JP2006058502A - Toner and developer for electrostatic image development, image forming apparatus, process cartridge using the same and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer and toner having good charging property and charge buildup performance of the toner and free of toner spent on a carrier, etc., and filming on a photoreceptor, to provide a developer and toner adaptable to a low temperature fixing system and having good offset resistance while maintaining cleanability, and to provide an image forming apparatus and an image forming method. <P>SOLUTION: In the toner for electrostatic image development including at least toner particles and inorganic fine particles, the inorganic fine particles consist of at least two kinds of inorganic fine particles and at least silica and titanium oxide are included as the inorganic fine particles. When ultrasonic vibration (output: 20 W, frequency: 20 kHz) is applied to the toner for 1 min, an attachment rate of the titanium oxide attached to the toner particles is ≥75 wt.% of that before applying the ultrasonic vibration, an attachment rate of the silica is ≤85 wt.% of that before applying the ultrasonic vibration, and the attachment rate of the titanium oxide is higher than that of the silica. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrostatic charge image developing toner and developer, an image forming apparatus and an image forming method, and a process cartridge using the same.

  In electrophotographic devices and electrostatic recording devices, toner is attached to an electrostatic latent image formed on a photoreceptor, transferred to a transfer material, and then fixed to the transfer material by heat to form a toner image. is doing. Also, full-color image formation is generally performed by using four color toners of black, yellow, magenta, and cyan. Each toner is developed and each toner layer is superimposed on a transfer material. To obtain a full-color image.

  However, for users who are familiar with printing in general, images on full-color copiers are not yet satisfactory, and there is a demand for higher image quality that satisfies photography, high-definition, and high resolution. It is known to use a toner having a small particle size and a narrow particle size distribution to improve the image quality.

Conventionally, an electrical or magnetic latent image has been visualized with toner. Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventing agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner.
On the other hand, in the polymerization method, for example, a suspension polymerization method described in Patent Document 1 and a method of obtaining resin particles obtained by associating resin fine particles obtained by an emulsion polymerization method described in Patent Document 2 are described in Patent Document 3. The toner is manufactured by the dissolution suspension method (EA; Emulsion-Aggregation method).
For the purpose of improving the flow characteristics and charging characteristics of toners produced by these various methods, methods for mixing toner particles with inorganic powders such as various metal oxides have been proposed. is called. If necessary, the surface of the inorganic powder may be treated with a specific silane coupling agent, titanate coupling agent, silicone oil, organic acid, etc., or a specific resin may be coated to improve the hydrophobicity or charging characteristics of the surface of the inorganic powder. A method to do this has also been proposed. As the inorganic powder, for example, silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide, tin oxide and the like are known. In particular, silica particles obtained by reacting silica or titanium oxide fine particles with an organosilicon compound such as dimethyldichlorosilane, hexamethyldisilazane, or silicone oil to replace the silanol groups on the surface of the silica fine particles with organic groups to make them hydrophobic are used.
Further, for example, Patent Documents 4 and 5 disclose ones in which the adhesion state of the external additive with the toner is set to a specific state.
However, it is stable and free of filming while supporting the reduction of the toner particle size by further improving the image quality and the low molecular weight of the toner resin design by energy saving fixing in response to environmental demands. In order to perform development and transfer, these techniques are still insufficient, and improvement is required.

Japanese Patent Laid-Open No. 9-43909 Japanese Patent No. 2537503 Japanese Patent No. 3141784 JP 2000-122336 A Japanese Patent No. 3129074

An object of the present invention is to provide the following stably even after outputting tens of thousands of images.
(1) To provide a toner, an image forming apparatus, and an image forming method that do not cause filming on a latent image carrier (typically on a photoconductor) and perform stable development and transfer.
(2) The charging ability of the toner is sufficiently high, the charging start-up property is good, and even if tens of thousands of images are output, the toner spent on the carrier is small, and high chargeability and fluidity can be maintained and sufficient It is an object of the present invention to provide a developer and a toner capable of obtaining an image density having an image density.
(3) To provide a developer and a toner that are compatible with a low-temperature fixing system while maintaining cleaning properties, have good offset resistance, and do not contaminate the fixing device and the image.

The inventors of the present invention have studied the above problems and have arrived at the present invention.
That is, the above-mentioned problem is (1) “in the electrostatic image developing toner particles containing at least a binder resin and a colorant, and in the electrostatic image developing toner containing at least inorganic fine particles. It consists of at least two types of inorganic fine particles, contains at least silica and titanium oxide as the inorganic fine particles, and adheres to the toner particles when ultrasonic vibration (output 20 W, frequency 20 KHz) is applied to the toner for 1 minute. Titanium oxide adhesion rate is 75% by weight or more before applying ultrasonic vibration, silica adhesion rate is 85% by weight or less before applying ultrasonic vibration, and titanium oxide adhesion rate> silica adhesion rate. (2) “Upper limit of titanium oxide adhesion rate after application of ultrasonic vibration is 98% by weight or less before applying ultrasonic vibration. The electrostatic charge image developing toner according to item (1) above, (3) “the lower limit of silica adhesion after applying ultrasonic vibration is 50% by weight or more before applying ultrasonic vibration” (4) “silica having an average primary particle size of at least 80 nm to 500 nm as the inorganic fine particles”, wherein the toner for developing an electrostatic charge image according to the above item (1) or (2) is characterized by The toner for developing an electrostatic charge image according to any one of items (1) to (3) ”, (5)“ further containing wax (1) to (5), wherein the toner is an electrostatic charge image developing toner according to any one of items (1) to (4), and (6) the wax is carnauba wax. Or the toner for developing an electrostatic image according to any one of (7) The toner for developing an electrostatic charge image according to (5) or (6) above, wherein the content of the toner in the toner is 5% by weight or more, (8) “Volume of the toner” the average particle diameter _{D V} is 4-8 [mu] m, the first (1) the ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn is characterized in that it is a 1.00 to 1.25 claim to The toner for developing an electrostatic charge image according to any one of Items (7), (9) “The fine powder having a volume average particle size of 3 μm or less is 10% or less”. (8) Item (1) to Item (9), wherein the electrostatic image developing toner according to any one of Items (10) and (10) “Circularity is 0.92 to 0.98”. The electrostatic charge image developing toner according to any one of the items is solved.
In addition, the above-mentioned problem is characterized by comprising the electrostatic charge image developing toner according to any one of (11) and (1) to (10) of the present invention and a carrier comprising magnetic particles. This is solved by a “two-component developer for developing electrostatic image”.
Further, the above-mentioned problems are solved by (12) “developing means for developing an electrostatic latent image formed on an image carrier with a developer containing toner, and toner formed on the image carrier. Fixing means for fixing the toner image, comprising: a transfer means for transferring an image onto an image support; a heating rotator having a heating member; and a pressure rotator arranged to face the heating rotator. In the image forming apparatus, the toner for developing an electrostatic image according to any one of the items (1) to (10) is used. ”(13) The fixing unit includes a heating body provided with a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and between the film and the pressure member Pass the recording material on which the toner image is formed on (14) “The heating member of the fixing device is made of a magnetic metal and is heated by electromagnetic induction, which is a fixing device for fixing”. This is solved by the image forming apparatus according to item (12) or (13).
Further, the above-mentioned problem is solved by (15) “Image forming method according to item (14), wherein the electromagnetic induction generating means is provided outside the heating rotator” of the present invention. The
In addition, the above-described problem is solved by (16) “having a photoreceptor and a developing unit, and further integrally supporting at least one unit selected from a charging unit and a cleaning unit. In the detachable process cartridge, the developing means includes toner, and the toner is the electrostatic image developing toner according to any one of the items (1) to (10). Is solved by a process cartridge.

