Magnetic carrier, two-component developer, and method for manufacturing magnetic carrier

Abstract

To provide a magnetic carrier which suppresses the abrasion of a coating layer of the magnetic carrier and shows the excellent charge-imparting property, leak suppression property and image density stability.SOLUTION: A magnetic carrier includes a magnetic core particle and a magnetic carrier particle that has a coating layer of an organic silicon polymer on the magnetic core particle surface. The organic silicon polymer has a structure expressed by the following formula (T3). In 29Si-NMR measurement for THF insoluble of the organic silicon polymer, a ratio ST3 of a peak area of the structure expressed by the following formula (T3) to the entire peak area of the organic silicon polymer is equal to or greater than 0.05. In the roughness curve measured by a scan type probe microscope of the magnetic carrier particle, a ratio (σ / RSm) to RSm of a standard deviation σ between the average length RSm of a roughness curve element of the magnetic carrier particle and the length of a portion having irregularity for one cycle is within a specific range. (T3) R-Si(O1 / 2)3. In the formula, R represents the specific substituent group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a magnetic carrier, a two-component developer, and a method for producing the magnetic carrier, which are used in electrophotography, electrostatic recording, electrostatic printing, and the like. [Background technology]

[0002] In recent years, as electrophotographic full-color copying machines have become widespread, there has been a demand for not only further speed and higher image quality, but also additional performance improvements in terms of maintenance costs, such as maintenance-free performance. Specific maintenance-free measures include the development of toners and magnetic carriers that are resistant to deterioration even during long-term image output, in order to reduce the frequency of developer replacement by service personnel. Therefore, Patent Document 1 proposes a magnetic carrier in which magnetic core particles are coated with a resin having a specific structure, thereby reducing the wear of the coating resin even during long-term image output and enabling stable charging of the toner. Furthermore, Patent Document 2 proposes a magnetic carrier that can stably impart a charge to toner by adding filler particles to the coating layer of the magnetic carrier, thereby suppressing wear of the coating resin due to collisions between magnetic carrier particles. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-244026 [Patent Document 2] Japanese Patent Application Laid-Open No. 2017-097290 Summary of the Invention [Problem to be solved by the invention]

[0004] All of the magnetic carriers described in the above documents exhibit a certain degree of effectiveness in suppressing wear of the coating layer. However, as the speed of copiers increases, the load on the magnetic carrier from factors such as the developer agitator screw tends to increase. It has been found that the magnetic carriers described in the above documents, in which the coating layer is mostly composed of organic materials, are unable to fully suppress wear of the coating resin. It has also been found that wear of the coating resin can cause changes in the ability to impart charge to the toner, leakage (charge is injected from the developer carrier to the electrostatic image through the magnetic carrier, causing the potential of the electrostatic latent image carrier to become equipotential), and fluctuations in image density. For these reasons, there is an urgent need to develop a magnetic carrier that can suppress wear of the coating layer of the magnetic carrier and that exhibits excellent charge imparting properties, leakage suppression properties, and image density stability even during long-term image output. The present disclosure provides a magnetic carrier that suppresses wear of the coating layer of the magnetic carrier and exhibits excellent charge imparting properties, leakage suppression properties, and image density stability, a two-component developer containing the magnetic carrier, and a method for producing the magnetic carrier. [Means for solving the problem]

[0005] The magnetic carrier of the present disclosure is A magnetic carrier having magnetic core particles and magnetic carrier particles having a coating layer of an organosilicon polymer on the surface of the magnetic core particles, The organosilicon polymer has a structure represented by the following formula (T3): The organosilicon polymer is a condensation polymer selected from the group consisting of the following (1) to (8): (1) a condensation polymer of 3-aminopropyltriethoxysilane and methyltriethoxysilane, (2) condensation polymer of methyltriethoxysilane, (3) condensation polymer of phenyltriethoxysilane, (4) Condensation polymer of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and methyltriethoxysilane, (5) Condensation polymer of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and ethyltriethoxysilane, (6) Condensation polymer of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and n-propyltriethoxysilane (7) Condensation polymer of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and hexyltriethoxysilane, (8) Condensation polymer of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and phenyltriethoxysilane, The tetrahydrofuran insoluble portion of the organosilicon polymer 29In Si-NMR measurement, the ratio ST3 of the peak area of ​​the structure represented by the following formula (T3) to the total peak area of ​​the organosilicon polymer is 0. 70 That's all, In the roughness curve of the magnetic carrier particles measured by a scanning probe microscope, The average length (RSm) of the roughness curve element of the magnetic carrier particle is 20 nm or more and 500 nm or less, and the standard deviation σ of the length of the portion where one period of unevenness occurs is The ratio (σ / RSm) is 0.80 or less. R-Si(O 1 / 2 )3(T3) In the formula, R represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a 3-aminopropyl group, or an N-2-(aminoethyl)-3-aminopropyl group. In addition, the two-component developer of the present disclosure is A two-component developer containing a toner and a magnetic carrier, the toner has toner particles containing a binder resin, The magnetic carrier is characterized by being the above-mentioned magnetic carrier. Furthermore, the method for producing the magnetic carrier of the present disclosure includes the steps of: Dispersing the magnetic core particles in an aqueous medium; and This method includes a step of coating the surface of the magnetic core particles with an organosilicon polymer. [Effects of the Invention]

[0006] The present disclosure can provide a magnetic carrier that suppresses wear of the coating layer of the magnetic carrier and exhibits excellent charge-imparting properties, leakage suppression properties, and image density stability, a two-component developer containing the magnetic carrier, and a method for producing the magnetic carrier. [Brief explanation of the drawings]

[0007] [Figure 1] Curve fitting example DETAILED DESCRIPTION OF THE INVENTION

[0008] The expressions "XX or more and YY or less" or "XX to YY" that represent a numerical range mean a numerical range including the endpoints, that is, the lower limit and the upper limit, unless otherwise specified. When numerical ranges are stated in stages, the upper and lower limits of each numerical range can be combined in any way.

[0009] The magnetic carrier of the present disclosure is A magnetic carrier having magnetic core particles and magnetic carrier particles having a coating layer of an organosilicon polymer on the surface of the magnetic core particles, The organosilicon polymer has a structure represented by the following formula (T3): The tetrahydrofuran insoluble portion of the organosilicon polymer 29 In Si-NMR analysis, the ratio ST3 of the peak area of ​​the structure represented by the following formula (T3) to the total peak area of ​​the organosilicon polymer is 0.05 or more: In the roughness curve of the magnetic carrier particles measured by a scanning probe microscope, The magnetic carrier particles are characterized in that the average length of the roughness curve elements (RSm) is 20 nm or more and 500 nm or less, and the ratio (σ / RSm) of the standard deviation σ of the length of the portion where one period of unevenness occurs to the RSm is 0.80 or less. R-Si(O 1 / 2 )3(T3) In the formula, R represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, an amino group, or an alkylamino group having 1 to 5 carbon atoms.

[0010] The present inventors have conducted research into suppressing wear of the coating layer of a magnetic carrier. In order to suppress wear of the coating layer, the present inventors have tried adding filler particles of various particle sizes and types to the coating layer, and changing the coating layer formation state, such as multi-layering or thick layering, but have not been able to fundamentally solve the problem. The reason for this is thought to be that the coating layer is mostly composed of organic matter. Therefore, the present inventors have also investigated magnetic carriers without a coating layer. However, the resistance adjustment by the metal element ratio of the magnetic core particles or the oxidation state due to the firing atmosphere is not sufficient without a coating layer. The magnetic carrier without a coating layer could not obtain the high surface resistance of the magnetic carrier with a coating layer, and the magnetic carrier without a coating layer could not stably impart a charge to the toner. On the other hand, no wear of the magnetic core particles themselves was observed. The inventors therefore believed that forming a coating layer using a material that is organic but exhibits inorganic properties could solve this problem, and came up with the idea of ​​coating the surface of the magnetic core particles with an organosilicon polymer.

[0011] Organosilicon polymers are tetrahydrofuran (THF) insoluble 29 In Si-NMR analysis, the ratio ST3 of the peak area of ​​the structure represented by formula (T3) to the total peak area of ​​the organosilicon polymer is 0.05 or more. An ST3 of 0.05 or more indicates the formation of a three-dimensional crosslinked siloxane structure, which results in the development of wear resistance. Therefore, even during long-term image output, wear of the coating layer of the magnetic carrier can be suppressed, and excellent charge imparting properties to the toner can be obtained. In addition, since the surface free energy of the magnetic carrier surface can be reduced, toner spent on the magnetic carrier surface can be suppressed, and excellent image density stability can be obtained. On the other hand, a silicone resin coating layer, for example, corresponds to a relationship where ST3 is less than 0.05. This means that a three-dimensional crosslinked structure is not formed, and abrasion resistance is not exhibited. As a result, over a long period of image output, the coating layer of the magnetic carrier wears out, and excellent charge imparting properties to the toner cannot be obtained. ST3 can be controlled by the type and amount of organosilicon compound used in forming the organosilicon polymer, as well as the reaction temperature, reaction time, and pH of the hydrolysis and condensation polymerization during formation of the organosilicon polymer. ST3 is preferably 0.40 or more, more preferably 0.50 or more, and even more preferably 0.60 or more. There is no particular upper limit, but it is preferably 0.85 or less, more preferably 0.75 or less.

[0012] In addition, in a roughness curve of the magnetic carrier particles measured with a scanning probe microscope, the average length of the roughness curve elements (RSm) of the magnetic carrier particles is 20 nm or more and 500 nm or less, and the ratio (σ / RSm) of the standard deviation σ of the length of the portion where one period of unevenness occurs to the RSm is 0.80 or less. The RSm in the above range means that minute irregularities are formed on the surface of the magnetic carrier, which prevents toner from being spent on the surface of the magnetic carrier, thereby achieving excellent image density stability. RSm can be controlled by the type and amount of organosilicon compound used to form the organosilicon polymer, the reaction temperature, reaction time, and pH of the hydrolysis and condensation polymerization during organosilicon polymer formation, and the type and amount of dispersion stabilizer and surfactant described below. Furthermore, σ / RSm in the above range means that minute irregularities exist continuously on the surface of the magnetic carrier, which suppresses toner spent at any part of the surface of the magnetic carrier, thereby achieving excellent image density stability. σ / RSm can be controlled by the type and amount of organosilicon compound used to form the organosilicon polymer, the reaction temperature, reaction time, and pH of the hydrolysis and condensation polymerization during organosilicon polymer formation, and the type and amount of dispersion stabilizer and surfactant, as described below.

[0013] RSm is preferably 20 nm or more and 300 nm or less. σ / RSm is preferably 0.60 or less. There is no particular lower limit to σ / RSm, but it is preferably 0.10 or more, and more preferably 0.20 or more.

[0014] R in the structure represented by the above formula (T3) is an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2, and even more preferably 1), a phenyl group, an amino group, or an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3, more preferably 1 or 2). When R is the above functional group, the molecular density is highly controlled due to the small steric hindrance, and a strong three-dimensional crosslinked structure is formed. This results in abrasion resistance. As a result, abrasion of the magnetic carrier coating layer can be suppressed even during long-term image output, and excellent charge imparting properties to the toner can be obtained. Furthermore, silicon atoms are preferably present on the surface of the magnetic carrier, and the surface free energy of the magnetic carrier surface can be reduced, so that toner spent on the magnetic carrier surface is suppressed, and excellent image density stability is obtained. On the other hand, if R is not one of the above functional groups, the molecular density is low, which means that a strong three-dimensional cross-linked structure is not formed, and wear resistance is not achieved. As a result, wear occurs in the coating layer of the magnetic carrier during long-term image output, and excellent charge imparting properties to the toner cannot be obtained. Furthermore, when R is an alkyl group having 1 to 6 carbon atoms or a phenyl group, the toner tends to be positively charged. When R is an amino group or an alkylamino group having 1 to 5 carbon atoms, the toner tends to be negatively charged. R can be selected appropriately according to the target chargeability of the toner. The alkylamino group preferably has the following structure: -(CH2) p -X-(CH2) q -NH2 X represents a single bond or —NH—, and p and q each independently represent an integer of 0 to 5, provided that p+q is 1 to 5, and preferably 2 to 4. The alkylamino group more preferably has the following structure: -(CH2) p -NH2 p represents an integer of 0 to 5, and preferably 2 to 4.

