 μm of primary particles, hydrophobic silica (H2000, Clariant). (Japan Co., Ltd.) 0.2 parts by mass was added and mixed at 6,000 rpm for 10 minutes while heating at an appropriate temperature using a Q mixer (Mitsui Mining Co., Ltd.). C1) was produced.

(Comparative Example 1)
-Production of black toner (bk1)-
In Example 1, except that the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer was changed to a zinc salicylate derivative (Bontron E84, manufactured by Orient Chemical Co., Ltd.), the black toner (bk1) was prepared in the same manner as in Example 1. Produced.

(Comparative Example 2)
-Production of yellow toner (y1)-
In Example 2, the yellow toner (y1) was prepared in the same manner as in Example 2 except that the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer was changed to a zinc salicylate derivative (Bontron E84, manufactured by Orient Chemical Co., Ltd.). Produced.

(Comparative Example 3)
-Production of magenta toner (m1)-
In Example 3, except that the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer was changed to a zinc salicylate derivative (Bontron E84, manufactured by Orient Chemical Co., Ltd.), magenta toner (m1) was prepared in the same manner as in Example 3. Produced.

(Comparative Example 4)
-Production of cyan toner (c1)-
In Example 4, except that the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer was changed to a zinc salicylate derivative (Bontron E84, manufactured by Orient Chemical Co., Ltd.), cyan toner (c1) was prepared in the same manner as in Example 4. Produced.

(Comparative Example 5)
-Preparation of black toner (bk2)-
In Example 1, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and hydrophobic silica were mixed with a Q mixer (manufactured by Mitsui Mining Co., Ltd.) at a rotational speed of 3,000 rpm for 10 minutes. Thus, a black toner (bk2) was produced.

(Comparative Example 6)
-Production of black toner (bk3)-
In Example 1, the toner pulverizer was changed to a so-called jet mill pulverizer of IDS-2 type (feed amount = 1.6 kg / hr) manufactured by Nippon Pneumatic Industry Co., Ltd. A black toner (bk3) having a volume average particle diameter of 6 μm and a particle diameter of 4 μm or less of 12% by number was prepared.

  Next, for each of the obtained toners, the volume average particle diameter (Dv), the proportion of particles having a particle diameter of 4 μm or less, the average circularity, and the liberation rate of the fluororesin fine particles were measured as follows. The results are shown in Table 1.

<Volume average particle diameter (Dv) and ratio of particles having a particle diameter of 4 μm or less>
The volume average particle size and particle size distribution of the toner were measured using a particle size measuring device (“Coulter Counter TAII”, manufactured by Coulter Electronics Co., Ltd.) under the condition of an aperture diameter of 100 μm.

<Measurement of liberation rate of fluororesin fine particles>
5 g of each toner toner obtained, 150 ml of an electrolyte adjusted to 15% NaCl, and 1 ml of a surfactant were mixed and then stirred well. The solution was dispersed at a temperature of 40 ° C. for 30 minutes using a homogenizer. The homogenizer conditions are arbitrarily adjusted according to the type of toner.
The obtained dispersion was vacuum filtered, dried at an appropriate temperature, and then the concentration of fluorine atoms contained in the charge control agent on the toner surface was measured by X-ray photoelectron spectroscopy under the following conditions. The fluorine atom concentration was calculated from the toner before and after the treatment, and the liberation rate of the fluorine resin fine particles was calculated by the following formula 1.
-Measurement of fluorine atom concentration-
The fluorine atom concentration was measured by X-ray photoelectron spectroscopy (XPS) under the following conditions. The result obtained is atomic% (number of atoms%). Here, it is the region of the extreme surface about several nm from the toner surface.
Apparatus: 1600S type X-ray photoelectron spectrometer manufactured by PHI X-ray source: MgKα (400 W)
Analysis area: 0.8mm x 2.0mm
Pretreatment: The sample was packed in an aluminum pan and measured by adhering to a sample holder with a carbon sheet.
Surface atom concentration calculation: Relative sensitivity factor provided by PHI was used.

<Formula 1>
Fluorine resin fine particle release rate (%) = (A / B) × 100
In Formula 1, A represents X-ray photoelectrons after mixing 5 g of toner, 150 ml of a 15% by weight NaCl aqueous solution, and 1 ml of a surfactant, and after stirring and dispersing for 30 minutes with a homogenizer while maintaining the temperature at 40 ° C. This represents the fluorine atom concentration (number of atoms%) on the toner surface measured by spectroscopy. B represents the fluorine atom concentration (number of atoms%) on the toner surface before the processing in A.

<Measurement of average circularity>
About each obtained toner, it measured on condition of the following using the flow type particle image analyzer (The Sysmex Corporation make, FPIA-2000).
〔Measurement condition〕
・ Dispersed medium: Cell sheath ・ Measurement mode: LPF → HPF
・ Analysis conditions Particle size cumulative frequency: Upper (predetermined value No. 12)% diameter, Lower (predetermined value No. 13)% diameter ・ Dilution ratio: 1.00 times

-Preparation of developer-
Next, 95 parts of a carrier in which Cu—Zn ferrite having a volume average particle size of 50 μm was coated with a silicone resin was mixed with 5 parts of each obtained toner to prepare each developer.

  Using each developer thus obtained, matting evaluation of 500,000 sheets was performed as follows, and OPC contamination, toner charging stability with time of the developing portion, image density, and background contamination were evaluated. The results are shown in Table 2.