The present invention has the following effects.
(1) It is possible to provide a toner, an image forming apparatus, and an image forming method that do not cause filming on a latent image carrier (typically, a photoreceptor) and perform stable development and transfer.
(2) The charging ability of the toner is sufficiently high, the charging start-up property is good, and even if tens of thousands of images are output, the toner spent on the carrier is small, and high chargeability and fluidity can be maintained and sufficient It is possible to provide a developer and a toner capable of obtaining an image density having an image density.
(3) It is possible to provide a developer and a toner that are compatible with a low-temperature fixing system while maintaining cleaning properties, have good offset resistance, and do not contaminate the fixing device and the image.

Hereinafter, the present invention will be described in detail. Here, as for the toner, the manufacturing method and material of the developer used in the present invention, and the overall system relating to the electrophotographic process, known ones can be used if the conditions are satisfied.
In the toner of the present invention, it is necessary that the inorganic fine particles contained in the toner comprise at least two types of inorganic fine particles, and that the inorganic fine particles contain at least silica and titanium oxide. Silica and titanium oxide play a very important role in charge control and ensuring fluidity. If only one of them is contained, the required charge amount cannot be obtained, causing problems such as toner scattering and scumming (fogging), fluidity deteriorates, toner clogging in the toner conveyance path, and agent flow This may cause problems such as a decrease in charge amount due to deterioration of the property.

  In the toner of the present invention, when ultrasonic vibration (output 20 W, frequency 20 KHz) is applied to the toner for 1 minute, the titanium oxide adhesion rate attached to the toner particles is 75% by weight before applying ultrasonic vibration. As described above, it is very important that the silica adhesion rate is 85% by weight or less before applying ultrasonic vibration, and that the titanium oxide adhesion rate> silica adhesion rate. Titanium oxide has an adverse effect on filming, so it must be firmly adhered to the toner. Silica needs to have a slightly weaker adhesive force than titanium oxide from the viewpoint of ensuring the fluidity of the toner and improving the cleaning properties. When the adhesion of titanium oxide is weak, image quality deterioration and photoreceptor deterioration due to filming, and when the adhesion of silica is strong, problems such as poor cleaning and a decrease in charge amount due to deterioration in fluidity of the agent occur.

  In the toner of the present invention, the upper limit of the titanium oxide adhesion rate after applying ultrasonic vibration is preferably 98% by weight or less before applying ultrasonic vibration. As described above, titanium oxide needs to be firmly attached to the toner in order to adversely affect filming. However, if there is no free titanium oxide at all, the effect of improving the fluidity will be almost eliminated, causing problems such as toner clogging in the toner transport path and a decrease in charge amount due to deterioration of the fluidity of the agent. is there.

  In the toner of the present invention, it is preferable that the lower limit of the silica adhesion rate after applying ultrasonic vibration is 50% by weight or more before applying ultrasonic vibration. As described above, silica preferably has a slightly weaker adhesive force than titanium oxide from the viewpoint of securing fluidity and improving cleaning properties. However, if the adhesion rate of silica after application of ultrasonic vibration is less than 50% by weight, the amount of free silica increases too much, causing problems such as filming.

The adhesion rate in the present invention represents the difficulty of detachment of the external additive from the toner particles, and the larger the adhesion rate, the more difficult the external additive is detached from the toner. Here, a method for measuring the adhesion rate is shown below. 4 g of toner is sufficiently dispersed in 100 ml of a 0.2 wt% aqueous surfactant solution. Thereafter, using an ultrasonic homogenizer (VCX-750 manufactured by SONICS & MATERIALS), the dispersion is irradiated with ultrasonic waves at a frequency of 20 kHz and an output of 20 W for 1 minute. As a result, the external additive is removed from the surface of the toner particles, and then the dispersion is allowed to stand to separate into a precipitate and a supernatant. After washing and drying the precipitate, a fluorescent X-ray analysis is performed on the dried product, and the amount of the remaining external additive is measured. The adhesion rate is calculated by taking the ratio of this value to the value before ultrasonic irradiation.
In order to obtain a desired adhesion rate, it can be obtained, for example, by appropriately adjusting the types of titanium oxide and silica and changing the processing conditions so that the external additive adheres more firmly to the toner surface. More specifically, silica particles having an average primary particle size larger than that of titanium oxide may be used, and surface treatment may be performed using a machine having a strong stirring force such as a Q mixer. In addition to this, a silica having a higher chargeability or resistance value than that of titanium oxide, or a method of surface-treating silica after treating only titanium oxide with toner is exemplified.