[0015] In X-ray photoelectron spectroscopy analysis of the magnetic carrier, it is preferable that the ratio of the silicon atom concentration dSi (dSi / [dSi+dO+dC]) to the sum (dSi+dO+dC) of the silicon atom concentration dSi, the oxygen atom concentration dO, and the carbon atom concentration dC in the surface layer of the magnetic carrier is 2.5 atomic % or more, from the viewpoint of excellent image density stability. The above proportion is more preferably 10.0 atomic % or more, even more preferably 15.0 atomic % or more, and even more preferably 20.0 atomic % or more. There is no particular upper limit, but it is preferably 40.0 atomic % or less, more preferably 30.0 atomic % or less. By ensuring that the silicon atom concentration is within the above range, silicon atoms are suitably present on the magnetic carrier surface, and the surface free energy of the magnetic carrier surface can be reduced, thereby suppressing toner spent on the magnetic carrier surface and achieving excellent image density stability. (dSi / [dSi+dO+dC]) can be controlled by the structure of R in the above formula (T3), as well as the reaction temperature, reaction time, and pH of the hydrolysis and condensation polymerization during the formation of the organosilicon polymer.

[0016] From the viewpoint of excellent charge stability, the tetrahydrofuran-insoluble portion of the organosilicon polymer 29 In Si-NMR measurements, the ratio of silicon-bonded O to the total peak area of ​​the organosilicon polymer 1 / 2 When the ratio of the peak area of ​​the structure in which the number of SX2 is 2.0 is defined as SX2, the ratio of ST3 to SX2, ST3 / SX2, is preferably 1.0 or more. ST3 / SX2 is preferably 1.5 or more, more preferably 2.0 or more. There is no particular upper limit, but it is preferably 3.5 or less, more preferably 2.5 or less. Satisfying the relationship ST3 / SX2 ≥ 1.0 means that a three-dimensional cross-linked structure with a siloxane structure is formed, resulting in wear resistance. As a result, even during long-term image output, wear on the coating layer of the magnetic carrier is suppressed, resulting in excellent charge imparting properties to the toner. ST3 / SX2 can be controlled by the type and amount of organosilicon compound used to form the organosilicon polymer, as well as the reaction temperature, reaction time, and pH of the hydrolysis and condensation polymerization during the formation of the organosilicon polymer.

[0017] The surface of the magnetic carrier preferably has irregularities. From the viewpoint of image density stability, the arithmetic mean surface roughness Ra of the magnetic carrier surface preferably satisfies 10 nm≦Ra≦2000 nm, more preferably 10 nm≦Ra≦200 nm, and even more preferably 50 nm≦Ra≦200 nm. When Ra is within the above range, the contact area between the toner and the magnetic carrier is reduced from the viewpoint of curvature, thereby reducing the non-electrostatic adhesion force, thereby suppressing toner spent on the magnetic carrier surface and achieving excellent image density stability. Ra can be controlled by the type and amount of organosilicon compound used to form the organosilicon polymer, the reaction temperature, reaction time, and pH of the hydrolysis and condensation polymerization during organosilicon polymer formation, and the type and amount of dispersion stabilizer and surfactant described below.

[0018] From the viewpoints of coating layer detachment, leakage suppression, and image stability, the magnetic carrier preferably has a primer layer containing a vinyl polymer between the magnetic core particle and the organosilicon polymer coating layer, and more preferably has a primer layer made of a vinyl polymer. The vinyl polymer preferably has a structure represented by the following formula (1):

[0019] [ka]

[0020] (R V1 represents H, CH3 or C2H5 (preferably H or CH3), R V2 indicates H or CH3.) When the vinyl polymer represented by formula (1) is present in the primer layer, the affinity between the ester moiety of the vinyl polymer and the silanol moiety of the organosilicon polymer enhances adhesion. This prevents peeling of the coating layer even during long-term image output, improving leak suppression and image stability. In addition, R V1 However, by being H, CH3 or C2H5, appropriate hydrophilicity is ensured, and the affinity with the silanol moiety of the organosilicon polymer increases adhesion. The content of the structure represented by formula (1) in the vinyl polymer is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.

[0021] The vinyl polymer preferably has a monomer unit derived from a cycloalkyl (meth)acrylate. The cycloalkyl group preferably has 4 to 10 carbon atoms, more preferably 5 to 8. The vinyl polymer more preferably has a monomer unit derived from a cyclohexyl (meth)acrylate. The content of the monomer unit derived from a cycloalkyl (meth)acrylate in the vinyl polymer is preferably 40 to 90% by mass, more preferably 50 to 80% by mass.

[0022] The content of the vinyl polymer in the primer layer is preferably 0.1 to 2.0 parts by mass relative to 100.0 parts by mass of the magnetic core particles, from the viewpoints of detachment of the coating layer, suppression of leakage, and image stability, more preferably 0.5 to 1.8 parts by mass, and even more preferably The content is generally 0.8 to 1.7 parts by mass. By ensuring that the amount of vinyl polymer is within this range, adhesion to the organosilicon polymer is enhanced, which in turn prevents peeling of the coating layer even during long-term image output, improving leak suppression and image stability.

[0023] When a degradation test was conducted using a two-component developer containing 92.0 parts of magnetic carrier and 8.0 parts of toner, in which 10,000 images with an image ratio of 1% were printed at a process speed of 377 mm / sec, it was preferable that the amount of abrasion of the organosilicon polymer coating layer be less than 2.0% by weight of the amount of organosilicon polymer before the test, from the viewpoints of coating layer detachment, leak suppression, and image stability. More preferably, it is less than 1.5% by weight, even more preferably less than 1.0% by weight, and even more preferably less than 0.5% by weight. There is no particular lower limit, but it is preferably 0.0% by weight or more, and more preferably 0.05% by weight or more. Having the amount of abrasion within the above range means that abrasion of the coating layer is suppressed, improving leak suppression and image stability. The amount of coating layer scraping can be controlled by the type and amount of organosilicon compound used to form the organosilicon polymer, the reaction temperature, reaction time, and pH of the hydrolysis and condensation polymerization during organosilicon polymer formation, and the type and amount of vinyl polymer.

[0024] <Magnetic Carrier Manufacturing Method> The magnetic carrier may be any generally known type, such as metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, oxide particles thereof, magnetic materials such as ferrite, and magnetic material-dispersed resin carriers containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state. There are no particular restrictions on the method for producing the magnetic carrier, and any known method may be used. The method for producing the magnetic carrier is preferably Dispersing the magnetic core particles in an aqueous medium; and This method includes a step of coating the surface of the magnetic core particles with an organosilicon polymer.

[0025] From the viewpoints of suppressing leakage and image stability, it is preferable that the magnetic core particles be magnetic-material-dispersed resin carrier cores in which amorphous magnetic material is dispersed in a resin. When the magnetic core particles are magnetic-material-dispersed resin carrier cores, the resistance is high and the particles are firmly held, which makes it easier to suppress leakage. Furthermore, when the dispersed magnetic particles are amorphous, the contact area with the toner is small and the non-electrostatic adhesion force is small, so toner spent on the magnetic carrier surface is suppressed, and excellent image density stability is obtained.

[0026] <Method of manufacturing magnetic core particles> Hereinafter, as an example of magnetic core particles, a manufacturing procedure for magnetic material-dispersed resin carrier cores will be described. The magnetic material-dispersed resin carrier core contains a magnetic material and a binder resin. The magnetic material preferably contains magnetic particles A and B. When magnetic particles A have a primary particle number-average particle diameter of ra (μm) and magnetic particles B have a primary particle number-average particle diameter of rb (μm), ra (μm) and rb (μm) preferably satisfy the relationship ra≧rb, and more preferably ra>rb. When ra and rb satisfy the above relationship, image stability is likely to be improved.

[0027] Examples of magnetic particles include magnetite particles and maghemite particles. A preferred embodiment of magnetic particles A and B is that they contain magnetite particles. Furthermore, it is more preferred that the surfaces of magnetic particles A are magnetite particles coated with an oxide of at least one non-ferrous metal element selected from the group consisting of manganese, aluminum, magnesium, titanium, and nickel. The magnetic particles B may also be coated with at least one non-ferrous metal element selected from the group consisting of manganese, aluminum, magnesium, titanium, and nickel, but more preferred are magnetite particles that are not coated with the above non-ferrous metal elements.

[0028] Furthermore, the number average particle size ra (μm) of the primary particles of magnetic particles A is preferably 0.30 μm or more and 3.00 μm or less, and more preferably 0.60 μm or more and 2.80 μm or less. The number average particle size rb (μm) of the primary particles of the magnetic particles B is preferably 0.10 μm or more and 2.50 μm or less, and more preferably 0.15 μm or more and 1.50 μm or less.

[0029] The content of at least one non-ferrous metal element selected from the group consisting of manganese, aluminum, magnesium, titanium, and nickel in magnetic particles A is preferably 20% by mass or more and 40% by mass or less, and more preferably 21% by mass or more and 35% by mass or less. The content of magnetic particles A in the magnetic particles used in the magnetic material-dispersed resin carrier core is preferably 2.0% by mass or more and 20.0% by mass or less, and the content of magnetic particles B in the magnetic particles is preferably 80.0% by mass or more and 98.0% by mass or less.

[0030] The magnetic particles A can be prepared, for example, by the following method: magnetite core particles are produced, and then a slurry containing the core particles is maintained at a temperature of 70°C to 95°C, and the pH of the slurry is controlled to a range of 8.0 to 9.0. If the non-ferrous metal element is aluminum, an aluminum salt is added at a rate of 0.015% by mass / min or less relative to the core particles. After aging for 30 minutes or more and adjusting the pH, the magnetic particles A can be obtained by washing with water and drying in the usual manner. When the non-ferrous metal element is magnesium, manganese, nickel, or titanium, the pH of the slurry containing the core particles is controlled within the range of 9.5 to 10.5 for magnesium, 8.0 to 9.0 for manganese, 7.5 to 8.5 for nickel, and 8.0 to 9.0 for titanium. Then, each metal salt is added at a rate of 0.015 mass% / min or less relative to the core particles, followed by aging for 30 minutes or more, pH adjustment, and then washing with water and drying according to the usual method to obtain magnetic particles A.

[0031] Furthermore, when magnetic particles B are also coated, they can be prepared in the same manner as magnetic particles A above, but when they are not coated, the magnetite core particles can be used as they are. In addition to the above magnetic particles (magnetic inorganic compound particles), non-magnetic iron oxide particles such as hematite particles, non-magnetic ferric oxide hydrous particles such as goethite particles, titanium oxide particles, silica particles, talc particles, alumina particles, barium sulfate particles, barium carbonate particles, cadmium yellow particles, calcium carbonate particles, zinc oxide particles, and other non-magnetic inorganic compound particles can be used in combination.

[0032] When magnetic inorganic compound particles and non-magnetic inorganic compound particles are used in combination, the mixing ratio of these particles is preferably 30 mass % or more of the magnetic inorganic compound particles based on the total mass of both particles.

[0033] It is preferable that all or part of the magnetic inorganic compound particles and non-magnetic inorganic compound particles are treated with a lipophilic treatment agent. Examples of lipophilic treatment agents include organic compounds having at least one functional group selected from the group consisting of an epoxy group, an amino group, a mercapto group, an organic acid group, an ester group, a ketone group, a halogenated alkyl group, and an aldehyde group, and mixtures of these organic compounds. As the organic compound having a functional group, a coupling agent is preferred. Among coupling agents, a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent are more preferred. Among these, a silane-based coupling agent is more preferred.

[0034] The binder resin used in the magnetic material-dispersed resin carrier core is preferably a thermosetting resin. Examples of thermosetting resins include phenolic resins, epoxy resins, and polyester resins (e.g., unsaturated polyester resins). Among these, phenolic resins are preferred from the viewpoints of low cost and ease of production. Examples of phenolic resins include phenol-formaldehyde resins.

[0035] The proportion of the binder resin constituting the magnetic material-dispersed resin carrier core is preferably 1% by mass or more and 20% by mass or less based on the total mass of the magnetic material-dispersed resin carrier core, and the proportion of the magnetic particles (magnetic inorganic compound particles) and, if necessary, non-magnetic inorganic compound particles is preferably 80% by mass or more and 99% by mass or less based on the total mass of the magnetic material-dispersed resin carrier core.