<OPC contamination>
For each developer, using a modified machine of an image forming apparatus (manufactured by Ricoh Co., Ltd., Imagio NEO C385), 10,000 images are put out, and the surface of the photoconductor after 10,000 sheets is finished with a microscope with a magnification of 1,000. Observation was performed, and the filming due to the toner on the photosensitive member was evaluated for rank and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Very good ○: Good △: Deteriorated ×: Not practical

<Toner charging stability of developing part over time>
For each developer, the image forming apparatus (Imagio NEO C385, manufactured by Ricoh Co., Ltd.) was used to perform 10,000 image extraction, and the difference in charge amount between the initial image extraction and the end of 10,000 image acquisition The rank was evaluated from the toner density at that time, and the evaluation was performed according to the following criteria.
〔Evaluation criteria〕
○: Good △: Bad ×: Not practical

<Image density>
For each developer, an image forming apparatus (Imagio Color 2800, manufactured by Ricoh Co., Ltd.) was used, and the amount of each developer adhered to plain paper (TYPE 6200, manufactured by Ricoh Co., Ltd.) was 1.00 ± 0.1 mg / cm ^2. The solid image was formed at a surface temperature of the fixing roller of 160 ± 2 ° C. The image density of arbitrary five places in the obtained solid image was measured using a spectrometer (938 Spectrodensitometer, manufactured by X-Rite). The image density value is shown as an average value of image densities at five locations. Note that the higher the obtained image density value, the higher the image density and the higher the density image can be formed.

<Soil dirt>
For each developer, an image forming apparatus (Imagio Color 2800, manufactured by Ricoh Co., Ltd.) is used to stop the blank image during development, and the developer on the photoconductor after development is transferred to tape, and the image of the untransferred tape The difference from the concentration was measured with a spectrometer (“938 Spectrodensitometer”, manufactured by X-Light).

  From the results of Tables 1 and 2, Examples 1 to 4 in which the average circularity of the toner is 0.88 to 0.96 and the liberation rate of the fluororesin fine particles is 60 to 99% are shown in Comparative Example 1. It was confirmed that in all cases, no OPC contamination occurred, the charging stability was excellent, the image density was high, and high-quality image formation with no background staining could be performed.

The toner of the present invention is excellent in toner charge rise and OPC contamination by controlling the liberation rate of fluororesin fine particles from the toner surface within a predetermined range, and has high image density and low background stain. Therefore, it is preferably used for high-quality image formation.
The developer, toner-containing container, process cartridge, image forming apparatus, and image forming method of the present invention using the toner of the present invention are suitably used for high-quality image formation.

FIG. 1 is a schematic view showing an example of the process cartridge of the present invention. FIG. 2 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 3 is a schematic view showing another example of the image forming apparatus of the present invention. FIG. 4 is a schematic view showing an example of the tandem type image forming apparatus of the present invention. FIG. 5 is a partially enlarged view of FIG.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developer 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Development roller Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Ejection Roller 57 Discharge tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 101 Photoconductor 102 Charging means 103 Exposure Means 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 110 Belt type image fixing device 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed capacity Set 145 Separating roller 146 Feeding path 147 Conveying roller 148 Feeding path 150 Copying device main body 200 Feeding table 210 Image fixing device 220 Heating roller 230 Pressure roller 300 Scanner 400 Automatic document feeder (ADF)

Claims (13)

A toner containing toner base particles containing at least a binder resin and a colorant, and fluorine resin fine particles,
A toner having an average circularity of 0.88 to 0.96 and a liberation rate of fluororesin fine particles represented by the following formula 1 in the toner of 60 to 99%.
<Formula 1>
Fluorine resin fine particle release rate (%) = (A / B) × 100
In Formula 1, A represents X-rays after mixing 5 g of toner, 150 ml of 15 mass% NaCl aqueous solution, and 1 ml of surfactant, stirring, and then dispersing with a homogenizer for 30 minutes while maintaining at 40 ° C. This represents the fluorine atom concentration (atomic number%) on the toner surface measured by photoelectron spectroscopy. B represents the fluorine atom concentration (number of atoms%) on the toner surface before the dispersion treatment in A is performed. The toner according to claim 1, wherein the fluororesin fine particles are a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer represented by the following general formula (1).
However, in said general formula (1), Rf represents a perfluoro group. m and n represent a positive integer.   The toner according to claim 2, wherein the fluorine-based resin fine particles have a number average particle diameter of primary particles of 5 to 2,000 nm.   The toner according to claim 1, wherein the binder resin is a polyester resin.   The toner according to claim 1, wherein the toner is a negatively chargeable toner.   The toner according to claim 1, wherein the toner has a volume average particle diameter of 5 to 10 μm and a toner having a particle diameter of 4 μm or less is 20% by number or less. A melt-kneading step of melting and kneading a toner material containing at least a binder resin and a colorant;
A toner base particle manufacturing step of pulverizing and classifying the obtained melt-kneaded product to manufacture toner base particles;
And a mechanical mixing step of adding fluorine resin fine particles to the obtained toner base particles and mechanically mixing the toner base particles.   The method for producing a toner according to claim 7, wherein 0.1 to 10 parts by mass of fluororesin fine particles are added to 100 parts by mass of the toner base particles and mechanically mixed.   A developer comprising the toner according to claim 1.   A toner-filled container filled with the toner according to claim 1.   An electrostatic latent image carrier, and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to claim 1 to form a visible image. A process cartridge having at least   An electrostatic latent image forming step for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image is developed using the toner according to any one of claims 1 to 6 to form a visible image. An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium. An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of claims 1 to 6. At least developing means for forming a visible image by developing the toner, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. An image forming apparatus.