The dry toner of the present invention can be produced by the following method, but is not limited thereto.
In the production of the toner of the present invention, an oil phase obtained by dispersing and / or dissolving a binder resin and a pigment in an organic solvent, for example, and a resin fine particle, a water-miscible solvent (in the case of a non-miscible solvent, both are compatible). A soluble third organic solvent, a surfactant or the like is added) and the aqueous phase is emulsified in a pipeline homomixer. Thereafter, after condensing and solvent removal, rough separation is performed using a centrifuge or a filter press. Finally, cleaning is performed and then drying is performed to complete the toner production.

  The aqueous phase used in the present invention is used by adding resin fine particles in advance. The water used for the aqueous phase may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  In the toner particles, a dispersion in which an oily phase containing a polyester prepolymer (A) having an isocyanate group dissolved or dispersed in an organic solvent is dispersed in an aqueous phase is reacted with amines (B) in the aqueous phase. It is obtained by forming. As a method for stably forming a dispersion comprising a polyester prepolymer (A) in an aqueous phase, a composition (oil phase) of a toner raw material comprising a polyester prepolymer (A) dissolved or dispersed in an organic solvent is used. In addition to the aqueous phase, there may be mentioned a method of dispersing by shearing force. Polyester prepolymer (A) dissolved or dispersed in an organic solvent and other toner composition (hereinafter referred to as toner raw material), colorant masterbatch, release agent, charge control agent, unmodified The polyester resin or the like may be mixed when forming the dispersion in the aqueous phase, but after the toner raw material is mixed in advance and dissolved or dispersed in an organic solvent, the mixture is added to the aqueous phase and dispersed. Is more preferable. In the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in the aqueous phase. It may be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the polyester prepolymer (A) has a low viscosity and is easy to disperse.

  The amount of the aqueous phase used relative to 100 parts of the toner composition (oil phase) containing the polyester prepolymer (A) is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkyls and the like as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed and / or dissolved in the aqueous phase Amine salt type such as amine salt, amino alcohol fatty acid derivative, polyamine fatty acid derivative, imidazoline, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, etc. Quaternary ammonium salt type cationic surfactants, nonionic surfactants such as fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-al Le -N, amphoteric surfactants such as N- dimethyl ammonium betaine.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), Mega-Fac F-l0, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C6 to C10) sulfonamidopropyltrimethylammonium salt which right the fluoroalkyl group, Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-21 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Kogyo Co., Ltd.) ), Megafuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.) and the like.

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

When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.
The elongation and / or crosslinking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.
In order to remove the organic solvent from the obtained emulsified dispersion, a method can be employed in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely evaporated and removed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used are generally used. Sufficient quality can be obtained by short-time treatment such as spray dryer, belt dryer, rotary kiln.
Further, as a method for removing the organic solvent, air can be blown away by a rotary evaporator or the like.
Thereafter, rough separation is performed by centrifugation, the emulsified dispersion is washed in a washing tank, the drying process is repeated in a hot air dryer, and finally, an aqueous solvent soda (containing a surfactant) in which the fluorine compound A is dispersed. In this case, the fluorine compound A is attached to the toner surface, and the solvent is removed and dried to obtain a toner base.

When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferably performed in a liquid in terms of efficiency. The obtained unnecessary fine particles or coarse particles can be returned to the kneading step and used for forming particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.
Mixing or giving mechanical impact force to the powder mixture after drying with different types of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles By immobilizing and fusing on the surface, it is possible to prevent detachment of foreign particles from the surface of the resulting composite particle.

  Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

Finally, an external additive such as inorganic fine particles and a toner base are mixed with a Henschel mixer or the like, and coarse particles are removed with an ultrasonic sieve or the like to obtain a final toner.
As a method of mixing the external additive and the toner base, a Henschel mixer, a super mixer, or a Q mixer is used to stir the mixture for 30 seconds or more, and after standing for a similar time, the mixing time is further 30 seconds or more. It is good to stir with. From the viewpoint of adjusting to an appropriate adhesion rate, it is preferable to carry out such a mixing-stationary cycle at least 2 cycles, more preferably 3 cycles or more, and even more preferably 5 cycles or more. The mixing time is preferably 60 seconds or longer, and more preferably 90 seconds or longer.
Examples of inorganic fine particles to be added to the toner base of the present invention include silica, titanium oxide, alumina, 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, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. be able to.

  Further, in the present invention, it is desirable that the average primary particle diameters of the two kinds of inorganic fine particles are different. These additives are known to be gradually embedded in the toner due to a load in the development process. However, when the two types of particle sizes are different, the inorganic fine particles having the larger particle size are separated from the toner particle surface. Plays a role of a spacer in contact with a latent image carrier (typically a photoreceptor) and a carrier surface, and prevents inorganic fine particles having a smaller particle diameter from being embedded in the toner particle surface. . Therefore, the toner surface covering state of the additive in the initial state is maintained for a long time, and the filming suppressing effect in the present invention can be further maintained.

  Furthermore, in the present invention, it is desirable that the amount of inorganic fine particles having a small average primary particle diameter of the two types of inorganic fine particles is larger than the amount of inorganic fine particles having a large average primary particle diameter. The smaller the additive amount in the larger particle size and the larger the additive amount in the smaller particle size, the smaller the change in toner characteristics over time. This is considered to be because the embedding proceeds first from the toner having a large particle diameter.

  Furthermore, it is preferable that at least one inorganic fine particle used in the present invention has an average primary particle size of 0.03 μm or less from the viewpoint of imparting fluidity. When the average primary particle size is 0.03 μm or less, necessary fluidity is obtained, toner charging becomes uniform, and toner scattering and background smearing are improved.

  The inorganic fine particles used in the present invention are required to have an average primary particle diameter of 80 to 500 nm for at least one silica from the viewpoint of cleaning residual toner on the photoreceptor. By setting the average primary particle diameter to 80 to 500 nm, silica adheres to the cleaning blade and the photosensitive member contact portion, and the cleaning is improved by the dam effect. Moreover, another kind needs to be a titanium oxide as mentioned above.