[0036] For example, a magnetic material-dispersed resin carrier core can be produced by first adding phenols and aldehydes to an aqueous medium in the presence of magnetic particles A and B (and optionally non-magnetic inorganic compound particles) and a basic catalyst, followed by stirring. The phenols and aldehydes are then reacted and cured to produce a magnetic material-dispersed resin carrier core containing magnetic particles A and B and a phenolic resin. Alternatively, magnetic material-dispersed resin carrier cores can be produced by a so-called kneading and grinding method, in which a resin containing magnetic particles A and B is ground. The former method is preferred from the viewpoint of ease of controlling the particle size of the magnetic carrier and of providing the magnetic carrier with a sharp particle size distribution.

[0037] <Organosilicon compounds> There are no particular restrictions on the method for producing the organosilicon polymer, and any known method can be used, such as the sol-gel method. The sol-gel method uses metal alkoxide M(OR) n This method uses starting materials (M: metal, O: oxygen, R: hydrocarbon, n: oxidation number of the metal) and involves hydrolysis and condensation polymerization in a solvent, which leads to a sol state and then to a gel. This method is used to synthesize glass, ceramics, organic-inorganic hybrids, and nanocomposites. Using this manufacturing method, functional materials in various shapes, such as surfaces, fibers, bulk materials, and microparticles, can be produced from the liquid phase at low temperatures.

[0038] Specifically, the organosilicon polymer present on the surface layer of the magnetic core particle is preferably produced by hydrolysis and condensation polymerization of an organosilicon compound, typically an alkoxysilane. By uniformly providing a surface layer containing this organosilicon polymer on the magnetic core particles, a magnetic carrier having superior abrasion resistance compared to conventional magnetic carriers can be obtained.

[0039] Furthermore, the sol-gel method starts with a solution and forms a material by gelling the solution, making it possible to create a variety of microstructures and shapes. In particular, when magnetic core particles are dispersed in an aqueous medium and the magnetic carrier is produced in an aqueous medium, if the organosilicon compound is highly hydrophobic (for example, if the hydrocarbon group of the organosilicon compound has a carbon number of more than 6), the condensation-polymerized organosilicon polymer tends to become unstable early in the condensation polymerization. Therefore, it tends to precipitate on the surface of the magnetic core particles early. As a result, the surface irregularities of the magnetic carrier tend to be reduced. On the other hand, when the carbon number of the hydrocarbon group of the organosilicon compound is 0, it becomes hydrophilic, so condensation polymerization proceeds easily, and after forming large particles, they tend to precipitate on the surface of the magnetic core particles. As a result, the surface irregularities of the magnetic carrier tend to become large. The shape described above is The reaction temperature, reaction time, reaction solvent, pH, and the type and amount of organosilicon compound can also be adjusted. The organosilicon polymer is preferably a condensation polymer of an organosilicon compound having a structure represented by the following formula (Z).

[0040] [ka]

[0041] (R1 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, an amino group, or an alkylamino group having 1 to 5 carbon atoms, and R2, R3, and R4 each independently represent a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group.) R1 is the same as R in the structure represented by formula (T3). The alkyl group, phenyl group, or alkylamino group of R1 can improve hydrophobicity, resulting in a magnetic carrier with excellent environmental stability. R1 is preferably an alkyl group or phenyl group having 1 to 6 carbon atoms. When R1 is an alkyl group or phenyl group having 1 to 6 carbon atoms, steric hindrance is small when the organosilicon compound undergoes condensation polymerization, resulting in a highly controlled molecular density and the formation of a strong three-dimensional crosslinked structure, which in turn exhibits wear resistance. Therefore, even during long-term image output, wear of the coating layer of the magnetic carrier can be suppressed, and excellent charge imparting properties to the toner can be obtained. Furthermore, since silicon atoms are suitably present on the surface of the magnetic carrier, the surface free energy of the magnetic carrier surface can be reduced, so toner spent on the magnetic carrier surface is suppressed, and excellent image density stability can be obtained. Furthermore, when R1 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, the toner tends to be positively charged. When R1 is an amino group or an alkylamino group having 1 to 5 carbon atoms, the toner tends to be negatively charged. These can be selected appropriately according to the desired chargeability of the toner.

[0042] R2, R3, and R4 are each independently a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups can be hydrolyzed, added, or condensed to form a crosslinked structure, thereby obtaining a magnetic carrier with excellent wear resistance. From the viewpoints of mild hydrolysis at room temperature and deposition and coating properties on the surface of the magnetic core particles, R2, R3, and R4 are preferably alkoxy groups, more preferably methoxy groups or ethoxy groups. Furthermore, the hydrolysis, addition polymerization, and condensation polymerization of R2, R3, and R4 can be controlled by the reaction temperature, reaction time, reaction solvent, and pH.

[0043] To obtain an organosilicon polymer, it is advisable to use one or a combination of several organosilicon compounds (hereinafter also referred to as trifunctional silanes) that have three reactive groups (R2, R3, and R4) in one molecule excluding R1 in the formula (Z) shown above. The content of the organosilicon polymer in the magnetic carrier is preferably 0.10% by mass or more and 20.00% by mass or less, and more preferably 0.25% by mass or more and 10.00% by mass or less.

[0044] Examples of the above formula (Z) include the following. Trifunctional methylsilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, and methyldiethoxyhydroxysilane. Trifunctional silanes such as ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, and hexyltrihydroxysilane. Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane. Trifunctional aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, and 3-phenylaminopropyltrimethoxysilane.

[0045] The content of the structure represented by formula (Z) in the monomers forming the organosilicon polymer is preferably 50 mol % or more, and more preferably 60 mol % or more. By making this content 50 mol % or more, the wear resistance of the magnetic carrier can be further improved.

[0046] Furthermore, the following may be used in combination with the organosilicon compound having the structure represented by formula (Z) to the extent that the effects of the present invention are not impaired: an organosilicon compound having four reactive groups per molecule (tetrafunctional silane), an organosilicon compound having two reactive groups per molecule (bifunctional silane), or an organosilicon compound having one reactive group (monofunctional silane). Examples include the following:

[0047] Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3 -Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, hexamethyldisilane, tetraisocyanatesilane, methyltriisocyanatesilane; vinyltriisocyanatesilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxy Trifunctional vinyl silanes such as dichlorosilane, vinyldimethoxychlorosilane, vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyltriacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyldimethoxyhydroxysilane, vinylethoxymethoxyhydroxysilane, and vinyldiethoxyhydroxysilane. Trifunctional allylsilanes such as allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, and allyltrihydroxysilane. t-Butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t-butyldiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chloro(decyl)dimethylsilane, methoxy(decyl)dimethylsilane, ethoxy(decyl)dimethylsilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, triphenylchlorosilane, triphenylmethoxysilane, triphenylethoxysilane, chloromethyl(dic) (chloro)methylsilane, chloromethyl(dimethoxy)methylsilane, chloromethyl(diethoxy)methylsilane, di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, dichloro(methyl)-n-octylsilane, dimethoxy(methyl)-n-octylsilane, diethoxy(methyl)-n-octylsilane.

[0048] <Step of dispersing magnetic core particles in an aqueous medium> When dispersing the magnetic core particles in an aqueous medium, a poorly water-soluble inorganic dispersion stabilizer may be used, and the amount of the poorly water-soluble inorganic dispersion stabilizer added is preferably 0.2 parts by mass or more and 2.0 parts by mass or less per 100.0 parts by mass of the magnetic core particles. It is also preferable to prepare the magnetic core particle dispersion medium using 300 parts by mass or more and 3,000 parts by mass or less of water per 100 parts by mass of the magnetic core particles.

[0049] When preparing an aqueous medium in which a poorly water-soluble inorganic dispersant is dispersed, a commercially available dispersion stabilizer may be used as is. Alternatively, to obtain a dispersion stabilizer having a fine and uniform particle size, the poorly water-soluble inorganic dispersant may be produced in a liquid medium such as water under high-speed stirring. Specifically, when using tricalcium phosphate as a dispersion stabilizer, a preferred dispersion stabilizer can be obtained by mixing an aqueous sodium phosphate solution with an aqueous calcium chloride solution under high-speed stirring to form tricalcium phosphate microparticles. Furthermore, using tricalcium phosphate as a dispersion stabilizer is preferred from the viewpoints of detachment of the organosilicon polymer coating layer, leakage suppression, and image stability. The reason for this is due to the crystalline structure of tricalcium phosphate. Tricalcium phosphate forms a hexagonal crystal structure with calcium ions at the center and phosphate ions arranged around them. This makes it easier for calcium ions to orient themselves in the aqueous medium on the magnetic carrier surface, increasing the electrical attraction with silanol groups, which are the hydrolyzed portions of organosilicon compounds in the aqueous medium, and facilitating the formation of an organosilicon polymer coating layer.

[0050] <Addition of surfactant> In the step of dispersing magnetic core particles in an aqueous medium, compound A is added, and compound A is represented by at least one selected from the group consisting of formulas (1-1), (1-2), (2-1) to (2-5), and (3-1) to (3-5), which is effective in preventing detachment of the coating layer, suppressing leakage, and improving image quality. This is preferable from the viewpoint of image stability. The presence of Compound A enhances adhesion due to the affinity between the hydrophilic groups of Compound A and the silanol moieties of the organosilicon polymer, thereby suppressing peeling and leakage of the coating layer even during long-term image output, and improving image stability. Adding compound A during the dispersion process of the magnetic core particles and adhering compound A to the surfaces of the magnetic core particles is preferred from the viewpoints of preventing detachment of the organosilicon polymer coating layer, suppressing leakage, and improving image stability. Among these, compounds represented by at least one selected from the group consisting of formulas (3-1) to (3-5) are more preferred. Compound A has a hydrophobic hydrocarbon group moiety with 3 to 30 carbon atoms and a hydrophilic moiety with higher polarity than the hydrocarbon group. As a result, the hydrophobic group tends to orient toward the magnetic core particle, and the hydrophilic group tends to orient toward the organosilicon polymer, increasing the adhesion between the magnetic core particle and the organosilicon polymer. The common feature of the compounds represented by formulas (1-1) and (1-2) is that the hydrocarbon group having 3 to 30 carbon atoms represented by R' is hydrophobic, and the positively charged nitrogen atom is highly polar, resulting in hydrophilic properties. Examples of the compounds represented by formula (1-1) include the following quaternary ammonium salt compounds.

[0051] [ka]

[0052] (In formula (1-1), R' represents a hydrocarbon group having 3 to 30 carbon atoms, R C1 ~R C3 are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (which may contain one or more ether bonds or may contain the same group). X is an element selected from Cl, Br, and I. Examples of R' include a C3 to C30 linear or branched alkyl group, a C3 to C30 linear or branched alkenyl group, and a benzyl group.

[0053] Specific examples of the compound include alkyltrimethylammonium chlorides where X is Cl, such as tetrabutylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, and behenyltrimethylammonium chloride; ammonium chloride salts containing a benzyl group, such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzalkonium chloride, and benzethonium chloride; and dialkyldimethylammonium chlorides, such as didecyldimethylammonium chloride and distearyldimethylammonium chloride. Further, examples of the above compounds include bromides where X is Br and iodides where X is I.

[0054] Further examples include hydrochlorides of alkylamines such as coconut amine acetate and stearyl amine acetate. Among these, preferred are those in which R' is a C8-18 hydrocarbon group, such as octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, benzyltrimethylammonium chloride; coconutamine acetate, and stearylamine acetate. The compound represented by formula (1-2) includes the following pyridinium salt.

[0055] [ka]

[0056] (In formula (1-2), R' is a hydrocarbon group having 3 to 30 carbon atoms, and X is an element selected from Cl, Br, and I.) Examples of R' include C3 to C30 linear or branched alkyl groups, C3 to C30 linear or branched alkenyl groups, benzyl groups, etc. Preferably, it is a C8 to C18 alkyl or alkenyl group. Specific examples of the compound include alkylpyridinium chlorides such as butylpyridinium chloride, dodecylpyridinium chloride, and cetylpyridinium chloride.

[0057] Examples of compound A include the compounds represented by formulae (2-1) to (2-5). The compounds represented by formulas (2-1) to (2-5) have a common feature in that the hydrocarbon group having 3 to 30 carbon atoms represented by R' is hydrophobic. In addition, they have a moiety derived from at least one selected from the group consisting of carboxylic acid, sulfonic acid, and phosphoric acid, and since these moieties have high polarity, the moiety is hydrophilic. For example, the compound represented by formula (2-1) is as follows: R´-ABX (2-1) In formula (2-1), R' is a hydrocarbon group having 3 to 30 carbon atoms, and X is CO2M 1 , SO3M 1 (M 1 is a hydrogen atom, sodium, potassium, lithium, ammonium or triethanoic acid A is a single bond, -O- (ether bond), or >C=O (carbonyl). B is a single bond or -(CH2CH2O) n -or-(CH2CH2O) n -CH2-, and n is an integer of 1 to 60.

