JP2014209186A - Magnetic toner and electrophotographic cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer used for a copier and an electrostatic recording device of an electrophotographic system, and an electrophotographic cartridge using the developer, in particular, to provide a magnetic toner that exhibits excellent image characteristics such as image density, resolution, and gradation even after continuous photographing, and prevents the occurrence of toner void and image unevenness in low temperature and low humidity called waves.SOLUTION: There is provided a magnetic toner containing a magnetic material, a charge control agent, and a wax, having the physical property values of the magnetic material, charge control agent, and wax obtained by measuring the magnetic toner satisfying a specific relationship, and including inorganic fine particles having an average primary particle diameter of 40 nm or more and 70 nm or less on the toner surface.

Description

  The present invention relates to a magnetic toner and an electrophotographic cartridge, and more particularly to a magnetic toner used in an electrophotographic copying machine and an electrostatic recording apparatus, and an electrophotographic cartridge using the toner. More specifically, the present invention relates to a magnetic toner that has excellent image characteristics such as image density, resolution, and gradation, does not cause image defects such as image unevenness called wave, and does not cause void even in a low temperature and low humidity environment.

  In general, dry development methods used in electrophotography include a two-component development method in which a carrier such as iron powder or ferrite powder and a toner are mixed and a one-component development method in which no carrier is used. Of these, the two-component development method requires a so-called toner density control mechanism that replenishes the required amount as the toner is consumed, and thus has a problem in terms of size and cost of the apparatus. On the other hand, there are two types of one-component development methods: magnetic one-component method and non-magnetic one-component method. These one-component development methods can reduce the size of the apparatus. Many have adopted a method.

  In recent years, the performance required for copiers and printers has become more sophisticated, but the performance required for toner is that the image density is sufficient when an image is formed and there is no image defect. It can be used stably for a long period of time, it is sufficiently fixed on paper, does not cause blocking during the toner production process, storage and transportation, has no un developable toner, and can suppress toner consumption. It has become a thing. Further, these required performances are greatly affected by the characteristics of the image forming apparatus to be used.

  Some toner performance requirements show conflicting tendencies, such as fixing properties and long-term durability, and it is not easy to achieve both of them. Many proposals have been made regarding the properties of ingredients, formulation, manufacturing methods, manufacturing conditions, and the like.

  Particularly in recent years, there is a tendency to reduce the energy of the fixing device in order to reduce power consumption. In this case, the toner needs to be sufficiently melted at a low temperature so as not to cause fixing failure. In general, it is effective to lower the softening point and glass transition point of the binder resin for such measures, but when using a binder resin having a low softening point or glass transition point in this way, the materials are mixed, kneaded, In the case of a pulverization method that is manufactured by pulverization, since the melt viscosity of the binder resin is low, sufficient shearing force during kneading cannot be ensured, and the dispersibility of each material in the toner is deteriorated, which adversely affects the image. It has become a problem. As a countermeasure, it has been reported that the problem can be solved by means of defining the endothermic peak area of a differential scanning calorimeter (DSC) of the wax to be added, but this is mainly related to fixing performance and printing durability. The relationship between the DSC endothermic peak area, the magnetic powder content, the strength ratio of the charge control agent and the like was not mentioned, and the printing durability was insufficient. (See Patent Document 1, Patent Document 2, and Patent Document 3)

In particular, in the case of a magnetic toner, the specific gravity of the binder resin and the magnetic powder differ greatly, resulting in non-uniform dispersibility. For this reason, the toner has less magnetic powder, more magnetic powder, and more free than the toner particles. As a result, there are overdevelopment of particles with a small amount of magnetic powder, and particles with a large amount of magnetic powder and free magnetic powder exhibit image defects such as drum deterioration, streaks, and uneven density. As a result, the toner remains in the developing tank as undeveloped toner, which is a cause of failure to obtain stable image characteristics not only in a low temperature and low humidity environment but also in a normal environment.
As a countermeasure, it has been reported that a means for defining the saturation magnetization of the magnetic powder and the DSC endothermic peak area of the wax is used, but the image formation and durability are more affected than the magnetic properties of the toner. Since there is no provision for the chargeability (charge control agent) of the toner, it is insufficient to obtain a more stable printing durability. (Refer to Patent Document 4) In addition, for stabilization of printing durability, external addition of titanium oxide as an external additive has been reported (see Patent Document 5), but the external additive reported here (titanium oxide) The primary particle size is 5 nm or more and 40 nm or less. In this particle size range, the effect of the external additive having the particle size between the toner and the toner and the member between the toner and the member is not effective. Opportunities due to direct contact with sufficient chargeable external additives such as silica increase the electrification of the toner, increase the charge of the toner, stabilize the durability, and image unevenness called wave in a low temperature and low humidity environment It was insufficient as a countermeasure.

Japanese Patent Laid-Open No. 2006-267142 Japanese Patent Application Laid-Open No. 2007-17962 JP 2009-25327 Japan Japanese Patent Laid-Open No. 2006-39366 JP 2011-248084 Japan

These problems have become apparent especially in copying machines and printers that perform high-speed printing, and there are unclear indicators that show how it is preferable to disperse magnetic powder, charge control agents, wax, etc. in the binder resin. Therefore, it has been difficult to obtain a toner that does not cause the above problems.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a developer used in an electrophotographic copying machine or an electrostatic recording apparatus and an electrophotographic cartridge using the developer, and more specifically. Another object of the present invention is to provide a magnetic toner that is excellent in image characteristics such as image density, resolution, gradation, and the like, has good voids, and does not cause image unevenness called wave under low temperature and low humidity.