  In addition, since at least one of the inorganic fine particles used in the present invention is a hydrophobic inorganic fine particle treated with an organic silane compound, it achieves high image quality with excellent environmental stability and fewer image defects such as missing characters. More preferred. Of course, both of the two inorganic fine particles used in the present invention may be hydrophobized.

Examples of the hydrophobizing agent include dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane. P-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, p-chlorophenyltrichlorosilane, 3-chloropropyltrichlorosilane, 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinylmethoxysilane, Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinyldichlorosilane, dimethylbi Luchlorosilane, octyltrichlorosilane, decyltrichlorosilane, nonyltrichlorosilane, (4-t-propylphenyl) trichlorosilane, (4-t-butylphenyl) trichlorosilane, dipentyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane , Dinonyl dichlorosilane, didecyl dichlorosilane, didodecyl dichlorosilane, dihexadecyl dichlorosilane, (4-t-butylphenyl) octyl dichlorosilane, dioctyl dichlorosilane, didecenyl dichlorosilane, Dinonenyldichlorosilane, di-2-ethylhexyldichlorosilane, di-3,3-dimethylpentyldichlorosilane, trihexylchlorosilane, trioctylchlorosilane, tridecylchlorosilane, dioctylmethyl Lorsilane, octyldimethylchlorosilane, (4-t-propylphenyl) diethylchlorosilane, isobutyltrimethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, trimethoxy (3,3,3-trifluoropropyl) silane, hexamethyl Organic silane compounds such as disilazane, hexaethyldisilazane, diethyltetratyldisilazane, hexaphenyldisilazane, hexatolyldisilazane, 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 modified silicone oil, epoxy Silicone oil such as xy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and other silylation Agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, and the like. Of these, organic silane compounds are preferred.
By treating these hydrophobizing agents with the inorganic fine particles, the hydrophobic inorganic fine particles used in the present invention are produced.

The trade names of hydrophobized silica fine particles include HDK H 2050EP, HVK21 (above Hoechst), R972, R974, RX200, RY200, R202, R805, R812 (above Nippon Aerosil), TS530, TS720 (above Cabot). is there.
As specific trade names of surface-treated titanium oxide fine particles, anatase-type or rutile-type crystalline or non-crystalline ones can be used, such as T-805 (Nippon Aerosil) or rutile. Examples of the mold include STT-30A (Titanium Industry), STT-30A-FS (Titanium Industry), and the like.

  The particle size of the inorganic fine particles used in the present invention can be measured by a particle size distribution measuring apparatus using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd. or Coulter N4 manufactured by Coulter Electronics. It is. However, since it is difficult to dissociate the secondary aggregation of the particles after the treatment with the organic silane compound, it is preferable to directly determine the particle diameter from a photograph obtained by a scanning electron microscope or a transmission electron microscope. In this case, at least 100 or more inorganic fine particles are observed, and the average value of the major axis is obtained.

  The toner of the present invention preferably contains a wax component, and particularly preferably contains carnauba wax. Carnauba wax is a natural wax obtained from the leaves of carnabay palm, but a low acid value type from which free fatty acids are eliminated is particularly preferable because it can be uniformly dispersed in the binder resin. In addition, a low acid value type carnauba wax from which free fatty acids are eliminated is particularly preferable because it has a small amount of volatile components and therefore has little filming on the photoconductor and little spent on the charging member.

  In the present invention, the content of wax inside the toner is preferably 5% by weight or more in terms of weight. If it is less than 5%, not only is the image quality deteriorated and the gloss is lowered, but also hot offset is likely to occur, which is not preferable.

  In the present invention, the toner has a volume average particle diameter of 4 to 8 μm for high image quality, and a ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn is 1.00 to 1.25. preferable. When the particle diameter is less than 4 μm, not only the productivity of the toner is remarkably deteriorated but also the durability and fluidity are deteriorated, which is not preferable. On the other hand, if it exceeds 8 μm, the effect of improving the image quality cannot be expected so much. Furthermore, when Dv / Dn is out of the range of 1.00 to 1.25, the particle size distribution becomes wide and the image quality deteriorates.

Volume average particle size, number average particle size, and measurement of 4% or less number% are measured by a Coulter Counter TAII manufactured by Coulter Electronics, USA, an interface (manufactured by Nikkiki) that outputs the number distribution and volume distribution, and a PC9801 personal computer (manufactured by NEC). ) And used. The electrolyte was adjusted to a 1% NaCl aqueous solution using primary sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzenesulfonate is added as a dispersant to 50 to 100 ml of the electrolytic solution, and 1 to 10 mg of a sample is added. This is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser, and 100 to 200 ml of an electrolytic aqueous solution is put into another beaker, and the sample dispersion is added to a predetermined concentration therein, and the Coulter Counter TA- Measure the particle size distribution of 30000 particles of 2 to 40 μm based on the number using a 100 μm aperture as an aperture according to type II, calculate the volume distribution and number distribution of 2 to 40 μm particles, and calculate the weight from the volume distribution The standard volume average particle size was determined.
In the present invention, the toner having a volume average particle diameter of 3 μm or less is preferably 10% or less for improving the image quality. When the fine powder having a volume average particle diameter of 3 μm or less exceeds 10%, it is not preferable because it causes the background of the photoreceptor and toner scattering in the machine.

A flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation) is used for measurement of the ultrafine toner and the circularity. As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the concentration of the dispersion is set to 3000 to 10,000 / μl, and the ultrafine powder is measured with the apparatus.
The toner of the present invention is obtained by a kneading and pulverizing method including a step of melting and uniformly dispersing a colorant, a charge control agent, a wax, and the like in a thermoplastic resin, and pulverizing and classifying the obtained composition. It can also be obtained by suspension polymerization, emulsion aggregation, and dissolution suspension.
The toner of the present invention is suitable for use in a full-color image forming apparatus because it does not cause filming even when it contains 5% by weight or more of wax and has excellent transferability and high image quality. Can do. In particular, it is suitable for a tandem development method having a photoconductor for each color in a two-component development capable of increasing the speed. Furthermore, since it has excellent transferability, it is suitable for a tandem type intermediate transfer system having a plurality of transfer steps.
In addition, since it is excellent in adapting to a low-temperature fixing system, it can be suitably used for a fixing device that has a short warm-up time, low pressure, and high speed and energy saving. As such a fixing device, a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, the film and the pressure Examples thereof include a fixing device that heats and fixes a recording material on which a toner image is formed between members, and a fixing device in which a heating member is made of a magnetic metal and is heated by electromagnetic induction.