[0058] Examples of R' include a C3 to C30 linear or branched alkyl group, a C3 to C30 linear or branched alkenyl group, a benzyl group, a phenyl group, a naphthyl group, a phenyl group or a naphthyl group in which a linear or branched alkyl group is bonded to a benzene ring, etc. Among these, a hydrocarbon group having 8 to 30 carbon atoms is particularly preferred because it is likely to exhibit hydrophobicity.

[0059] Specific examples of compounds in which A and B are single bonds include higher fatty acids such as lauric acid, stearic acid, oleic acid, and palmitic acid, and their sodium salts, potassium salts, and lithium salts; alkanesulfonic acids such as octanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, tetradecanesulfonic acid, hexadecanesulfonic acid, and octadecanesulfonic acid, and their sodium salts, potassium salts, and triethanolamine salts; alkylbenzenesulfonic acids such as toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, and dodecylbenzenesulfonic acid, and their sodium salts, potassium salts, and triethanolamine salts; and sodium salts, potassium salts, and triethanolamine salts of naphthalenesulfonic acid and alkylnaphthalenesulfonic acids.

[0060] Examples of compounds in which A is an ether bond (-O-) and B is a single bond include sodium lauryl sulfate, sodium myristyl sulfate, ammonium lauryl sulfate, and lauryl sulfate. Examples include triethanolamine, alkyl sulfates such as sodium cetyl sulfate and sodium stearyl sulfate. B is -(CH2CH2O) n Examples of compounds in which - is sodium include sodium, triethanolamine polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate such as sodium polyoxyethylene stearyl ether sulfate, and the like.

[0061] B is -(CH2CH2O) n Examples of the compound having the formula -CH2- include polyoxyethylene alkyl ether carboxylates such as sodium polyoxyethylene lauryl ether acetate and sodium polyoxyethylene stearyl ether acetate. Among these, fatty acid salts such as sodium laurate and sodium stearate, sulfonates such as sodium dodecanesulfonate and sodium octadecanesulfonate, and alkyl sulfates such as sodium lauryl sulfate and sodium stearyl sulfate, in which R' has 8 to 18 carbon atoms, are preferred. In addition, R' has 8 to 18 carbon atoms, (CH2CH2O) n Polyoxyethylene alkyl ether sulfates and polyoxyethylene alkyl ether carboxylates, which have the structure (CH2CH2O) within the compound, are more preferred. n This structure is preferred because it has a high affinity with organosilicon polymers and improves adhesion. The compound represented by formula (2-2) is as follows:

[0062] [ka]

[0063] (R' is a hydrocarbon group having 3 to 30 carbon atoms, R C4 is hydrogen, a methyl group, or an ethyl group; Y is hydrogen, a methyl group, a carboxy group, a carboxymethyl group, or a carboxyethyl group; M 2is sodium, potassium or triethanolamine. Specific examples include N-acylamino acid derivative salts such as sodium N-lauroyl sarcosine, sodium cocoyl glutamate, N-lauroyl glutamate salts (such as sodium lauroyl glutamate), N-lauroylmethyl-β-alanine salt, N-acylglycine salt, and N-acyl glutamate salt. Among these, N-lauroyl glutamic acid salts, N-lauroyl glycine salts, and N-lauroyl alanine salts, in which R' has 8 to 18 carbon atoms, are preferred. The compound represented by formula (2-3) is as follows:

[0064] [ka]

[0065] (R' is a hydrocarbon group having 3 to 30 carbon atoms, R C5 is hydrogen or hydrocarbons with 1 to 30 carbon atoms are elementary groups, R' and R C5 may be the same or different, and B 1 , B 2 are each independently a single bond, -(CH2CH2O) n -or-(CH2) m - and M 3 is sodium or potassium, and n is an integer from 1 to 60. Specifically, for example, sodium octyl sulfosuccinate, dioctyl sulfosuccinate Examples thereof include sodium and potassium salts of alkyl sulfosuccinates such as sodium lauryl sulfosuccinate and sodium dilauryl sulfosuccinate, sodium and potassium salts of polyoxyethylene alkyl sulfosuccinate, and sodium and potassium salts of polyoxyethylene alkyl sulfosuccinates. Among these, alkyl sulfosuccinates in which R' has 8 to 18 carbon atoms are preferred. In addition, R' has 8 to 18 carbon atoms, (CH2CH2O) nMore preferred are sodium and potassium salts of polyoxyethylene alkyl ether sulfosuccinate, which have the structure (CH2CH2O) in the compound. n This structure is preferred because it has a high affinity with organosilicon polymers and improves adhesion. The compounds represented by formulas (2-4) and (2-5) are as follows:

[0066] [ka]

[0067] (R' is a hydrocarbon group having 3 to 30 carbon atoms, R C6 is hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and R' and R C6 may be the same or different. B 3 , B 4 , B 5 are each independently a single bond, -(CH2CH2O) n -or-(CH2CH2O) n -CH2-, and M 4 and M 5 are each independently sodium or potassium, and n is an integer of 1 to 60. Specific examples of the compound include alkyl phosphates such as sodium lauryl phosphate, sodium dilauryl phosphate, potassium lauryl phosphate, and potassium dilauryl phosphate; polyoxyethylene alkyl ether phosphates such as polyoxyethylene lauryl ether sodium phosphate; polyoxyethylene alkyl phenyl ether phosphates such as polyoxyethylene lauryl phenyl ether sodium phosphate; and polyoxyethylene styrenated phenyl phosphates such as polyoxyethylene styrenated phenyl ether sodium lauryl phosphate. Among these, alkyl phosphates in which R' has 8 to 18 carbon atoms are preferred. In addition, R' has 8 to 18 carbon atoms, (CH2CH2O) nMore preferred are polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, and polyoxyethylene styrenated phenyl phosphates, which have the structure (CH2CH2O) in the compound. n This structure is preferred because it has a high affinity with organosilicon polymers and improves adhesion.

[0068] Examples of compound A include the compounds represented by formulas (3-1) to (3-5). The compounds represented by formulas (3-1) to (3-5) have a common feature in that the hydrocarbon group having 3 to 30 carbon atoms represented by R' is hydrophobic. n As exemplified by the structure shown in (CH2CH2O), the presence of multiple oxyethylene or similar structures within a compound makes the structure hydrophilic. n This structure is preferred because it has a high affinity with organosilicon polymers and improves adhesion. The compound represented by formula (3-1) is as follows.

[0069] [ka]

[0070] (R' is a hydrocarbon group having 3 to 30 carbon atoms. D is a single bond, an ether bond (-O-), an ester bond (-COO-), an amide group (-CONR C7 -), or amino group (-NR C7 -)(R C7 is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. E is a hydrogen atom or an acyl group having 2 to 31 carbon atoms, and n is an integer of 1 to 60. Specific examples of the compound include polyoxyethylene alkyl ethers or polyoxyethylene alkenyl ethers such as pentaethylene glycol dodecyl ether, octaethylene glycol dodecyl ether, polyoxyethylene lauryl ether, polyoxyethylene monocetyl ether, and polyoxyethylene stearyl ether; polyoxyethylene alkylphenyl ethers such as octylphenol ethoxylate and nonylphenol ethoxylate; polyoxyethylene tribenzyl phenyl ether and polyoxyethylene styrenated phenyl ether; polyoxyethylene fatty acid esters such as polyoxyethylene laurate, polyoxyethylene cetylate, and polyoxyethylene stearate; polyoxyethylene alkylamines such as polyoxyethylene laurylamine, polyoxyethylene cetylamine, and polyoxyethylene stearylamine; fatty acid diesters of ethylene glycol such as ethylene glycol distearate, ethylene glycol dilaurate, ethylene glycol dioleate, ethylene glycol dipalmitate, and ethylene glycol dimyristate; and polyoxyethylene fatty acid diesters such as polyethylene glycol dilaurate, polyethylene glycol distearate, polyethylene glycol dipalmitate, and polyethylene glycol dioleate.

[0071] Among these, polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene tribenzylphenyl ethers, polyoxyethylene styrenated phenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fatty acid diesters of ethylene glycol, and polyoxyethylene fatty acid diesters, in which R' has 8 to 18 carbon atoms, are preferred. Furthermore, when the resin constituting the core particle has a structure containing a benzene ring, it is preferable to use compounds such as polyoxyethylene alkyl phenyl ether, polyoxyethylene tribenzyl phenyl ether, and polyoxyethylene styrenated phenyl ether, which have a benzene ring within the compound, as this further improves the adhesion between the core particle and the organosilicon polymer. The compound represented by formula (3-2) is as follows.

[0072] [ka]

[0073] (G is a single bond or -(CH2-CH2-O) q and m, n, and q each independently represent an integer of 1 to 60. Specific examples of the compound include polyoxyethylene polyoxypropylene polyol and polyoxyethylene polyoxypropylene glycol. The compound represented by formula (3-3) is as follows.

[0074] [ka]

[0075] (R' is a hydrocarbon group having 3 to 30 carbon atoms, and E is a hydrogen atom or an acyl group having 2 to 31 carbon atoms.) Specific examples of the compound include fatty acid monoesters of glycerin such as glyceryl monostearate and glyceryl monooleate; fatty acid diesters of glycerin such as glyceryl distearate and glyceryl dioleate; and the like. Among these, fatty acid esters of glycerin in which R' has 8 to 18 carbon atoms are preferred. The compound represented by formula (3-4) is as follows.

[0076] [ka]

[0077] (R' is a hydrocarbon group having 3 to 30 carbon atoms. 6 , B 7 , B 8 , B 9 are each independently a single bond, -(CH2CH2O) n -or-(CH2CH2O) n -CH2-. E 1 , E 2 , E 3 are each independently a hydrogen atom or an acyl group having 2 to 31 carbon atoms, and n is an integer of 1 to 60. Specific examples of the compound include fatty acid monoesters of sorbitan such as sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, and sorbitan monostearate; fatty acid diesters of sorbitan such as sorbitan dilaurate, sorbitan dioleate, sorbitan dipalmitate, and sorbitan distearate; fatty acid triesters of sorbitan such as sorbitan trilaurate, sorbitan trioleate, sorbitan tripalmitate, and sorbitan tristearate, or mixtures of monoesters and diesters of sorbitan sesquioleate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene monooleate. fatty acid monoesters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan monoisostearate; fatty acid diesters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan dilaurate, polyoxyethylene sorbitan dipalmitate, polyoxyethylene sorbitan distearate, polyoxyethylene sorbitan dioleate, and polyoxyethylene sorbitan diisostearate; fatty acid triesters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trilaurate, polyoxyethylene sorbitan tripalmitate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan triisostearate. Among these, fatty acid esters of sorbitan in which R' has 8 to 18 carbon atoms are preferred. Even more preferred are fatty acid esters of polyoxyethylene sorbitan in which some of the hydroxyl groups of sorbitan are polyoxyethylated. (CH2CH2O) n This structure is preferred because it has a high affinity with organosilicon polymers and improves adhesion. The compound represented by formula (3-5) is as follows.

[0078] [ka]

[0079] (R' is a hydrocarbon group having 3 to 30 carbon atoms. J is a single bond or a carbonyl bond (>C=O). n is an integer of 1 to 60, and p is an integer of 0 to 60.) Specific examples of the compound include fatty acid alkylolamides and polyoxyethylene fatty acid amides such as lauric acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, and palmitic acid diethanolamide; and polyoxyethylene alkylamines such as polyoxyethylene laurylamine, polyoxyethylene stearylamine, and polyoxyethylene oleylamine. Among these, fatty acid alkylolamides and alkylamines in which R' has 8 to 18 carbon atoms are preferred. More preferably, polyoxyethylene fatty acid amides and polyoxyethylene alkylamines having a (CH2CH2O) structure within the compound are preferred. (CH2CH2O) n This structure is preferred because it has a high affinity with organosilicon polymers and improves adhesion.

[0080] These compounds A may be used alone or in combination. When using a combination of a plurality of compounds, for example, they may be used in combination from the group of compounds represented by formula (1-1), or one or more compounds selected from formula (1-1) and one or more compounds selected from formula (1-2) may be used in combination. Furthermore, one or more compounds selected from each group of compounds represented by formulas (1-1) and (1-2) and compounds represented by formulas (3-1) to (3-5) may be used in combination.