  As a result of intensive studies in order to overcome the problems of the prior art, the present inventor has found that a magnetic toner containing a magnetic material, a charge control agent, and a wax can be obtained by measuring the magnetic toner. The present invention has found that the above problems can be solved by having inorganic particles having an average primary particle size of 40 nm or more and 70 nm or less on the toner surface satisfying a specific relationship between the physical properties of the toner, the charge control agent, and the wax. Reached.

That is, the gist of the present invention resides in the following [1] to [5].
[1] A magnetic toner containing at least a binder resin, wax, and magnetic powder, wherein the content ratio of the magnetic powder to the toner determined by measurement with a thermal balance of the magnetic toner is X (%). Y (arbitrary unit) is the strength ratio of the charge control agent determined from the calibration curve representing the amount of the charge control agent added, determined by measurement with a UV / visible spectrophotometer of the solution dissolved in THF and filtered. X, Y and Z satisfy the following formula (1), where Z (mJ / mg) represents the peak area of the wax that appears from 60 ° C. to 160 ° C. determined by measurement with a differential scanning calorimeter of the magnetic toner. And a toner having inorganic fine particles having an average primary particle size of 40 nm to 70 nm on the surface of the magnetic toner.

160 <X · Z / Y <270 Formula (1)
[2] The magnetic toner according to [1], wherein the inorganic fine particles are titanium oxide.
[3] The magnetic toner according to [2], wherein the titanium oxide is an anatase type.
[4] The magnetic toner according to [2] or [3], wherein the titanium oxide contains an organosilane compound.
[5] An electrophotographic cartridge having the magnetic toner according to any one of [1] to [4], a photosensitive member, and a developing sleeve provided on the photosensitive member so that the magnetic toner can be conveyed and developed. An electrophotographic cartridge, wherein the developing sleeve is a nickel-plated aluminum substrate.

According to the present invention, there is provided a magnetic toner that has stable image characteristics and does not cause voids or image unevenness even in a low temperature and low humidity environment.
In addition, the above-described problem becomes more noticeable when the developing sleeve provided in the electrophotographic cartridge is a nickel-plated aluminum substrate. Therefore, the magnetic toner of the present invention and the nickel-plated aluminum substrate are used. By using an electrophotographic cartridge having a developing sleeve, the effects of the present invention can be exhibited more remarkably.

Hereinafter, the present invention will be described. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented.
The magnetic toner of the present invention contains a binder resin, a charge control agent, wax and magnetic powder, and it is essential that the toner surface has inorganic fine particles having an average primary particle size of 40 nm to 70 nm. Further, other inorganic fine particles may be provided on the toner surface.

In the magnetic toner of the present invention, the content ratio of the magnetic powder determined by measurement with a thermal balance of the magnetic toner is X (%), and the solution obtained by dissolving the magnetic toner in THF and filtering the solution is measured with an ultraviolet / visible spectrophotometer. The strength ratio of the charge control agent determined from the calibration curve representing the addition amount of the corresponding charge control agent determined by measurement is Y (arbitrary unit), and from 60 ° C. to 160 ° C. determined by the DSC measurement of the magnetic toner. The peak area of the wax that appears is Z (mJ / mg)
The magnetic toner having X, Y and Z satisfying the following formula (1) and having inorganic fine particles having an average primary particle size of 40 nm or more and 70 nm or less on the surface of the magnetic toner is provided. Can be solved.

160 <X · Z / Y <270 Formula (1)
<1. Content ratio of magnetic powder to toner (X)>
In the magnetic toner of the present invention, it is necessary to control the content ratio (X) of the magnetic powder, which is determined by measuring the magnetic toner with a thermal balance, within a range that satisfies the above formula (1).

Here, the content ratio (X) of the magnetic powder is not particularly limited as long as it satisfies the formula (1) and the effect of the present invention is not significantly impaired, but the magnetic toner of the present invention is a magnetic one component that does not use a carrier. When used as a developer, the content of the magnetic powder in the magnetic toner is usually 15% by weight or more, preferably 20% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less. desirable. If the content of the magnetic powder is less than the above range, the magnetic force required for the magnetic toner may not be obtained, and if it exceeds the above range, it may cause poor fixing properties. The magnetic powder containing the magnetic toner of the present invention includes spherical, hexahedral and octahedral shapes, but is not particularly limited. Here, the spherical magnetic powder refers to a magnetic powder in which no corners are observed when the magnetic powder particles are observed with an electron microscope. Examples of such spherical magnetic powder include Toda Kogyo Co., Ltd., MTS005-NS, EPT305, MAT305, and the like. On the other hand, magnetic powders that are distinguished from spherical magnetic powders include those that are observed in a hexahedral shape, an octahedral shape, etc. when observed with an electron microscope, such as EPT1000 manufactured by Toda Kogyo Co., Ltd. . Depending on the shape of the magnetic powder, the dispersion in the toner is better in the spherical magnetic powder than in the octahedral and hexahedral magnetic powders. Also, due to the magnetic force of the magnetic powder, if the magnetic force is large, the dispersibility in the toner will be poor, the image will be poorly developed due to the spread of the magnetic force distribution, and streaky due to the generation of free magnetic powder in the pulverization classification process. Cause image defects.