  According to the present invention, there is provided a two-component developer containing the toner and carrier. As the carrier, known ones can be used, and examples thereof include magnetic powders such as iron powder, ferrite powder and nickel powder, glass beads, and the like whose surfaces are treated with a resin or the like.

  Examples of the resin powder that can be coated on the carrier in the present invention include a styrene-acrylic copolymer, a silicone resin, a maleic acid resin, a fluorine resin, a polyester resin, and an epoxy resin. In the case of a styrene-acrylic copolymer, those having a styrene content of 30 to 90% by weight are preferred. In this case, if the styrene content is less than 30% by weight, the development characteristics are low, and if it exceeds 90% by weight, the coating film becomes hard and easily peeled, and the life of the carrier is shortened.

  Moreover, the resin coating of the carrier in the present invention may contain an adhesion-imparting agent, a curing agent, a lubricant, a conductive agent, a charge control agent and the like in addition to the resin.

  The toner according to the present invention is more effective when it has a specific shape. The toner shape is charged by contact with a carrier, and the chargeability of the toner sandwiched between the developing roll and the toner layer regulating member or the supply roller. And almost uniform thin layer properties. In the case of an irregular shape that is too far from the spherical shape, the toner thin layer is too thin and a sufficient development amount cannot be obtained. Further, in order to provide a clearer, better color reproducibility and high quality image, it is desirable that the toner has a uniform spherical shape. Therefore, in the present invention, it is preferable that the toner has a specific shape in order to form a high-definition image having a reproducibility with an appropriate density. In the present invention, the circularity is regulated to 0.92 or more. It is preferable to do.

  As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. is there. A toner having a circularity in the range of 0.92 to 0.98, which is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle, has a high reproducibility with an appropriate density. It has been found that it is effective for forming a fine image. This value can be measured as an average circularity by a flow type particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape of the toner is measured by the above apparatus with a dispersion concentration of 3000 to 10,000 / μl.

The process cartridge of the present invention uses the toner of the present invention, may have a photosensitive member and a developing unit, and may integrally support at least one unit selected from a charging unit and a cleaning unit. The process cartridge is detachable.
FIG. 1 shows a schematic configuration of an image forming apparatus having a process cartridge of the present invention.
In the figure, (10) shows the entire process cartridge, (11) shows a photoconductor, (12) shows charging means, (13) shows developing means, and (14) shows cleaning means.
In the present invention, a plurality of components such as the above-described photoreceptor (11), charging means (12), developing means (13), and cleaning means (14) are integrally combined as a process cartridge. The process cartridge is configured to be detachable from an image forming apparatus main body such as a copying machine or a printer.

  In the image forming apparatus having the process cartridge of the present invention, the photosensitive member is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the charging unit, and then receives image exposure light from an image exposing unit such as slit exposure or laser beam scanning exposure. An electrostatic latent image is sequentially formed on the peripheral surface of the body, and the formed electrostatic latent image is then developed with toner by a developing unit, and the developed toner image is transferred between the photosensitive member and the transfer unit from the paper feeding unit. Then, the image is sequentially transferred to the transfer material fed in synchronization with the rotation of the photosensitive member by the transfer means. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed on the image, and printed out as a copy (copy). The surface of the photoconductor after the image transfer is cleaned by removing toner remaining after transfer by a cleaning unit, and after being further neutralized, it is repeatedly used for image formation.

FIG. 2 shows an example of a belt induction heating fixing device.
The fixing device shown in FIG. 2 includes a heating roller (1) heated by electromagnetic induction of induction heating means (6), a fixing roller (2) (opposite rotating body) arranged in parallel with the heating roller (1), and the like. An endless belt-like heat-resistant belt that is stretched between the heating roller (1) and the fixing roller (2), is heated by the heating roller (1), and is rotated in the direction of arrow A by the rotation of at least one of these rollers. A heating rotator having (toner heating medium) (3), and a pressure roller (4) that is pressed against the fixing roller (2) via the belt (3) and rotates in the forward direction with respect to the belt (3). ) (Pressurizing rotator).

  The heating roller (1) is made of a hollow cylindrical magnetic metal member such as iron, cobalt, nickel, or an alloy of these metals, and has an outer diameter of 20 to 40 mm and a wall thickness of 0.3 to 1.0 mm, for example. It has a low heat capacity and high temperature rise.

The fixing roller (2) (opposing rotating body) is made of, for example, a metal core (2a) made of stainless steel or the like, and a heat-resistant silicone rubber that is solid or foamed and covered with the core (2a). It consists of a member (2b). Then, in order to form a contact portion having a predetermined width between the pressure roller (4) and the fixing roller (2) by the pressing force from the pressure roller (4), the heating roller has an outer diameter of about 20 to 40 mm. (1) It is larger. The thickness of the elastic member (2b) is about 4 to 6 mm. With this configuration, since the heat capacity of the heating roller (1) is smaller than the heat capacity of the fixing roller (2), the heating roller (1) is rapidly heated and the warm-up time is shortened.
The belt (3) stretched between the heating roller (1) and the fixing roller (2) is heated at the contact portion (W1) with the heating roller (1) heated by the induction heating means (6). Then, the inner surface of the belt (3) is continuously heated by the rotation of the rollers (1) and (2). As a result, the entire belt is heated.

  The pressure roller (4) includes, for example, a metal core (4a) made of a metal cylindrical member having high thermal conductivity such as copper or aluminum, and heat resistance and toner separation provided on the surface of the metal core (4a). It is comprised from the highly elastic elastic member (4b). In addition to the above metal, SUS may be used for the core metal (4a). The pressure roller (4) presses the fixing roller (2) via the belt (3) to form the fixing nip portion N. In this embodiment, the hardness of the pressure roller (4) is fixed. By making it harder than the roller (2), the pressure roller (4) bites into the fixing roller (2) (and the belt (3)), and by this biting, the recording material (11) becomes the pressure roller ( 4) The recording material (21) has an effect of being easily separated from the surface of the belt (3) because it follows the circumferential shape of the surface. The outer diameter of the pressure roller (4) is about 20 to 40 mm, which is the same as that of the fixing roller (2), but the wall pressure is about 0.5 to 2.0 mm and is thinner than the fixing roller (2).