[0081] As mentioned above, the hydrophobic moiety represented by R' preferably has 8 to 18 carbon atoms, as this will exhibit high hydrophobicity and will tend to have affinity with the magnetic core particle. Also, in the compound (CH2CH2O) n (n is an integer of 1 to 60), this is preferred because it has a high affinity with the organosilicon polymer and improves the adhesion between the magnetic core particle and the organosilicon polymer. The compounds represented by formulas (3-1) to (3-5) differ from the compounds represented by formulas (1-1), (1-2), and (2-1) to (2-5) in that they contain no ionized elements. Therefore, they are more preferable because they tend to improve charge stability compared to the compounds represented by formulas (1-1), (1-2), and (2-1) to (2-5). Furthermore, the compounds represented by formula (3-1) are particularly preferable from the viewpoint of charge stability.

[0082] <Primer treatment> It is preferable to form a primer layer on the surface of the magnetic core particles before the dispersion step of the magnetic core particles from the viewpoints of preventing the organosilicon polymer coating layer from being detached, suppressing leakage, and image stability. The method for forming a primer layer on the surface of the magnetic core particles is to dilute a vinyl polymer in a solvent. The solvent used here may be any solvent that can dissolve the vinyl polymer. In the case of a vinyl polymer that is soluble in an organic solvent, examples of the organic solvent include toluene, xylene, cellosolve butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and methanol.

[0083] The method for forming the primer layer is not particularly limited, but examples thereof include a dipping method, a spraying method, a brush coating method, a dry method, and a coating method such as a fluidized bed method. Among these, the dipping method is more preferable in order to control the uniformity of the primer layer. A preferred immersion method is to add a vinyl polymer solution, which is a mixture of a vinyl polymer and a solvent, to the magnetic core particles under reduced pressure, and then remove the solvent by degassing or heating. By controlling the solvent removal speed by the degassing rate or heating temperature, it is possible to control the state of the vinyl polymer on the surface of the magnetic core particles. The degree of reduced pressure is preferably 10 mmHg to 700 mmHg. If the pressure is 10 mmHg or more, the vinyl polymer solution is less likely to boil during the primer treatment step, and a good primer layer is formed.

[0084] The amount of vinyl polymer used in the primer treatment is adjusted depending on the specific surface area of ​​the magnetic core particles, but generally, the amount of vinyl polymer is preferably 0.1 to 3.0 parts by mass per 100 parts by mass of magnetic core particles, and more preferably 0.1 to 2.0 parts by mass. This range is preferred from the viewpoint of improving adhesion with the organosilicon polymer. The vinyl polymer used to form the primer layer preferably has the structure shown in formula (1) above, from the viewpoint of improving adhesion to the organosilicon polymer coating layer. When the vinyl polymer has the structure shown in formula (1) above, the affinity between the ester moieties of the vinyl polymer and the silanol moieties of the organosilicon polymer increases adhesion. Specific examples of the monomer capable of forming the structure represented by formula (1) include acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, and ethyl methacrylate.

[0085] In order to adjust the glass transition temperature (Tg), other monomers may be further contained as constituent components of the vinyl polymer. Other monomers used as components of the coating resin composition include known monomers, such as styrene, ethylene, propylene, butylene, butadiene, vinyl chloride, vinylidene chloride, vinyl acetate, propyl methacrylate, vinyl methyl ether, vinyl ethyl ether, and vinyl methyl ketone.

[0086] <Step of Coating the Surface of the Magnetic Core Particles with an Organosilicon Polymer> A method of forming a coating layer by coating the surface of the magnetic core particles with an organosilicon polymer will be described, but the method is not limited to this. In the first production method, magnetic core particles are first obtained, and then the magnetic core particles are placed in an aqueous medium to form a coating layer of an organosilicon polymer on the magnetic core particles in the aqueous medium. The second manufacturing method involves spraying a solvent containing an organosilicon compound for forming an organosilicon polymer onto the surface of the magnetic core particles using a spray drying method, and then polymerizing or drying the surface with hot air and cooling, thereby coating the magnetic core particles with the organosilicon polymer.

[0087] Of the above-mentioned production methods, the first production method is preferred, since it is easy to control the degree of condensation polymerization of the organosilicon compound, and therefore it is easy to control the surface irregularities of the magnetic core particles. The condensation step can be carried out under any pH conditions. However, the condensation of the organosilicon compound is carried out under the conditions of water. Therefore, by controlling the pH of the aqueous medium, it is possible to further enhance the effects of the present disclosure. Under acidic conditions, the hydrolysis of alkoxy groups proceeds electrophilically with protons as a catalyst, so the hydrolysis of alkoxy groups within the molecule proceeds sequentially. As a result, silanol groups tend to remain in the condensation product of the organosilicon compound, making it difficult for hydrophobicity to progress. In addition, three-dimensional condensation reactions are unlikely to occur, and molecular weights are also unlikely to increase. On the other hand, under basic conditions, the hydrolysis of alkoxy groups proceeds nucleophilically with hydroxide ions as a catalyst, and the hydrolysis of all alkoxy groups within the molecule proceeds simultaneously. This means that silanol groups are less likely to remain in the condensed product of the organosilicon compound, making it easier to hydrophobize. Furthermore, three-dimensional condensation reactions are more likely to occur, increasing the molecular weight. As a result, large organosilicon polymers can be formed in aqueous media.

[0088] Furthermore, as the hydrophobicity of the organosilicon polymer increases, its stability in aqueous media decreases, making it more likely to migrate to magnetic core particles. As a result, the surface of the resulting magnetic carrier can become uneven, so it is preferable to carry out the condensation process under basic conditions. Furthermore, when the condensation process is carried out under basic conditions, the molecular weight of the organosilicon polymer tends to increase, making it possible to reduce the amount of organosilicon compound dissolved in the aqueous medium. Therefore, it is possible to reduce the amount of organosilicon compound in the wastewater, which is also preferable from the perspective of reducing the load on wastewater treatment. Specifically, the pH of the aqueous medium in the condensation step is preferably 7.5 or more and 12.0 or less, and more preferably 8.0 or more and 11.0 or less. The pH in the condensation step can be controlled with a known acid or base.

[0089] Examples of acids that adjust the pH include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, boric acid, hydrofluoric acid, hydrobromic acid, permanganic acid, thiocyanic acid, phosphonic acid, phosphoric acid, diphosphoric acid, hexafluorophosphoric acid, tetrafluoroboric acid, and tripolyphosphoric acid; and organic acids such as aspartic acid, o-aminobenzoic acid, p-aminobenzoic acid, isonicotinic acid, oxaloacetic acid, citric acid, 2-glyceric acid, glutamic acid, cyanoacetic acid, oxalic acid, trichloroacetic acid, o-nitrobenzoic acid, nitroacetic acid, picric acid, picolinic acid, pyruvic acid, fumaric acid, fluoroacetic acid, bromoacetic acid, o-bromobenzoic acid, maleic acid, and malonic acid. These acids can be used without any particular limitation, and these acids may be used alone or in combination of two or more.

[0090] Examples of bases for adjusting the pH include alkali metals such as lithium, sodium, and potassium, and aqueous solutions thereof, alkali metal salts and aqueous solutions thereof, alkaline earth metals such as calcium and magnesium, and aqueous solutions thereof, alkaline earth metal salts, ammonia, and amines including urea. More specifically, examples of the base include an aqueous solution of lithium hydroxide, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of calcium hydroxide, an aqueous solution of magnesium hydroxide, an aqueous solution of lithium carbonate, an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, an aqueous solution of ammonia, and urea. These bases can be used without any particular limitations. These bases may be used alone or in combination of two or more.

[0091] The volume distribution 50% particle size (D50) of the magnetic carrier is preferably 20.0 μm or more and 70.0 μm or less. This can prevent carrier adhesion. The resistivity of the magnetic carrier at an electric field strength of 1000 V / cm measured by resistivity measurement method is 1.0 x 10 6 Ω cm or more 1.0×10 9 A resistivity of Ω·cm or less is preferable from the viewpoint of improving developability and image stability. In the developing field, the magnetic carrier is exposed to a higher electric field strength together with the toner, but since the toner is an insulator, the electric field strength is dominant. Therefore, the electric field strength applied to the magnetic carrier is lower, at about 1000 V / cm. Therefore, it is preferable that the resistivity at an electric field strength of 1000 V / cm is within the above range.

[0092] <Toner manufacturing method> Next, the toner contained in the two-component developer together with the magnetic carrier will be described. Examples of methods for producing toner particles include the following methods. A pulverization method in which a binder resin and, if necessary, additives such as a colorant and wax are melted and kneaded, and the kneaded mixture is cooled, pulverized, and classified; a suspension granulation method in which a solution prepared by dissolving or dispersing a binder resin and, if necessary, additives such as a colorant in a solvent is introduced into an aqueous medium, followed by suspension granulation, and the solvent is removed to obtain toner particles; A suspension polymerization method in which a monomer composition, in which additives such as a colorant are uniformly dissolved or dispersed in a monomer as needed, is dispersed in a continuous phase (for example, an aqueous phase) containing a dispersion stabilizer, and a polymerization reaction is carried out to produce toner particles; Dispersion polymerization method in which a polymer dispersant is dissolved in an aqueous organic solvent and the monomer is polymerized to produce particles that are insoluble in the solvent, thereby obtaining toner particles; Emulsion polymerization method in which toner particles are produced by direct polymerization in the presence of a water-soluble polar polymerization initiator; The emulsion aggregation method includes a step of aggregating at least polymer fine particles and, if necessary, colorant fine particles to form fine particle aggregates, and a ripening step of causing fusion between the fine particles in the fine particle aggregates. In particular, for toner produced by the pulverization method, it is preferable to add large inorganic fine particles of about 100 nm after pulverization or after pulverization and classification, and modify the toner surface by thermal treatment, from the viewpoint of fixing the large inorganic fine particles that tend to become loose during durability, etc. Fixing the large inorganic fine particles creates a spacer effect, improving transferability.

[0093] Examples of binder resins contained in the toner include the following. polyester, polystyrene; polymers of styrene derivatives such as poly-p-chlorostyrene and polyvinyltoluene; styrene copolymers such as styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, and styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenolic resin, modified phenolic resin, maleic resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin; polyester resin having as a structural unit a monomer selected from aliphatic polyhydric alcohols, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, aromatic dialcohols, and diphenols; polyurethane resin, polyamide resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum resin, and hybrid resin having a polyester unit and a vinyl polymer unit.

[0094] In order to achieve both the storage stability and low-temperature fixability of the toner, the peak molecular weight (Mp) of the molecular weight distribution of the binder resin measured by gel permeation chromatography (GPC) is preferably 2000 or more and 50000 or less. Furthermore, the binder resin preferably has a number average molecular weight (Mn) of 1500 or more and 30000 or less, a weight average molecular weight (Mw) of 2000 or more and 1000000 or less, and a glass transition temperature (Tg) of 40°C or more and 80°C or less.

[0095] The toner particles may contain a wax. The wax is preferably used in an amount of 0.5 to 20.0 parts by mass per 100 parts by mass of the binder resin, since this allows for the production of a high gloss image. The peak temperature of the toner is preferably 45° C. or more and 140° C. or less, which is preferable because it allows the toner to have both good storage stability and good hot offset resistance. Examples of waxes include hydrocarbon waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes containing fatty acid esters as the main component such as carnauba wax, behenyl behenate wax, and Montan acid ester wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax. Among these, hydrocarbon waxes such as Fischer-Tropsch wax are preferred because they can provide images with high gloss.

[0096] The toner particles may contain a colorant. Examples of the colorant include the following: Examples of black colorants include carbon black, magnetic materials, and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. Examples of magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Examples of cyan colorants include CI Pigment Blue 1, 2, 3, 7, 15:2, 15:3, 15:4, 16, 17, 60, 62, and 66; CI Vat Blue 6; and CI Acid Blue 45, and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton. Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal compounds, methine compounds, and allylamide compounds. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment in combination to improve the clarity of the image in terms of the quality of the full-color image. The amount of colorant used is preferably 0.1 to 30.0 parts by mass, more preferably 0.5 to 20.0 parts by mass, relative to 100 parts by mass of binder resin, except when a magnetic material is used.

[0097] The toner may contain a charge control agent as needed. Known charge control agents can be used. A metal compound of an aromatic carboxylic acid is preferred, as it is colorless, provides a high charging speed for the toner, and can stably maintain a constant charge amount. The charge control agent may be added internally or externally to the toner particles. The amount of charge control agent added is preferably 0.2 to 10 parts by weight per 100 parts by weight of the binder resin.