The magnetic powder applicable to the present invention can be obtained by appropriately selecting from commercially available magnetic powders, and the material of the magnetic powder is at the use environment temperature of the copying machine or the like (around 0 ° C. to 60 ° C.). A ferromagnetic substance exhibiting ferrimagnetism or ferromagnetism, for example, magnetite (Fe ₃ O ₄ ), maghemite (γ-Fe ₂ O ₃ ), an intermediate between magnetite and maghematite, ferrite (M _X Fe _{3 -X} O ₄ ; in the formula, M includes Mn, Fe, Co, Ni, Cu, Mg, Zn, Cd, etc., or mixed crystals thereof), among which magnetite or an intermediate between magnetite and maghematite is preferable.

<2. Strength ratio of charge control agent (Y)>
The magnetic toner of the present invention is a strength ratio of the charge control agent determined from a calibration curve representing the amount of the charge control agent added, determined by measurement with a UV / visible spectrophotometer of a solution obtained by dissolving the toner in THF and filtering. Is set to Y (arbitrary unit), and it is necessary to control within a range satisfying the above expression (1).

  Here, the strength ratio (Y) of the charge control agent obtained from a calibration curve representing the amount of the charge control agent added is not particularly limited as long as it satisfies the formula (1) and does not significantly impair the effects of the present invention. Is usually from 0.5 to 1.5, preferably from 0.7 to 1.2, but the strength ratio of the charge control agent determined from the calibration curve representing the amount of the charge control agent added is the above. If the value is too small, the toner charge amount becomes low, causing problems such as fogging and toner scattering. On the other hand, if the value is too large, the toner charge becomes high and the image density may be lowered.

  As the charge control agent contained in the magnetic toner of the present invention, known positive charge or negative charge control agents may be used alone or in combination. The charge control agent is not limited, but as the positive charge control agent, for example, nigrosine dye, quaternary ammonium salt, triaminotriphenylmethane compound, imidazole compound, polyamine resin, etc., negative charge control Examples of the agent include metal-containing azo dyes such as Cr, Co, Al, and Fe, salicylic acid metal compounds, curixarene compounds, and alkylsalicylic acid metal compounds. In selecting the charge control agent, it is preferable to use a metal-containing azo dye such as Cr, Co, Al, Fe or the like that contains as little volatile impurities as possible.

  The amount of the charge control agent used varies depending on the target charge amount, but is usually 0.05 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the binder resin. If the content of the charge control agent is less than the above range, an effect of improving the chargeability cannot be expected. If the content exceeds the above range, a free charge control agent is generated, and the chargeability of the toner is reduced, and fogging or the like is caused. Although it is not preferable because it may cause a problem, the problem is how much the charge control agent is exposed on the toner surface. This is a solution in which a solvent such as THF is dissolved and filtered. Can be confirmed from the absorbance measured with an ultraviolet / visible spectrophotometer.

<3. Wax peak area (Z)>
In the magnetic toner of the present invention, it is necessary to control the peak area (Z) of the wax appearing from 60 ° C. to 160 ° C. determined by measurement with a differential scanning calorimeter (DSC) within a range satisfying the above formula (1). is there.
Here, the peak area (Z) of the wax appearing from 60 ° C. to 160 ° C. determined by the DSC measurement of the toner is not particularly limited as long as the formula (1) is satisfied and the effect of the present invention is not significantly impaired. In general, it is 1.0 to 5.0, preferably 1.5 to 4.0. If the peak area (Z) of the wax is too smaller than the above range, the fixing performance may be deteriorated. On the other hand, if it is too large, the wax on the surface of the toner may adhere to the photosensitive drum, causing filming image failure, or lowering the chargeability of the toner, causing fogging and toner scattering.
The peak area (Z) of the wax is determined by measuring the toner with DSC, and the measurement is performed according to the description in the examples.

  The magnetic toner of the present invention contains a wax in order to improve characteristics such as offset resistance. The wax to be included in the present invention includes polyethylene wax, polypropylene wax, paraffin wax, carnauba wax, rice wax, sausage wax. Examples thereof include sol wax, montan ester wax, Fischer-Tropsch wax, higher fatty acid, fatty acid amide, metal soap, and silicone oil. It is preferable to add 0.1 to 30 parts by weight of the wax with respect to 100 parts by weight of the binder resin because offset resistance can be improved without causing problems such as filming. What has an endothermic peak at 60-160 degreeC is more preferable.

  The content of the wax with respect to the toner is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 2 to 10 parts by weight, more preferably 4 parts by weight with respect to 100 parts by weight of the binder resin. To 8 parts by weight. If the content of the wax is less than the above range, fixing defects such as offset may occur easily. On the other hand, if the content of the wax is too large, the wax on the toner surface may adhere to the photosensitive drum, resulting in filming image defects. Or the chargeability of the toner may decrease, causing fogging and toner scattering.