As shown in FIG. 2, the induction heating means (6) for heating the heating roller (1) by electromagnetic induction includes an exciting coil (7) as a magnetic field generating means and a coil around which the exciting coil (7) is wound. And a guide plate (8). The coil guide plate (8) has a semi-cylindrical shape disposed close to the outer peripheral surface of the heating roller (1), and the excitation coil (7) has a single long excitation coil wire as the coil guide plate (8). Along the axial direction of the heating roller (1). The exciting coil (7) has an oscillation circuit connected to a drive power supply (not shown) whose frequency is variable.
On the outside of the exciting coil (7), a semi-cylindrical exciting coil core (9) made of a ferromagnetic material such as ferrite is fixed to the exciting coil core support member (20) and arranged close to the exciting coil (7). Yes.

FIG. 3 shows the configuration of the belt (3). The configuration of the belt 3 is as follows, and the following four layers are formed from the inner layer to the surface layer.
・ Substrate (resin layer: polyimide (PI) resin, etc.)
-Heat generation layer (Ni, Ag, SUS, etc. as magnetic metal): 3a
・ Intermediate layer (Aiming for uniform fixing with an elastic layer): 3b
・ Surface layer (release layer) (Aimed at release effect and oil-less with fluororesin material): 3c

  The thickness of the release layer (3c) is preferably about 10 μm to 300 μm, particularly about 200 μm. By doing so, the toner image T formed on the recording material (21) is sufficiently wrapped by the surface layer of the belt (3), so that the toner image T can be uniformly heated and melted.

The thickness of the release layer (c), that is, the surface release layer, is required to be at least 10 μm in order to ensure wear resistance over time.
On the other hand, when the thickness of the release layer (3c) is larger than 300 μm, the heat capacity of the belt (3) increases and the time required for warm-up becomes longer. In addition, in the toner fixing process, the belt surface temperature is difficult to decrease, the agglomeration effect of the melted toner at the fixing portion outlet cannot be obtained, the belt releasability is reduced, and the toner adheres to the belt. Hot offset occurs.
Further, by providing a heat generating layer by electromagnetic induction heating such as silver foil inside the belt, the belt surface can be efficiently heated. A combination with a heating roller heated by electromagnetic induction is preferable because the thermal efficiency is further improved.

  The electromagnetic induction generating means is preferably provided outside for the following reasons. That is, when the electromagnetic induction generating means is provided inside the heating roller, it is necessary to extremely increase the diameter of the heating roller, and in accordance with this, it is necessary to improve pressure resistance for internal protection. It is necessary to thicken the layer. This thick layer around the periphery reduces thermal efficiency. In addition, by providing it outside the electromagnetic induction generating means, convenience such as temperature controllability and arrangement applicability is high.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
Hereinafter, a part shows a weight part.
(Evaluation of two-component developer)
When evaluating an image with a two-component developer, a ferrite carrier having an average particle diameter of 35 μm coated with a silicone resin at an average thickness of 0.5 μm is used as follows, and toner 7 of each color is used with respect to 100 parts by weight of the carrier. The developer was prepared by uniformly mixing and charging the parts by weight using a tumbler mixer of the type in which the container rolls and stirs.

(Carrier production)
・ Core material Mn ferrite particles (weight average diameter: 35 μm) 5000 parts ・ Coating material Toluene 450 parts Silicone resin SR2400
(Toray Dow Corning Silicone, nonvolatile content 50%) 450 parts Aminosilane SH6020 (Toray Dow Corning Silicone) 10 parts Carbon Black 10 parts The coating material is dispersed with a stirrer for 10 minutes to prepare a coating solution, The coating liquid and the core material were put into a coating apparatus for coating while forming a swirling flow in which a rotating bottom plate disk and a stirring blade were provided in the fluidized bed, and the coating liquid was applied onto the core material. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to obtain the carrier.

(Image evaluation)
-Toner scattering The toner contamination state in the copying machine after carrying out a continuous 100,000 sheet output durability test with an image area ratio of 7% using each toner was visually evaluated. ◎ indicates that the toner stain is not observed at all and is in a good state, ○ indicates that the slight stain is observed, no problem, Δ indicates a slight stain is observed, and × indicates that the stain is not within the allowable range. There is a problem.
-Graininess A photographic image was output in a single color, and the degree of graininess and sharpness was visually evaluated. Evaluations were made from GOOD, ◎, ○, Δ, and ×.並 is equivalent to offset printing, ◯ is slightly worse than offset printing, Δ is much worse than offset printing, and × is very bad compared to conventional electrophotographic images.
-Soil stain Using each toner, evaluation was performed using ΔID after an image area ratio 7% chart continuous 100,000 sheet output durability test. A is less than 0.01 for ΔID, ΔID is 0.01 to 0.02 for Δ, and ΔID is 0.02 or more for x.
・ Filming When the image endurance 15% chart continuous 100,000 sheet output durability test using each toner was performed, the case where filming appeared in the middle was indicated as “X”, the case where it was slightly visible was indicated as “△”, and the case where it did not appear was indicated as “◯”. did.
-Charging stability Using each toner, an image area ratio 7% chart continuous 100,000 sheet output durability test was conducted, and the change in charge amount at that time was evaluated. 1 g of developer was weighed and the change in charge amount was determined by the blow-off method. When the change in the charge amount was 5 μc / g or less, it was evaluated as ◯, when it was 10 μc / g or less, Δ when it exceeded 10 μc / g.
・ Cleaning After printing 1,000 sheets of image area ratio 95% chart using each toner, transfer residual toner on the photoreceptor that passed the cleaning process is transferred to white paper with Scotch tape (manufactured by Sumitomo 3M), and it is reflected by Macbeth Measured with a densitometer RD514, and evaluated as “◯” when the difference from the blank is less than 0.01, “Δ” when 0.01 to 0.02, and “×” when exceeding 0.02. did.