[0098] Toner preferably contains an external additive to improve fluidity. The external additive is preferably inorganic fine particles such as silica, titanium oxide, or aluminum oxide. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof. The external additive is preferably used in an amount of 0.1 to 5.0 parts by mass relative to 100 parts by mass of toner particles. The toner particles and the external additive can be mixed using a known mixer such as a Henschel mixer.

[0099] The procedure for producing toner by the pulverization method will be described. In the raw material mixing step, predetermined amounts of materials constituting the toner particles, such as a binder resin and, if necessary, other components such as a colorant, wax, and charge control agent, are weighed, blended, and mixed. Examples of mixing equipment include double cone mixers, V-type mixers, drum mixers, super mixers, Henschel mixers, Nauta mixers, and Mechano Hybrid (Mitsui Mining Co., Ltd.). Yamasha) are examples.

[0100] Next, the mixed materials are melt-kneaded to disperse the colorant and other ingredients in the binder resin. In this melt-kneading process, a batch-type kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used, but single-screw or twin-screw extruders are the mainstream due to their advantage of being able to produce continuously. Examples include a KTK type twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Iron Works), a twin-screw extruder (manufactured by KCK Corporation), a Co-kneader (manufactured by Buss Co., Ltd.), and a Kneedex (manufactured by Mitsui Mining Co., Ltd.).

[0101] Furthermore, the colored resin composition obtained by melt-kneading may be rolled using a two-roll mill or the like, and cooled with water or the like in a cooling step. The cooled resin composition is then pulverized to a desired particle size in a pulverization step, which involves coarse pulverization using a pulverizer such as a crusher, hammer mill, or feather mill, followed by further pulverization using a pulverizer such as a Kryptron System (Kawasaki Heavy Industries), a Super Rotor (Nisshin Engineering), a Turbo Mill (Turbo Kogyo), or an air jet pulverizer.

[0102] Thereafter, if necessary, the mixture is classified using a classifier or sieve such as an inertial classification type Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification type Turboplex (manufactured by Hosokawa Micron Corporation), a TSP Separator (manufactured by Hosokawa Micron Corporation), or a Faculty (manufactured by Hosokawa Micron Corporation) to obtain toner particles.

[0103] Furthermore, if necessary, after pulverization, the toner particles may be subjected to a surface modification treatment such as spheronization using a Hybridization System (manufactured by Nara Machinery Works), a Mechanofusion System (manufactured by Hosokawa Micron Corporation), a Faculty (manufactured by Hosokawa Micron Corporation), or a Meteor Rainbow MR Type (manufactured by Nippon Pneumatic Co., Ltd.). Furthermore, if necessary, inorganic fine particles may be added using the mixer before the surface modification treatment. The toner particles may be used as they are as a toner. From the viewpoint of imparting fluidity to the toner particles, inorganic fine particles may be added using the mixer. It is preferable that the toner has toner particles and inorganic fine particles on the surfaces of the toner particles. The coverage of the toner with the inorganic fine particles is preferably 10% or more and 80% or less, and more preferably 25% or more and 65% or less.

[0104] <Method of manufacturing two-component developer> The two-component developer contains a toner and the magnetic carrier. The toner has toner particles containing a binder resin. In a two-component developer, the mixing ratio of toner to magnetic carrier is preferably 2 to 15 parts by weight, more preferably 4 to 12 parts by weight, per 100 parts by weight of magnetic carrier. By keeping the ratio within this range, toner scattering is reduced and the amount of triboelectric charge is stabilized over a long period of time. When preparing a two-component developer, the desired amounts of magnetic carrier and toner are weighed and mixed in a mixer. Examples of mixing devices include a double-con mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, and a Nauta mixer. Among these, a V-type mixer is preferred from the viewpoint of the dispersibility of the magnetic carrier.

[0105] The methods for measuring various physical properties are explained below. <Method for confirming the partial structure represented by formula (T3)> Confirmation of the structure represented by formula (T3) in the organosilicon polymer contained in the magnetic carrier The following method is used for recognition: The presence or absence of an alkyl group, a phenyl group, or an alkylamino group represented by R in formula (T3) is determined by the following: 13 The detailed structure of formula (T3) is 1 H-NMR, 13 C-NMR and 29 The measurement was confirmed by Si-NMR. The equipment and measurement conditions used are as follows: (Measurement conditions) Equipment: BRUKER AVANCE III 500 Probe: 4mm MAS BB / 1 H Measurement temperature: room temperature Sample rotation speed: 6kHz Sample: 150 mg of the measurement sample (tetrahydrofuran (THF) insoluble portion of organosilicon polymer for NMR measurement) is placed in a sample tube with a diameter of 4 mm. Using this method, the presence or absence of an alkyl group, phenyl group, or alkylamino group represented by R in formula (T3) is confirmed. If a signal is confirmed, the structure of formula (T3) is deemed to be "present."

[0106] ( 13 C-NMR (solid state) measurement conditions Measurement nuclear frequency: 125.77MHz Reference substance: Glycine (external standard: 176.03ppm) Observation width: 37.88kHz Measurement method: CP / MAS Contact time: 1.75ms Repeat time: 4 seconds Accumulation count: 2048 times LB value: 50Hz

[0107] ( 29 Si-NMR (Solid State) Measurement Method (Measurement conditions) Equipment: BRUKER AVANCE III 500 Probe: 4mm MAS BB / 1H Measurement temperature: room temperature Sample rotation speed: 6kHz Sample: 150 mg of the measurement sample (tetrahydrofuran-insoluble portion of organosilicon polymer for NMR measurement) is placed in a sample tube with a diameter of 4 mm. Measurement nuclear frequency: 99.36MHz Reference material: DSS (external standard: 1.534ppm) Observation width: 29.76kHz Measurement method: DD / MAS, CP / MAS 29Si 90° Pulse width: 4.00μs@-1dB Contact time: 1.75ms to 10ms Repeat time: 30 s (DD / MAS), 10 s (CP / MAS) Accumulation count: 2048 times LB value: 50Hz

[0108] In the organosilicon polymer contained in the magnetic carrier, the partial structure represented by formula (T3) (T3 structure) and the O bonded to silicon 1 / 2 How to calculate the percentage of structures where the number of The T3 structure, X1 structure, X2 structure, X3 structure and X4 structure are 1 H-NMR, 13 C-NMR and 29 This can be confirmed by Si-NMR. Tetrahydrofuran insoluble fraction of organosilicon polymers 29 After Si-NMR measurement, multiple silane components with different substituents and bonding groups in the magnetic carrier were subjected to curve fitting to determine the O bonded to silicon represented by the following formula (X4): 1 / 2 X4 structure, where the number of is 4.0, O bonded to silicon represented by (X3) 1 / 2 X3 structure in which the number of O bonded to silicon represented by the following formula (X2) 1 / 2 X2 structure in which the number of O bonded to silicon represented by the following formula (X1) 1 / 2 The peaks are separated into the X1 structure where the number of units is 1.0 and the T unit structure represented by formula (T3), and the mole percentage of each component is calculated from the area ratio of each peak.

[0109] [ka] (In the formula, Ri, Rj, Rk, Rg, Rh, and Rf represent an organic group, a halogen atom, a hydroxy group, or an alkoxy group bonded to a silicon atom.)

[0110] For curve fitting, EXcalibur for Windows (product name) version 4.2 (EX series), software for the JNM-EX400 manufactured by JEOL Ltd., is used. Click "1D Pro" from the menu icon to load the measurement data. Next, select "Curve fitting function" from "Command" on the menu bar and perform curve fitting. An example is shown in Figure 1. Peak division is performed so that the peak of the composite peak difference (a), which is the difference between the composite peak (b) and the measurement result (d), is the smallest. Calculate the areas of the X1 structure, X2 structure, X3 structure, and X4 structure, and then calculate SX1, SX2, SX3, and SX4 using the following formulas.

[0111] Identify the silane monomer by chemical shift value. 29 In Si-NMR measurements, the total peak area of ​​the organosilicon polymer is the sum of the areas of the X1 structure, X2 structure, X3 structure, and X4 structure, excluding the monomer components from the total peak area. SX1+SX2+SX3+SX4=1.00 SX1 = {Area of ​​X1 structure / (Area of ​​X1 structure + Area of ​​X2 structure + Area of ​​X3 structure + X 4) Area of ​​structure SX2 = {Area of ​​X2 structure / (Area of ​​X1 structure + Area of ​​X2 structure + Area of ​​X3 structure + Area of ​​X4 structure)} SX3 = {Area of ​​X3 structure / (Area of ​​X1 structure + Area of ​​X2 structure + Area of ​​X3 structure + Area of ​​X4 structure)} SX4 = {Area of ​​X4 structure / (Area of ​​X1 structure + Area of ​​X2 structure + Area of ​​X3 structure + Area of ​​X4 structure)} ST3 = {Area of ​​T3 structure / (Area of ​​X1 structure + Area of ​​X2 structure + Area of ​​X3 structure + Area of ​​X4 structure)} The chemical shift values ​​of silicon in the X1 structure, X2 structure, X3 structure and X4 structure are shown below. An example of X1 structure (Ri = Rj = -OC2H5, Rk = -CH3): -47 ppm An example of X2 structure (Rg = -OC2H5, Rh = -CH3): -56 ppm An example of X3 structure (Rf=-CH3): -65 ppm The chemical shift values ​​of silicon in the presence of the X4 structure are shown below. X4 structure: -108ppm

[0112] <Method for separating organosilicon polymer contained in magnetic carrier> To obtain the THF-insoluble organosilicon polymer from the magnetic carrier, first the magnetic core particles are eluted with a strong acid, and the remaining organosilicon polymer is dried and solidified. Then THF is added to obtain the THF-insoluble portion.

[0113] <Method for measuring the concentration of silicon element present on the magnetic carrier surface> The silicon concentration (atomic %) relative to the total concentration (dC+dO+dSi) of carbon concentration dC, oxygen concentration dO, and silicon concentration dSi present on the magnetic carrier surface is measured by ESCA (X-ray photoelectron spectroscopy). The ESCA equipment and measurement conditions are as follows: Equipment used: ULVAC-PHI Quantum2000 X-ray photoelectron spectrometer measurement conditions: X-ray source Al Kα X-ray: 100μm 25W 15kV Raster: 300μm x 200μm Pass Energy: 58.70 eV Step Size: 0.125 eV Neutralization electron gun: 20 μA, 1 V Ar ion gun: 7 mA, 10 V Sweep number: Si 15 times, C 10 times, O 5 times From the measured peak intensity of each element, the surface atomic concentration (atomic %) is calculated using the relative sensitivity factor provided by PHI.

[0114] <Measurement of the arithmetic mean surface roughness Ra of the magnetic carrier surface> The magnetic carriers are placed on a sample plate, and those having a particle size within ±10% of the volume average particle size of the magnetic carriers are selected. Using a violet color laser microscope (Keyence Corporation, model name "VK-9500"), the roughness curve of a 4 μm diameter magnetic carrier particle surface is measured. The measurement is performed under the conditions of a lens magnification of 150x, an optical zoom of 20x, a pitch of 0.05 μm, and a cutoff of a curvature of 0.08 mm or more. The arithmetic mean surface roughness Ra is then calculated using three-dimensional surface shape analysis software (Mitani Corporation, product name "SurftopEye"). The Ra is determined for each of the 100 magnetic carriers, and the arithmetic mean value is used as the Ra in the present invention.