<4. Configuration of toner>
As the binder resin, various known resins suitable for developers can be used. For example, styrene resin, vinyl chloride resin, rosin modified maleic resin, phenol resin, epoxy resin, saturated polyester resin, unsaturated polyester resin, low molecular weight polyethylene, low molecular weight polypropylene, ionomer resin, polyurethane resin, silicone resin, ketone resin , Ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, and the like. Preferred resins for use in the present invention include styrene resins, saturated polyester resins, unsaturated polyester resins, and epoxy resins. Can do. These resins may be used alone or in combination. These resins are used as a non-crosslinked resin, a crosslinked resin, or a mixture thereof according to the fixing method.

  Styrene resins include polystyrene, polychlorostyrene, poly-α-methylstyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene. -Vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer) Styrene-octyl acrylate copolymer and styrene-phenyl acrylate copolymer), styrene-methacrylic acid ester copolymer (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-metac Octyl copolymer Le acid and styrene - phenyl methacrylate copolymer), methyl methacrylate copolymer styrene -α- chloromethyl acrylate and styrene - acrylonitrile - acrylic acid ester copolymers and the like. These styrenic resins can be used as a crosslinked resin by copolymerizing a crosslinkable monomer as required. In addition, as a method for producing the binder resin, there are bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, and the like, which can be used regardless of the polymerization method.

  The polyester resin is a polycondensation of a divalent carboxylic acid monomer, a divalent alcohol monomer and, if necessary, a trivalent or higher polyvalent carboxylic acid monomer or a polyhydric alcohol monomer, or urethane. It can be obtained by increasing the molecular weight by crystallization or by a crosslinking reaction. Divalent alcohol monomers include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol. Diols such as bisphenol A, etherified bisphenols such as bisphenol A, polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A, and other divalent alcohol monomers. The divalent carboxylic acid monomer is mainly composed of isophthalic acid, terephthalic acid, adipic acid, sebacic acid, diphenic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, anhydrides or lower alkyl esters of these acids. Is mentioned. Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid, cyclohexanetricarboxylic acid, naphthalenetricarboxylic acid, butanetricarboxylic acid, hexanetricarboxylic acid, octanetetracarboxylic acid, anhydrides of these acids, and the like. Examples of the trihydric or higher polyhydric alcohol monomer include trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol.

  Colorants include carbon black, lamp black, iron black, ultramarine, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine dyes, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallyl Any known dyes and pigments such as methane dyes, monoazo dyes, disazo dyes, and condensed azo dyes and pigments can be used alone or in combination.

The method for producing the magnetic toner of the present invention is not limited, and a polymerization method such as a pulverization method, a suspension polymerization method or an emulsion polymerization aggregation method can be used, but from the viewpoint of uniform dispersibility of the magnetic powder and toner components. The pulverization method is preferable.
When the magnetic toner of the present invention is produced by a pulverization method, it can be carried out according to a conventionally known method. That is, usually, first, a binder resin, magnetic powder, and other components such as a colorant other than the magnetic powder added as necessary, a charge control agent and wax are uniformly dispersed and mixed in a mixer, and then the mixture is mixed. It is melt-kneaded with a closed kneader or a single-screw or twin-screw extruder, etc., cooled, coarsely crushed with a crusher, hammer mill, etc., finely crushed with a jet mill, high-speed rotor rotary mill, etc., and an air classifier (for example, Toner base particles containing magnetic powder are obtained by classification using an inertia class elbow, centrifugal class microplex, DS separator, or the like. The toner base particles obtained have a particle size of preferably 4 to 15 μm, more preferably 5 to 9 μm. Here, the particle size can be measured using a multisizer (manufactured by Coulter).

After these steps, it is preferable to add externally added fine particles to the toner base particles in order to improve fluidity, charging stability, anti-blocking property at high temperature, etc. Alternatively, various organic fine powders can be added. This inorganic fine powder is composed of various carbides such as silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, boron nitride, nitride Various nitrides such as titanium and zirconium nitride, various borides such as zirconium boride, various oxides such as titanium oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, cerium oxide, silica, colloidal silica, Various titanate compounds such as calcium titanate, magnesium titanate, strontium titanate, phosphate compounds such as calcium phosphate, sulfides such as molybdenum disulfide, fluorides such as magnesium fluoride and fluorocarbon, aluminum stearate, stearin acid Examples include various metal soaps such as lucium, zinc stearate and magnesium stearate, various nonmagnetic inorganic fine particles such as talc, bentonite and carbon black, magnetic inorganic fine particles such as magnetite and ferrite, and titanium oxide. Particularly preferred. In addition to the inorganic fine powder, resin fine particles made of styrene resin, acrylic resin, benzoguanamine resin, melamine resin, silicone resin, vinylidene fluoride resin and the like can be used as a fluidity adjusting agent or a charge adjusting agent, for example.

  The externally added fine particles to be externally added to the surface of the toner base particles can be appropriately selected from various inorganic or organic fine particles. Among these externally added fine particles, silica, titanium oxide, alumina, zinc oxide and the like are suitably used as the inorganic fine particles, and styrene resins, acrylic resins, epoxy resins, melamine resins, etc. are used as the organic fine particles. Fine particles can be used. In particular, the externally added fine particles are formed on the surface of the inorganic or organic fine particles by using a silane coupling agent, a titanate coupling agent, a silicone oil, a modified silicone oil, a silicone varnish, a fluorinated silane coupling agent, or a fluorinated silicone oil. In addition, it is also possible to use those that have been subjected to a surface treatment such as hydrophobization with a treating agent such as a coupling agent having an amino group or a quaternary ammonium base. Two or more kinds of the treatment agents can be used in combination.