(Manufacture of toner)
~ Synthesis of organic fine particle emulsion ~
Production Example 1
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, 110 butyl acrylate Parts and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Furthermore, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and an aqueous dispersion of vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). [Fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 58 ° C., and the weight average molecular weight was 130,000.

-Adjustment of aqueous phase-
Production Example 2
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 7 hours at normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. By reacting for 3 hours, [low molecular weight polyester 1] was obtained. [Low molecular polyester 1] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, Tg of 43 ° C., and an acid value of 25.

~ Synthesis of intermediate polyester ~
Production Example 4
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 7 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

~ Synthesis of ketimine ~
Production Example 5
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 hours and half to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

~ Synthesis of master batch (MB) ~
Production Example 6
1200 parts of water, 540 parts of carbon black (made by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin are added and mixed with a Henschel mixer (made by Mitsui Mining Co., Ltd.). After kneading at 130 ° C. for 1 hour using two rolls, rolling and cooling and pulverizing with a pulverizer, [Masterbatch 1] was obtained.

~ Creation of oil phase ~
Production Example 7
In a container equipped with a stirring bar and a thermometer, 378 parts of [Low molecular weight polyester 1], Carnauba WAX10O part, 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
Production Example 8
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 1].

~ Washing⇒Drying ~
Production Example 9
[Dispersion Slurry 1] After 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was.
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer. Thereafter, sieved with a mesh of 75 μm, [Toner Base Particle 1] was obtained.
The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.

Example 1
The toner base particles prepared by the polymerization method using carnauba wax are finely divided and coarse powders are cut, 1.5 parts by weight of silica fine particles having an average primary particle diameter of 10 nm and an average primary particle diameter of 140 nm with respect to 100 parts by weight of the toner base. 1.0 part by weight of silica fine particles and 0.5 part by weight of titanium oxide fine particles having an average primary particle diameter of 15 nm were blended to form a Henschel mixer (rotation speed 2000 rpm, mixing time 90 seconds, rest time 120 seconds, 5 And used as an electrophotographic toner.

Example 2
The toner base particles prepared by the polymerization method using carnauba wax are finely divided and coarse powders are cut, 1.5 parts by weight of silica fine particles having an average primary particle diameter of 10 nm and an average primary particle diameter of 140 nm with respect to 100 parts by weight of the toner base. 1 part by weight of silica fine particles and 0.5 part by weight of titanium oxide fine particles having an average primary particle diameter of 15 nm were mixed to form a super mixer (rotation speed 2400 rpm, mixing time 90 seconds, rest time 120 seconds, 5 And used as an electrophotographic toner.

Example 3
The toner base particles prepared by the polymerization method using carnauba wax are finely divided and coarse powders are cut, 1.5 parts by weight of silica fine particles having an average primary particle diameter of 10 nm and an average primary particle diameter of 140 nm with respect to 100 parts by weight of the toner base. 1 part by weight of silica fine particles and 0.5 part by weight of titanium oxide fine particles having an average primary particle diameter of 15 nm were mixed in a Q mixer (rotation speed: 6000 rpm, mixing time: 90 seconds, rest time: 120 seconds, 5 And used as an electrophotographic toner.

Comparative Example 1
The toner base particles prepared by the polymerization method using carnauba wax are finely divided and coarse powders are cut, 1.5 parts by weight of silica fine particles having an average primary particle diameter of 10 nm and an average primary particle diameter of 140 nm with respect to 100 parts by weight of the toner base. 1.0 part by weight of silica fine particles and 0.5 part by weight of titanium oxide fine particles having an average primary particle diameter of 15 nm were mixed to form a Henschel mixer (rotation speed: 1000 rpm, mixing time: 90 seconds, rest time: 120 seconds, 5 And used as an electrophotographic toner.

Comparative Example 2
The toner base particles prepared by the polymerization method using carnauba wax are finely divided and coarse powders are cut, 1.5 parts by weight of silica fine particles having an average primary particle diameter of 10 nm and an average primary particle diameter of 140 nm with respect to 100 parts by weight of the toner base. 1.0 part by weight of silica fine particles and 0.5 part by weight of titanium oxide fine particles having an average primary particle diameter of 15 nm were blended to form a Henschel mixer (rotation speed: 3000 rpm, mixing time: 90 seconds, rest time: 120 seconds, 5 Cycle), the toner was then heated to fix the external additive and used as an electrophotographic toner.

Comparative Example 3
Toner base particles prepared by polymerization using carnauba wax are cut into fine powder and coarse powder, and titanium oxide fine particles having an average primary particle diameter of 15 nm are blended to 0.5 parts by weight with respect to 100 parts by weight of the toner base. The mixture was stirred and mixed with a Henschel mixer (rotation speed 2000 rpm, mixing time 90 seconds, stationary time 120 seconds, 5 cycles), and used as an electrophotographic toner.

Comparative Example 4
The toner base particles prepared by the polymerization method using carnauba wax are finely divided and coarse powders are cut, 1.5 parts by weight of silica fine particles having an average primary particle diameter of 10 nm and an average primary particle diameter of 140 nm with respect to 100 parts by weight of the toner base. The silica fine particles were mixed so as to be 1.0 part by weight, and stirred and mixed with a Henschel mixer (rotation speed 2000 rpm, mixing time 90 seconds, stationary time 120 seconds, 5 cycles) to be used as an electrophotographic toner.

Comparative Example 5
The toner base particles produced by the polymerization method using carnauba wax are finely divided and coarse powders are cut, and 1.5 parts by weight of silica fine particles having an average primary particle diameter of 10 nm and an average primary particle diameter of 15 nm with respect to 100 parts by weight of the toner base. The titanium oxide fine particles were mixed so as to be 0.5 parts by weight, and stirred and mixed using a Henschel mixer (rotation speed 2000 rpm, mixing time 90 seconds, stationary time 120 seconds, 5 cycles) to be used as an electrophotographic toner. .