[0115] <Average length of roughness curve element of magnetic carrier particle (RSm), unevenness of one period Standard deviation of part length σ> Measurements are carried out using the following measuring equipment and conditions. Scanning probe microscope: Hitachi High-Tech Science Corporation Measurement unit: E-sweep Measurement mode: DFM (resonance mode) shape image Resolution: X data number 256, Y data number 128 Measurement area: 1 μm square Particles to be measured: Particles having a particle size within ±10% of the volume average particle size of the magnetic carrier are selected. RSm and σ for each magnetic carrier particle are calculated as follows. Ten cross sections (cross section 1 to cross section 10) are arbitrarily selected from the measured 1 μm square measurement area. Here, cross section 1 will be used as an example. The length RSm of the part where one period of unevenness occurs is calculated based on the average line of the roughness curve. i is measured for all irregularity periods. The average length RSm' of the roughness curve element is calculated using the following formula:

[0116]

number

[0117] n: Total number of concave and convex cycles in the roughness curve The RSm' is calculated for all of cross sections 1 to 10. Furthermore, the same measurement is carried out for 10 magnetic carrier particles. The average value is calculated and is defined as the average length (RSm) of the roughness curve element in the present invention. In addition, the length of the part where one period of unevenness occurs RSm i The standard deviation σ (=σRSm') is defined as follows:

[0118]

number

[0119] <Method for quantifying the amount of vinyl polymer contained in a magnetic carrier> The amount of vinyl polymer can be measured from the magnetic carrier by the following method. A 100 ml beaker is precisely weighed (measurement value 1), and then approximately 5 g of the sample to be measured is placed in it, and the total mass of the sample and the beaker is precisely weighed (measurement value 2). B. Add approximately 50 ml of toluene to a beaker and shake with an ultrasonic shaker for 5 minutes. C After shaking, let stand for a few minutes, then stir the sample in the beaker by tracing the bottom of the beaker 20 times with a neodymium magnet, and then drain only the toluene solution in which the vinyl polymer has dissolved as waste liquid. D. While holding the sample in the beaker with the neodymium magnet from the outside, add approximately 50 ml of toluene to the beaker again and repeat steps B and C above 10 times. E. Change the solvent to chloroform and repeat steps B and C above once more. F. Place the beaker in a vacuum dryer and dry off the solvent (use a vacuum dryer equipped with a solvent trap, set the temperature to 50°C, vacuum level to -0.093 MPa or less, and dry for 12 hours). G Remove the beaker from the vacuum dryer, leave it for about 20 minutes to cool, and then weigh it. (Measurement value 3). H The amount of coating resin (mass %) is calculated from the measured values ​​obtained as above according to the following formula. Amount of vinyl polymer (mass%) = (Sample mass - Sample mass after dissolving vinyl polymer) / Sample mass x 100 In the above formula, the mass of the sample is determined by calculating (measured value 2 - measured value 1), and the mass of the sample after dissolving the vinyl polymer is determined by calculating (measured value 3 - measured value 1).

[0120] <Amount of coating layer scraped off in magnetic carrier deterioration test> 92.0 parts of the magnetic carrier and 8.0 parts of the toner are mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to prepare a two-component developer. The image forming device used was a modified Canon imageRUNNER ADVANCE C5560, and a two-component developer was placed in the cyan developer. The modifications to the device included the fixing temperature, process speed, and DC voltage V of the developer carrier. DC , the charging voltage V of the electrostatic latent image carrier D The image output evaluation is performed by outputting a FFh image (solid image) with a desired image ratio, and adjusting V so that the amount of toner on the FFh image on the paper is as desired. DC , V D and laser power are adjusted and the following durability test is carried out. In the durability test, 10,000 copies of the following image were printed. Paper: GFC-081 (81.0g / m 2 ) (Canon Marketing Japan Inc.) Toner amount on paper before durability test: 0.35 mg / cm 2 (Before the durability test, the DC voltage V DC , the charging voltage V of the electrostatic latent image carrier D (Adjusted by laser power. Do not change during or after the durability test.) Evaluation image: A band chart image with an image ratio of 1% FFh is placed in the center of the A4 paper. Fixing test environment: High temperature and humidity environment: Temperature 30°C / Humidity 80%RH (hereinafter referred to as "H / H") Process speed: 377 mm / sec The amount of Si in the initial magnetic carrier and the magnetic carrier separated after the durability test is measured by fluorescent X-ray (wavelength dispersive fully automatic fluorescent X-ray analyzer manufactured by PANalytical) and the amount of scraping is calculated. Amount of organosilicon polymer scraped off = (initial amount of organosilicon polymer - amount of organosilicon polymer after vibration) / initial amount of organosilicon polymer x 100 The toner used is the same as Toner 1 in the examples described below. The procedure for measuring fluorescent X-rays is as follows. The included dedicated software "SuperQ ve" is used to set measurement conditions and analyze measurement data. r.4.0F" (PANalytical) is used. A 10 g sample is weighed into a cup for powder measurement recommended by PANalytical with a special film attached, and quantified using the FP method under atmospheric pressure in a He atmosphere. Measurements are carried out under the above conditions, and elements are identified based on the peak positions of the obtained X-rays. Their concentrations are then calculated from the counting rate (unit: cps), which is the number of X-ray photons per unit time.

[0121] <Toner inorganic fine particle coverage> The coverage of inorganic fine particles is calculated from the atomic weight of silicon (hereinafter abbreviated as Si) derived from silica present on the surface of the toner particles, as measured by ESCA (X-ray photoelectron spectroscopy). ESCA is an analytical method that detects atoms in a depth range of a few nanometers or less from the surface of a sample. This makes it possible to detect atoms on the surface of toner particles. The sample holder is a 75 mm square platen (equipped with a screw hole approximately 1 mm in diameter for fixing the sample) that comes with the device. The screw hole in the platen is a through hole, so it is plugged with resin or similar to create a recess approximately 0.5 mm deep for powder measurement. The sample is prepared by packing the measurement sample into the recess with a spatula or similar tool and leveling it off. The ESCA equipment and measurement conditions are as follows: Equipment used: ULVAC-PHI PHI5000VersaProbe II Analysis method: Narrow analysis Measurement conditions: X-ray source: Al-Kα X-ray conditions: 100μ25W15kV Photoelectron capture angle: 45° Pass Energy: 58.70 eV Measurement range: 300 μm x 200 μm Measurements are performed under the above conditions. The analysis method involves first correcting the peak derived from the C-C bond of the carbon 1s orbital to 285 eV. Then, from the peak area derived from the silicon 2p orbital, where the peak top is detected between 100 eV and 105 eV, the amount of Si derived from silica relative to the total amount of constituent elements is calculated using the relative sensitivity factor provided by ULVAC-PHI. Next, the silica alone applied to the toner is measured using the same method as above, and the amount of Si derived from the silica relative to the total amount of constituent elements is calculated. The ratio of the amount of Si when the toner is measured to the amount of Si when the external additive alone is measured is taken as the silica coverage rate. [Example]

[0122] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the scope of the present invention. In the following formulations, parts are by weight unless otherwise specified.

[0123] <Production example of magnetic core particle 1> <Production example of irregular magnetic particles a> Fe3O4 was mixed and pulverized in a wet ball mill for 10 hours. 1 part polyvinyl alcohol was added to 100 parts of Fe3O4, and the mixture was granulated and dried in a spray dryer. The mixture was then fired in an electric furnace at 900°C for 10 hours in a nitrogen atmosphere with an oxygen concentration of 0.0% by volume. The obtained magnetic material was pulverized in a dry ball mill for 5 hours, and then classified using a wind classifier (Elbow Jet Lab EJ-L3, manufactured by Nittetsu Mining Co., Ltd.) to simultaneously remove fine and coarse powders, yielding irregular shaped magnetic particles a with a number average particle size of 1.7 μm.

[0124] <Preparation of irregular magnetic particles A> To 100 L of a slurry containing 90 g / L of the above-mentioned irregular magnetic particles a, adjusted to a number-average particle size of 1.7 μm, was added sodium hydroxide solution at 90° C. to adjust the pH to 8.5, and then 30 L of a 2.5 mol / L aqueous manganese sulfate solution and an aqueous sodium hydroxide solution were added simultaneously over 190 minutes while adjusting the pH to 8.5±0.2. Next, after aging for 60 minutes, dilute sulfuric acid was added to adjust the pH to 7.0, followed by filtration, washing with water, and drying to obtain Mn-surface-treated irregular magnetic particles A. The resulting amorphous magnetic particles A and a silane coupling agent (3-(2-aminoethylamino)propyltrimethoxysilane) (0.2 parts per 100 parts of particles A) were then introduced into a container. The mixture was then mixed and stirred at high speed at 100°C for 1 hour in the container to perform a surface treatment, yielding amorphous magnetic particles A for magnetic core particles 1 of a magnetic material dispersion type.

[0125] <Production example of irregular magnetic particles b> Fe3O4 was mixed and pulverized in a wet ball mill for 10 hours. 1 part polyvinyl alcohol was added to 100 parts of Fe3O4, and the mixture was granulated and dried in a spray dryer. The mixture was then fired in an electric furnace at 900°C for 10 hours in a nitrogen atmosphere with an oxygen concentration of 0.0% by volume. The obtained magnetic material was pulverized in a dry ball mill for 10 hours, and then classified using a wind classifier (Elbow Jet Lab EJ-L3, manufactured by Nittetsu Mining Co., Ltd.) to simultaneously remove fine and coarse powders, yielding irregular shaped magnetic particles b with a number average particle size of 0.3 μm.

[0126] <Preparation of irregular magnetic particles B> The obtained irregular magnetic particles b and a silane coupling agent (3-glycidoxypropylmethyldimethoxysilane) (1.2 parts per 100 parts of particles b) were introduced into a container, and the mixture was then surface-treated by high-speed mixing and stirring at 100°C for 1 hour to obtain irregular magnetic particles B for magnetic material-dispersed magnetic core particles 1.

[0127] (Dispersion process) Phenol: 10.0 parts Formaldehyde solution (37% by mass aqueous formaldehyde solution): 15.0 parts ·Amorphous magnetic particles A: 10.0 parts ·Amorphous magnetic particles B: 90.0 parts 25% by weight ammonia water: 3.5 parts ·Wednesday: 15.0 copies The above materials were introduced into a reactor, heated to 40°C, and mixed thoroughly. The mixture was then heated to 85°C at an average rate of 1.5°C / min while stirring, and maintained at 85°C for 3 hours to polymerize and harden the mixture. The peripheral speed of the stirring blade was 1.96 m / s. After the polymerization reaction, the mixture was cooled to 30°C and water was added. The supernatant was removed and the resulting precipitate was washed with water and then air-dried. The air-dried product was dried under reduced pressure (5 mmHg or less) at 180°C for 5 hours to obtain magnetic core particles 1 of a magnetic material dispersion type. The D50 of the magnetic core particles 1 of a magnetic material dispersion type was 43.1 μm.

[0128] <Production example of magnetic core particle 2> Process 1 (weighing and mixing process) ·Fe2O370.4 parts ·MnCO325.0 parts ·Mg(OH)23.5 parts ·SrCO31.1 parts The ferrite raw materials were weighed, and 20 parts of water were added to 100 parts of the ferrite raw materials. Then, the mixture was wet mixed in a ball mill using zirconia with a diameter (φ) of 10 mm for 3 hours to prepare a slurry. The solid content of the slurry was 80 mass %. Process 2 (pre-firing process) The mixed slurry was dried using a spray dryer (manufactured by Okawahara Chemical Engineering Co., Ltd.) and then fired in a batch electric furnace in a nitrogen atmosphere (oxygen concentration 1.0% by volume) at a temperature of 1070°C for 3.0 hours to produce calcined ferrite.

[0129] Process 3 (crushing process) The calcined ferrite was crushed to about 0.5 mm using a crusher, and water was added to prepare a slurry. The solid content of the slurry was adjusted to 70 mass %. The slurry was crushed for 3.5 hours using a wet ball mill with 1 / 8-inch stainless steel beads to obtain a slurry. This slurry was further crushed for 4 hours using a wet bead mill with 1 mm diameter zirconia to obtain a calcined ferrite slurry with a volume-based 50% particle size (D50) of 1.1 μm. Process 4 (granulation process) To 100 parts of the calcined ferrite slurry, 1.0 part of ammonium polycarboxylate as a dispersant and 1.5 parts of polyvinyl alcohol as a binder were added, and the mixture was granulated into spherical particles using a spray dryer (manufactured by Okawara Kakoki Co., Ltd.) and dried. The resulting granules were subjected to particle size adjustment and then heated at 720°C for 2 hours in a rotary electric furnace to remove organic substances such as the dispersant and binder.

[0130] Step 5 (baking process) In a nitrogen atmosphere (oxygen concentration 0.3% by volume), the temperature was raised from room temperature to the firing temperature (1250°C). The time at 1300°C was set to 1.7 hours, and the firing was carried out by holding at a temperature of 1300°C for 4.5 hours. Thereafter, the temperature was lowered to 60°C over 8 hours, and the nitrogen atmosphere was returned to the air, and the mixture was taken out at a temperature of 40°C or below. Process 6 (sorting process) After crushing the agglomerated particles, the particles were sieved through a sieve with 150 μm openings to remove coarse particles, air classification was carried out to remove fine powder, and further low magnetic force particles were removed by magnetic separation to obtain magnetic core particles 2. The D50 of the obtained magnetic core particles 2 was 41.3 μm.