  The externally added fine particles preferably have an average particle diameter of 0.001 to 3 μm. However, the magnetic toner of the present invention includes an inorganic fine powder having a primary particle diameter of 40 nm to 70 nm as an inorganic fine powder. It is essential to be added. Examples of the inorganic fine powder include titanium oxide, magnetite, ferrite, cerium oxide, strontium titanate, barium titanate, talc, talcite, silicon nitride, silicon carbide, titanium nitride, and silica. preferable.

  Titanium oxide includes rutile type, anatase type, a mixture of anatase type and rutile type. Each surface is made of alkylsilane, octyltrimethoxysilane, isobutyltrimethoxysilane, organosilane, organosilane, silicone oil, etc. Some of them are surface-treated, and among them, anatase-type titanium oxide surface-treated with organosilane and silicon oil is preferable.

  When the primary particle size is 40 nm or more and 70 nm or less, it functions as a buffer between the toner and the toner or member, the contact between both is relaxed, and the increase in charge of the toner is smaller than that with a primary particle size of less than 40 nm. It is stable and easy to make uniform, and density unevenness under low image density and low temperature and low humidity environment is eliminated. On the other hand, if the primary particle size is larger than 70 nm, the chances of contact between the toner and the toner, and the toner and the charge imparting member are reduced, and the toner is not sufficiently charged. It is easy to cause. If an inorganic fine powder having a primary particle size of 40 nm or more and 70 nm or less is added, there may be no problem even if an inorganic fine powder having a primary particle size of less than 40 nm is added. A plurality of these can also be blended. Further, the externally added fine particles may be used in combination of two or more different types, and may be used in combination with a surface-treated and non-surface-treated one or with a different surface-treated one. In addition, a positively chargeable one and a negatively chargeable one can be used in appropriate combination. The amount of the additive used depends on the type and purpose of the additive, but is usually about 0.05 to 10 parts by weight with respect to 100 parts by weight of the developer. The average particle diameter of the externally added fine particles can be determined by observation with an electron microscope.

As a method for externally adding externally added fine particles to toner base particles, a method of adding and blending using a high-speed stirrer such as a Henschel mixer is also known, but in order to improve blocking resistance at high temperatures, The additive fine particles are preferably fixed on the surface of the toner base particles. As a fixing method, use of an apparatus capable of applying a compressive shear stress (hereinafter referred to as a compression shearing apparatus) or an apparatus capable of melting or softening the surface of a toner base particle (hereinafter referred to as a particle surface melting apparatus). Etc. By this fixing treatment, the externally added fine particles are firmly fixed to the surface of the toner base particles without substantial pulverization of the toner base particles, so that the blocking resistance under high temperature storage is improved and even during continuous shooting. It is possible to produce toner that is less likely to be fused to the copier / printer member.

  The compression shearing apparatus generally has a narrow gap composed of a head surface and a head surface, a head surface and a wall surface, or a wall surface and a wall surface that move relative to each other while maintaining a gap. By forcibly passing through the gap portion, compressive stress and shear stress are applied to the particle surface without being substantially pulverized. Examples of the compression shearing apparatus used include a mechanofusion apparatus manufactured by Hosokawa Micron Corporation.

In general, the particle surface melting apparatus is configured so that a mixture of base fine particles and externally added fine particles can be instantaneously heated to a melting start temperature of the base fine particles or higher by using a hot air stream or the like to fix the externally added fine particles. Examples of the particle surface melting apparatus used include a surfing system manufactured by Nippon Pneumatic Co., Ltd.
Further, a lubricant such as a metal soap or a metal stearate can be added internally or externally. These additives are usually used in an amount of 0.05 to 10 parts by weight with respect to 100 parts by weight of the developer. Production of the developer according to the present invention from each of the components described above can be performed according to a conventional method. Usually, first, a binder resin, a charge control agent and a magnetic material, and a colorant, an additive and other components added as necessary are uniformly dispersed and mixed with a mixer, and the resulting mixture is then sealed in a sealed kneader or It is melt-kneaded with a single-screw or twin-screw extruder, etc., cooled, coarsely crushed with a crusher, hammer mill, etc., finely pulverized with a jet mill, a high-speed rotor rotary mill, etc., and an air classifier (for example, an inertia classifier) A method of classification using an elbow jet, a centrifugal classification microplex, a DS separator, or the like is employed.

Formula (1) 160 <X · Z / Y <270
X: Magnetic powder content ratio [%],
Y: Charge control agent strength ratio Z: endothermic peak [mJ / mg] obtained from a calibration curve representing the amount of charge control agent added, measured with an ultraviolet / visible spectrophotometer after the solution dissolved in THF and filtered ]
Here, X represents the magnetic powder content in the toner calculated by measuring the amount of magnetic powder in the toner using a thermobalance, and Y represents a solution obtained by dissolving the toner in THF and filtering the ultraviolet / visible light spectrometer. The strength ratio of the charge control agent determined from the calibration curve representing the amount of the charge control agent added measured in (1), Z is a DSC curve measured by a differential scanning calorimeter (DSC), from 60 ° C. when the temperature rises The peak area appearing between 160 ° C is shown.