Example 4
The toner base particles of Example 1 were finely divided and the coarse powder was not cut, and 1.5 parts by weight of silica fine particles having an average primary particle diameter of 10 nm and silica fine particles having an average primary particle diameter of 140 nm were added to 100 parts by weight of the toner base. 1.0 part by weight of titanium oxide fine particles having an average primary particle size of 15 nm are blended so as to be 0.5 part by weight and stirred by a Henschel mixer (rotation speed 2000 rpm, mixing time 90 seconds, rest time 120 seconds, 5 cycles). The toner was mixed and used as an electrophotographic toner.

Example 5
The toner base particles of Example 1 are classified to a volume average particle diameter of 9 μm by classification, and then fine powder and coarse powder are cut by centrifugation, and silica fine particles having an average primary particle diameter of 10 nm are added to 1.5 parts by weight of the toner base. Part by weight, 1.0 part by weight of silica fine particles having an average primary particle diameter of 140 nm and 0.5 part by weight of titanium oxide fine particles having an average primary particle diameter of 15 nm were blended, and a Henschel mixer (rotation speed 2000 rpm, mixing time 90). Second, rest time 120 seconds, 5 cycles) and used as an electrophotographic toner.

Example 6
The toner base particles of Example 1 were used as an electrophotographic toner in the same manner as in Example 1 except that ester wax was used instead of carnauba wax.

Example 7
The toner base particles of Example 1 were produced by the following pulverization method instead of the polymerization method, and then used as an electrophotographic toner in the same manner as in Example 1.
・ Binder resin: 100 parts of polyester resin
Number average molecular weight (Mn); 3700
Weight average molecular weight (Mw); 21000
Glass transition point (Tg); 61 ° C
Softening point: 118 ° C
Colorant: Copper phthalocyanine pigment 8 parts
C. I. P. B. 15: 3
-Charge control agent: 1 part of zinc salicylate-Mold release agent: 6.5 parts of carnauba wax
Melting point: 82 ° C
Were mixed, melt kneaded, cooled, coarsely pulverized with a hammer mill, and finely pulverized with an air jet pulverizer to classify toner base particles having a weight average particle diameter of 5 μm.

  In addition, the capacity | capacitance of the mixer used in the Example and the comparative example is 20L for a Henschel mixer, 200L for a super mixer, and 20L for a Q mixer.

1 is a diagram showing a schematic configuration of an image forming apparatus having a process cartridge of the present invention. It is a figure which shows the fixing device of the belt dielectric heating of this invention. It is a figure which shows the structure of the belt used for this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Heating roller 2 Fixing roller 2a Metal core 2b Elastic member 3 Endless belt-like heat-resistant belt (toner heating medium)
3a Heat generation layer 3b Intermediate layer 3c Surface layer (release layer)
4 Pressure roller (Pressure rotating body)
4a Metal core 4b Elastic member 5 Temperature sensor 6 Induction heating means 7 Excitation coil 8 Coil guide plate 9 Excitation coil core 10 Process cartridge 11 Photoconductor 12 Charging means 13 Developing means 14 Cleaning means 20 Excitation coil core support member 21 Recording material

Claims (16)

An electrostatic charge image developing toner particle containing at least a binder resin and a colorant, and an electrostatic charge image developing toner containing at least inorganic fine particles, wherein the inorganic fine particles comprise at least two kinds of inorganic fine particles, and the inorganic fine particles When at least silica and titanium oxide are contained and ultrasonic vibration (output 20 W, frequency 20 KHz) is applied to the toner for 1 minute, the adhesion rate of titanium oxide adhering to the toner particles is before the ultrasonic vibration is applied. A toner for developing an electrostatic charge image, wherein the silica adhesion rate is 85% by weight or less before applying ultrasonic vibration, and the titanium oxide adhesion rate> silica adhesion rate. 2. The electrostatic image developing toner according to claim 1, wherein the upper limit of the titanium oxide adhesion rate after application of ultrasonic vibration is 98% by weight or less before application of ultrasonic vibration. 3. The electrostatic charge image developing toner according to claim 1, wherein the lower limit of the silica adhesion rate after applying ultrasonic vibration is 50% by weight or more before applying ultrasonic vibration. 4. The electrostatic image developing toner according to claim 1, wherein the inorganic fine particles contain at least an average primary particle size silica of 80 nm to 500 nm. The electrostatic image developing toner according to claim 1, further comprising a wax. 6. The electrostatic image developing toner according to claim 1, wherein the wax is carnauba wax. The toner for developing an electrostatic charge image according to claim 5, wherein the content of the wax inside the toner is 5% by weight or more. The volume average particle diameter _{D V} of the toner is the 4-8 [mu] m, according to claim 1, the ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn is characterized in that it is a 1.00 to 1.25 The toner for developing an electrostatic charge image according to any one of Items 1 to 7. 9. The electrostatic charge image developing toner according to claim 1, wherein fine powder having a volume average particle diameter of 3 μm or less is 10% or less. 10. The electrostatic image developing toner according to claim 1, wherein the toner has a circularity of 0.92 to 0.98. A two-component electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to claim 1 and a carrier comprising magnetic particles. Developing means for developing the electrostatic latent image formed on the image carrier with a developer containing toner, and transfer means for transferring the toner image formed on the image carrier onto the image support 11. An image forming apparatus comprising: a heating rotator having a heating member; and a pressure rotator disposed opposite to the heating rotator, and a fixing unit for fixing the toner image. An image forming apparatus using the electrostatic image developing toner according to any one of the above. The fixing unit includes a heating body provided with a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, the film and the pressure member The image forming apparatus according to claim 12, wherein the image forming apparatus is a fixing device that heats and fixes a recording material on which a toner image is formed. 14. The image forming apparatus according to claim 12, wherein the heating member of the fixing device is made of a magnetic metal and is heated by electromagnetic induction.   The image forming method according to claim 14, wherein the electromagnetic induction generating unit is provided outside the heating rotator. In the process cartridge that includes a photosensitive member and a developing unit, and further supports at least one unit selected from a charging unit and a cleaning unit, and is detachable from the image forming apparatus main body, the developing unit includes: A process cartridge comprising a toner, wherein the toner is the electrostatic image developing toner according to claim 1.

Images