Up to now, the usage amount of magnetic powder, charge control agent, wax, etc. has been added to each 100 parts by weight of the binder resin so that individual effects can be manifested. Not necessarily. Therefore, it has been found that the formula (1) is an indicator of whether each raw material is dispersed to function effectively or whether the dispersed state is good or bad.
Although the toner that does not have inorganic fine particles having a primary particle size of 40 nm or more and 70 nm or less but satisfies the formula (1) has excellent performance in image characteristics such as image density, resolution, and gradation in a normal environment, In a low-temperature and low-humidity environment, voids and image density unevenness may appear. As defined in the present invention, the toner satisfying the formula (1) is added, and inorganic fine particles having a primary particle size of 40 nm or more and 70 nm or less are added to the surface of the toner, thereby preventing the occurrence of image density unevenness called wave. be able to. This is because the primary particle size is 40 nm or more and 70 nm or less, so that the contact between the toners and between the toner and the member that imparts charge to the toner is alleviated, and the increase in charge of the toner and the non-uniform charging are suppressed. It is.

  In the present invention, from the viewpoint of more remarkably exhibiting the effect of suppressing the occurrence of image density unevenness in a low-temperature and low-humidity environment, the ratio X / Y of X to Y is preferably 70.0 or less. It is more preferably 0 or less, and further preferably 60.0 or less. Although a minimum is not specifically limited, Usually, it is 40.0 or more.

<Electrophotographic cartridge>
The electrophotographic cartridge in which the magnetic toner of the present invention is used is not particularly limited as long as it has a developing sleeve provided so that the photosensitive member and the magnetic toner are conveyed onto the photosensitive member and can be developed. From the viewpoint of exerting the effect more remarkably, it is preferable that the developing sleeve is an aluminum base subjected to nickel plating.
Regarding other members of the electrophotographic cartridge, known members may be appropriately selected and used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. “Parts” means “parts by weight” unless otherwise specified.

<Measurement Method of Magnetic Powder Content (X) in Toner>
The magnetic powder content (X) in the toner is determined as follows using a thermobalance (TGA) and fluorescent X-rays. Using a thermobalance (TGA), about 15 mg of toner is placed in a platinum pan and the ash content (a%) after heating in air at 800 ° C. for 5 minutes is determined. Here, the ash content is defined as a (%) = (sample weight after heating at 800 ° C. in air for 5 minutes) ÷ (initial sample weight at room temperature) × 100. Next, about 5 g of toner is put into a die having a diameter of 40 mm, and pressed with a hydraulic press at 25 tons for 30 seconds to form a pellet. Rigaku X-ray device ZSX Pri
The order analysis is performed with mus, and the oxide equivalent concentration of the detection element is determined for the non-standard sample by the software and coefficient of the apparatus. The total concentration of metal oxides excluding iron and manganese is b%. Thus, the amount X of magnetic powder in the toner is calculated by (a−b)%.

<Intensity ratio (Y) of charge control agent in toner>
The strength ratio (Y) of the charge control agent in the toner is about 30 times when 10 ± 1 mg of toner is put in a glass vial, precisely weighed to the order of 0.1 mg, 10 mL of tetrahydrofuran (THF) is added and then the lid is closed. After shaking, the toner is dissolved by treating in an ultrasonic dissolution tank for 5 minutes.
Next, the vial is allowed to stand, and after the magnetic powder has generally settled, the supernatant is filtered through a syringe filter (Whatman GD / X 25 mm diameter, 0.2 μm pore diameter) into a spectrophotometer cell (optical path length 10 mm). When the sedimentation of the magnetic powder is insufficient, the vial may be placed on a strong magnet and the magnetic powder may be attracted to the bottom.

  A wavelength range of 300 nm to 800 nm is scanned at 400 nm / min with an ultraviolet / visible spectrophotometer, and the absorbance of the peak due to the charge control agent is determined. When the baseline is not zero, 700 to 800 nm is taken as the baseline, and it is extrapolated to the absorption peak position of the charge control agent to obtain the baseline absorbance, and is subtracted from the peak absorbance. Based on a calibration curve prepared by dissolving the charge control agent in THF in advance and measuring the absorbance under the same conditions, the absorbance by the charge control agent is converted into the concentration in the toner.

<Peak area (Z) of wax in toner>
The peak area (Z) of the wax in the toner is determined by a differential scanning calorimeter (DSC) as follows. 10 ± 1 mg of toner is put in an aluminum pan, precisely weighed to the order of 0.01 mg, and an aluminum pan filled with 7 mg of aluminum oxide is used as a reference and measured under the same temperature conditions as wax in a nitrogen stream. The wax endothermic peak area Z (mJ / mg) per unit weight of toner is determined from the peak due to wax at the second temperature rise.

[Example 1]
100 parts by weight of styrene acrylic resin, 85 parts by weight of magnetite magnetic substance A, 2 parts by weight of a charge control agent, and 6 parts by weight of wax were dispersed and mixed, and then melt-kneaded using a twin screw extruder. After cooling, it was coarsely pulverized with a hammer mill and then finely pulverized with a supersonic jet mill pulverizer. The obtained powder is classified with an air classifier to obtain a toner having a particle size of 8.5 μm, and further, 0.9 parts by weight of hydrophobic silica and 100 parts by weight of hydrotalcite are added to 100 parts by weight of the toner using a super mixer. 0.1 part by weight and 0.6 part by weight of titanium oxide (anatase type) having a primary particle diameter of 50 nm were externally added to obtain toner 1.

  At this time, the value of X · Z / Y of the toner 1 was 171. Subsequently, the toner 1 is inserted into a 35 ppm printer with an organic photoreceptor and a magnetic one-component electrostatic printing recording method, and an endurance test of image characteristics is performed under a normal environment, and a black solid portion is measured with a Macbeth densitometer. As a result, the change in image density immediately after the start of durability and after the end of durability was 0.08. In addition, when an actual image was taken at a temperature of 10 ° C. and a humidity of 20% RH, no image defects such as uneven image density and voids occurred.

[Example 2]
100 parts by weight of styrene acrylic resin, 95 parts by weight of magnetite magnetic substance A, 2 parts by weight of charge control agent, and 6 parts by weight of wax were dispersed and mixed, and then melt-kneaded using a twin screw extruder. After cooling, it was coarsely pulverized with a hammer mill and then finely pulverized with a supersonic jet mill pulverizer. The obtained powder was classified with an air classifier to obtain a toner having a particle size of 8.5 μm, and further, 0.9 parts by weight of hydrophobic silica and 100% by weight of hydrotalcite with respect to 100 parts by weight of the toner by a super mixer. Toner 2 was obtained by externally adding 1 part and 0.6 parts by weight of titanium oxide (anatase type) having a primary particle diameter of 50 nm.

  At this time, the value of X · Z / Y of toner 2 was 210. Next, the toner 2 is inserted into a 35 ppm printer with an organic photoreceptor and a magnetic one-component electrostatic printing recording method, and an endurance test of image characteristics is performed under a normal environment, and a black solid portion is measured with a Macbeth densitometer. As a result, the change in image density immediately after the start of durability and after the end of durability was 0.09. Further, when an actual image was taken at a temperature of 10 ° C. and a humidity of 20 RH%, image defects such as uneven image density and voids did not appear.

[Example 3]
After 100 parts by weight of styrene acrylic resin, 110 parts by weight of magnetite magnetic substance A, 2 parts by weight of charge control agent and 6 parts by weight of wax A were dispersed and mixed, they were melt-kneaded using a twin screw extruder. After cooling, it was coarsely pulverized with a hammer mill and then finely pulverized with a supersonic jet mill pulverizer. The obtained powder is classified with an air classifier to obtain a toner having a particle size of 8.0 μm, and further, 0.9 part by weight of hydrophobic silica and 100% by weight of hydrotalcite with respect to 100 parts by weight of the toner by a super mixer. Toner 3 was obtained by externally adding 1 part by weight and 0.6 part by weight of titanium oxide (anatase type) having a primary particle diameter of 50 nm.

  The value of X · Z / Y of toner 3 at this time was 254. Subsequently, the toner 3 is inserted into a 35 ppm printer with an organic photoreceptor and a magnetic single component electrostatic printing recording method, and an endurance test of image characteristics is performed under a normal environment, and a black solid portion is measured with a Macbeth densitometer. As a result, the change in image density immediately after the start of durability and after the end of durability was 0.10. Further, when an actual image was taken at a temperature of 10 ° C. and a humidity of 20 RH%, image defects such as uneven image density and voids did not appear.

[Comparative Example 1]
100 parts by weight of a styrene acrylic resin, 95 parts by weight of magnetite magnetic substance B, 1 part by weight of a charge control agent, and 4 parts of wax B were dispersed and mixed, and then melt-kneaded using a twin screw extruder. After cooling, it was coarsely pulverized with a hammer mill and then finely pulverized with a supersonic jet mill pulverizer. The obtained powder was classified with an air classifier to obtain a toner having a particle size of 8.5 μm, and 0.9 parts by weight of hydrophobic silica and 0.3 parts by weight of magnetite were externally added by a super mixer. Toner 4 was obtained.

  The value of X · Z / Y of toner 4 at this time was 159. Subsequently, the toner 4 is inserted into a 35 ppm printer with a magnetic one-component electrostatic printing method having an organic photoconductor, and an endurance test of image characteristics is performed under a normal environment, and a black solid portion is measured with a Macbeth densitometer. As a result, the change in image density immediately after the start of durability and after the end of durability was 0.17. Further, when an actual image was taken at a temperature of 10 ° C. and a humidity of 20 RH%, image density unevenness appeared.

[Comparative Example 2]
After 100 parts by weight of styrene acrylic resin, 85 parts by weight of magnetite magnetic substance A, 2 parts by weight of charge control agent, and 4 parts by weight of wax B were dispersed and mixed, they were melt-kneaded using a twin screw extruder. After cooling, it was coarsely pulverized with a hammer mill and then finely pulverized with a supersonic jet mill pulverizer. The obtained powder was classified with an air classifier to obtain a toner having a particle size of 8.5 μm, and further, 0.9 parts by weight of hydrophobic silica and 100% by weight of hydrotalcite with respect to 100 parts by weight of the toner by a super mixer. Toner 5 was obtained by externally adding 1 part by weight.

  The value of X · Z / Y of toner 5 at this time was 81. Subsequently, the toner 5 is inserted into a 35 ppm printer with a magnetic one-component electrostatic printing method having an organic photoconductor, and an endurance test of image characteristics is performed under a normal environment, and a black solid portion is measured with a Macbeth densitometer. As a result, the change in image density immediately after the start of durability and after the end of durability was 0.15. Further, when an actual image was taken at a temperature of 10 ° C. and a humidity of 20 RH%, image density unevenness appeared.

[Comparative Example 3]
100 parts by weight of styrene acrylic resin, 105 parts by weight of magnetite magnetic substance C, 1 part by weight of a charge control agent, and 6 parts by weight of wax A were dispersed and mixed, and then melt-kneaded using a twin screw extruder. After cooling, it was coarsely pulverized with a hammer mill and then finely pulverized with a supersonic jet mill pulverizer. The obtained powder is classified with an air classifier to obtain a toner having a particle size of 8.5 μm. Further, with a super mixer, 1.5 parts by weight of hydrophobic silica and 0.3 parts by weight of magnetite with respect to 100 parts by weight of the toner. Toner 6 was obtained by externally adding parts.

  At this time, the value of X · Z / Y of the toner 6 was 431. Subsequently, the toner 6 is inserted into a 35 ppm printer with an organic photoreceptor and a magnetic one-component electrostatic printing recording system, and an endurance test of image characteristics is performed under a normal environment, and a black solid portion is measured with a Macbeth densitometer. As a result, the change in image density immediately after the start of durability and after the end of durability was 0.14. Further, when an actual image was taken at a temperature of 10 ° C. and a humidity of 20 RH%, image density unevenness appeared.

[Comparative Example 4]
100 parts by weight of a styrene acrylic resin, 95 parts by weight of magnetite magnetic substance A, 2 parts by weight of a charge control agent and 6 parts by weight of wax A were dispersed and mixed, and then melt-kneaded using a twin screw extruder. After cooling, it was coarsely pulverized with a hammer mill and then finely pulverized with a supersonic jet mill pulverizer. The obtained powder is classified with an air classifier to obtain a toner having a particle size of 8.5 μm, and further 0.9 parts by weight of hydrophobic silica, 0.1 parts by weight of hydrotalcite and primary particles by a super mixer. Toner 7 was obtained by externally adding 0.6 parts by weight of titanium oxide having a diameter of 15 nm.

  At this time, the value of X · Z / Y of the toner 7 was 171. Next, the toner 7 is inserted into a 35 ppm printer with a magnetic one-component electrostatic printing method having an organic photoconductor, and an endurance test of image characteristics is performed under a normal environment, and a black solid portion is measured with a Macbeth densitometer. As a result, the change in image density immediately after the start of durability and after the end of durability was 0.06. Further, when an actual image was taken at a temperature of 10 ° C. and a humidity of 20% RH, an image defect with uneven image density appeared.

[Comparative Example 5]
100 parts by weight of styrene acrylic resin, 105 parts by weight of magnetite magnetic substance C, 1 part by weight of a charge control agent, and 6 parts by weight of wax A were dispersed and mixed, and then melt-kneaded using a twin screw extruder. After cooling, it was coarsely pulverized with a hammer mill and then finely pulverized with a supersonic jet mill pulverizer. The obtained powder is classified with an air classifier to obtain a toner having a particle size of 8.5 μm, and further, 0.9 parts by weight of hydrophobic silica and 0.4 parts by weight of magnetite with respect to 100 parts by weight of the toner by a super mixer. Toner 8 was obtained by externally adding 0.6 parts by weight of 0.1 part of hydrotalcite, 0.03 part of zinc stearate, and titanium oxide (anatase type) having a primary particle diameter of 50 nm.

  At this time, the value of X · Z / Y of the toner 8 was 445. Subsequently, the toner 8 is inserted into a 35 ppm printer of an organic photosensitive member having a magnetic one-component electrostatic printing method, and an endurance test of an image characteristic is performed under a normal environment, and a black solid portion is measured with a Macbeth densitometer. As a result, the change in image density immediately after the start of durability and after the end of durability was 0.27. In addition, when the environment was photographed at a temperature of 10 ° C. and a humidity of 20 RH%, image density unevenness did not appear.

Claims (5)

A magnetic toner containing at least a binder resin, wax, and magnetic powder, wherein the content ratio of the magnetic powder to the toner determined by measurement with a thermal balance of the magnetic toner is X (%), and the magnetic toner is added to THF. The strength ratio of the charge control agent determined from the calibration curve representing the amount of the charge control agent added to the dissolved and filtered solution measured with an ultraviolet / visible spectrophotometer, 60 ° C. determined by the DSC measurement of the magnetic toner When the peak area appearing at 160 ° C. is Z (mJ / mg),
A toner having X, Y and Z satisfying the following formula (1) and having inorganic fine particles having an average primary particle size of 40 nm or more and 70 nm or less on the surface of the magnetic toner.
160 <X · Z / Y <270 Formula (1)   The magnetic toner according to claim 1, wherein the inorganic fine particles are titanium oxide.   The magnetic toner according to claim 2, wherein the titanium oxide is an anatase type.   The magnetic toner according to claim 2, wherein the titanium oxide contains an organosilane compound.   An electrophotographic cartridge comprising the magnetic toner according to any one of claims 1 to 4, a photosensitive member, and a developing sleeve provided on the photosensitive member so that the magnetic toner can be conveyed and developed. An electrophotographic cartridge, wherein the developing sleeve is a nickel-plated aluminum substrate.