[0131] <Production Example of Magnetic Core Particle 3> ·Fe2O369.3 parts ·MnCO327.5 parts ·Mg(OH)21.7 parts ·SrCO31.5 parts In the manufacturing example of magnetic core particle 2, the raw materials were changed as described above, and the reaction was carried out in the same manner except that the oxygen concentration in step 5 (firing step) was changed to 1.0 volume % and the firing temperature to 1150°C, thereby obtaining porous magnetic core pre-filled particle 3 for magnetic core particle 3.

[0132] <Production Example of Filled Resin Composition> Methyl silicone oligomer (KR-400: Shin-Etsu Silicone Co., Ltd.) 95.0 parts γ-aminopropyltriethoxysilane (KBM-903: Shin-Etsu Silicone Co., Ltd.) 5.0 copies The above materials were mixed to obtain a filled resin composition 1.

[0133] (filling process) 100 parts of porous magnetic core pre-filled particles 3 were placed in a stirring vessel of a mixer (NDMV type universal stirrer manufactured by Dalton), and 6 parts of filled resin composition 1 were added dropwise at normal pressure while maintaining the temperature at 60°C. After the dropwise addition was completed, stirring was continued while adjusting the time, and the temperature was raised to 70° C., whereby the resin composition was filled into the porous magnetic core pre-filled particles 3 . After cooling, the resulting resin-filled magnetic core particles were transferred to a mixer (UD-AT type drum mixer manufactured by Sugiyama Heavy Industries Co., Ltd.) equipped with a spiral blade in a rotatable mixing container, and heated to a curing temperature of 140°C at a rate of 2°C / min while stirring under a nitrogen atmosphere. After that, heating and stirring were continued at 140°C for a curing time of 50 minutes. The mixture was then cooled to room temperature, and the resin-filled and hardened resin-filled magnetic core particles were removed and non-magnetic materials were removed using a magnetic separator. Furthermore, coarse particles were removed using a vibrating sieve to obtain resin-filled magnetic core particles 3. The D50 of resin-filled magnetic core particles 3 was 41.3 μm.

[0134] <Production Example of Vinyl Polymer 1> Solvent: toluene 50.0 parts Solvent: methyl ethyl ketone 50.0 parts Monomer composition 100.0 parts (The monomer composition is a mixture of the following cyclohexyl methacrylate and methyl methacrylate in the ratio shown below.) Cyclohexyl methacrylate 62.7 parts (49.4 mol%) Methyl methacrylate 38.3 parts (50.6 mol%) Polymerization initiator: azobisisobutyronitrile 2.0 parts The above materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. The reaction vessel was heated to 80°C while stirring at 200 rpm, and a polymerization reaction was carried out for 5 hours to obtain a solution in which vinyl polymer 1 of the monomer composition was dissolved. After cooling the solution to 25°C, the solution was poured into 1000.0 parts of methanol with stirring to precipitate a methanol-insoluble matter. The resulting methanol-insoluble matter was filtered, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain vinyl polymer 1. When the vinyl polymer 1 was analyzed by NMR, it was found to contain 49.4 mol % of monomer units derived from cyclohexyl methacrylate and 50.6 mol % of monomer units derived from methyl methacrylate.

[0135] <Production Examples of Vinyl Polymer 2 and Vinyl Polymer 3> Vinyl polymers 2 and 3 were obtained by carrying out the reaction in the same manner as in the production example of vinyl polymer 1, except that the polymerizable monomers and the number of parts thereof were changed as shown in Table 1.

[0136] [Table 1] The abbreviations in Table 1 are as follows: CHMA: Cyclohexyl methacrylate MMA: methyl methacrylate EMA: Ethyl methacrylate

[0137] <Production Example of Vinyl Polymer Solution 1> Vinyl polymer 1: 10.0 parts Solvent: Toluene: 50.0 parts Solvent: Methyl ethyl ketone: 40.0 parts The above materials were placed in a reaction vessel equipped with a stirrer, and vinyl polymer 1 was dissolved therein to obtain vinyl polymer solution 1 (solid content: 10% by mass).

[0138] <Production Examples of Vinyl Polymer Solutions 2 and 3> Vinyl polymer solutions 2 and 3 were obtained by dissolving in the same manner as in the production example of vinyl polymer solution 1, except that the vinyl polymer was changed to vinyl polymer 2 or 3, respectively.

[0139] <Production example of dispersion stabilizer aqueous solution 1> Na3PO4 aqueous solution (0.1 mol / L) 100.0 parts 70.0 parts ion-exchanged water HCl aqueous solution (1.0 mol / L) 2.4 parts The above materials were placed in a reaction vessel equipped with a reflux condenser and a thermometer. Subsequently, the contents of the reaction vessel were stirred at 12,000 rpm using a high-speed stirring device, TK-Homomixer, while maintaining the temperature at 60°C. CaCl2 aqueous solution (1.0 mol / L) 85.0 parts The above materials were gradually added to the mixture to obtain a dispersion stabilizer aqueous solution 1 containing fine, poorly water-soluble dispersion stabilizer Ca3(PO4)2.

[0140] <Production Example of Silane Compound Hydrolyzed Solution 1> 3-aminopropyltriethoxysilane 10.0 parts Methyltriethoxysilane 36.0 parts 54.0 parts ion-exchanged water The above materials were placed in a reaction vessel equipped with a stirrer, the pH was adjusted to 3.0 with 10% by mass hydrochloric acid, and hydrolysis was carried out with stirring to obtain a silane compound hydrolyzed liquid 1. Completion of hydrolysis was confirmed when the liquid, which was initially separated into two phases, became a single phase.

[0141] <Production Examples of Silane Compound Hydrolyzed Solutions 2 to 16> Silane compound hydrolyzed solutions 2 to 16 were obtained by carrying out the reaction in the same manner as in the production example of silane compound hydrolyzed solution 1, except that the silane compounds were changed as shown in Table 2.

[0142] [Table 2]

[0143] <Production example of surfactant aqueous solution 1> Polyoxyethylene styrenated phenyl ether 10.0 parts 90.0 parts ion-exchanged water The above materials were placed in a reaction vessel equipped with a stirrer and dissolved under stirring to obtain surfactant aqueous solution 1.

[0144] <Production Examples of Surfactant Aqueous Solutions 2 and 3> Surfactant aqueous solutions 2 and 3 were obtained by carrying out the reaction in the same manner as in the production example of surfactant aqueous solution 1, except that the surfactants were changed as shown in Table 3.

[0145] [Table 3]

[0146] <Magnetic Carrier 1 Manufacturing Example> Step 1 (primerization step) Magnetic core particles 1 100.0 parts 15.0 parts of vinyl polymer solution 1 (solid content 10% by mass) The above materials were put into a planetary mixer (Nauta Mixer VN type manufactured by Hosokawa Micron Corporation), and the screw-shaped mixing blade was rotated at 3.5 revolutions per minute and 100 revolutions per minute while stirring. Nitrogen was supplied at a flow rate of 0.1 m 3 The mixture was heated to 70°C and then applied for 20 minutes to form a primer. The mixture was then transferred to a mixer (UD-AT type drum mixer manufactured by Sugiyama Heavy Industries Co., Ltd.) equipped with a spiral blade in a rotatable mixing container, and heat-treated for 2 hours at 150°C in a nitrogen atmosphere while stirring at 10 revolutions per minute. The mixture was then separated by magnetic separation to separate out low-magnetic-force particles, which were passed through a sieve with 70µm openings and then classified with an air classifier to obtain primer-modified magnetic core particles 1 with a volume-based 50% particle size (D50) of 40.2µm.

[0147] Step 2 (slurrying step) Primer magnetic core particles 1: 15.0 parts Dispersion stabilizer aqueous solution 1: 100.0 parts Surfactant aqueous solution 1: 0.8 parts The above materials were placed in a reaction vessel equipped with a thermometer. The reaction vessel was kept at 25°C and dispersed at 5000 rpm for 6 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA Japan Co., Ltd.) to obtain primer-modified magnetic core particle dispersion liquid 1.

[0148] Process 3 (condensation process) Primer magnetic core particle dispersion 1: 100.0 parts Silane compound hydrolysis solution 1: 1.8 parts The above materials were placed in a reaction vessel equipped with a stirrer and a thermometer. The temperature inside the reaction vessel was raised to 70°C while stirring at 200 rpm. The pH was adjusted to 9.0 with 1 mol / L NaOH aqueous solution and stirred for 240 minutes to carry out a condensation reaction. Next, the pH was adjusted to 1.5 with dilute hydrochloric acid to remove the dispersion stabilizer. After that, the mixture was filtered using Kiriyama filter paper (No. 5C: pore size 1 μm) to separate the particles from the filtrate. The obtained particles were further washed with ion-exchanged water and vacuum-dried at 30°C for 24 hours to obtain magnetic carrier 1. The obtained magnetic carrier 1 had an ST3 of 0.70, a silicon atom concentration of 23.4 atomic %, an ST3 / SX2 of 2.4, and an arithmetic mean surface roughness Ra of 100 nm.

[0149] <Manufacturing Examples of Magnetic Carriers 2 to 36> Magnetic Carriers 2 to 36 were obtained in the same manner as in the production example of Magnetic Carrier 1, except that the magnetic core particles, vinyl polymer solution, amount of vinyl polymer solution added, aqueous surfactant solution, amount of aqueous surfactant solution added, type and amount of silane compound hydrolyzed solution, and pH were changed as shown in Table 4. The physical properties are shown in Table 5.

[0150] [Table 4] [Table 5]

[0151] <Production example of silicone resin solution 1> Silicone varnish (KR255, manufactured by Shin-Etsu Chemical Co., Ltd.) (solid content 20% by mass) 100.0 parts Solvent: toluene 100.0 parts The above materials were placed in a reaction vessel equipped with a stirrer and mixed for 1 hour to obtain silicone resin solution 1( A solid content of 10% by mass was obtained.

[0152] <Magnetic Carrier 37 Manufacturing Example> (Coating process) Magnetic core particles 3 100.0 parts Silicone resin solution 1 (solid content 10% by mass) 30.0 parts The above materials were put into a planetary mixer (Nauta Mixer VN type manufactured by Hosokawa Micron Corporation), and the screw-shaped mixing blade was rotated at 3.5 revolutions per minute and 100 revolutions per minute while stirring. Nitrogen was supplied at a flow rate of 0.1 m 3 The flow rate was adjusted to / min and the pressure was reduced (75 mmHg). After heating to a temperature of 70°C, the coating operation was carried out for 20 minutes to complete the coating. The mixture was then transferred to a mixer (a UD-AT type drum mixer manufactured by Sugiyama Heavy Industries Co., Ltd.) equipped with a spiral blade in a rotatable mixing container, and heat-treated for 2 hours at 150°C in a nitrogen atmosphere while stirring at 10 revolutions per minute. The mixture was then separated into low magnetic particles by magnetic separation, passed through a sieve with 70μm openings, and then classified with an air classifier to obtain magnetic carrier 37 having a 50% particle size (D50) of 40.2μm based on volume distribution. The magnetic carrier 31 had an ST3 of 0.00, a silicon atom concentration of 10.5 atomic %, an ST3 / SX2 of 0.0, and an arithmetic mean surface roughness Ra of 15 nm.

[0153] <Production example of methylol melamine solution 1> Melamine powder 100.0 parts 260.0 parts of 37% formalin 300.0 parts ion-exchanged water The above materials were placed in a reaction vessel equipped with a stirrer and a thermometer, and the temperature was raised to 60°C, after which the mixture was mixed for 1 hour. The mixture was combined to obtain a clear methylolmelamine solution 1 (solid content: 30% by mass).

[0154] <Magnetic Carrier 38 Manufacturing Example> (Coating process) Magnetic core particles 2 100.0 parts Methylol melamine solution 1 (solid content 30% by mass) 10.0 parts The above materials were placed in a planetary mixer (Nauta Mixer VN type manufactured by Hosokawa Micron Corporation) and heated to a temperature of 85°C. After that, a glacial acetic acid aqueous solution acid catalyst was added, and the mixture was stirred while the screw-shaped stirring blade was revolving at 3.5 revolutions per minute and rotating at 100 revolutions per minute. The coating operation was carried out for 20 minutes to form a coating. The mixture was then transferred to a mixer (UD-AT type drum mixer manufactured by Sugiyama Heavy Industries Co., Ltd.) equipped with a spiral blade in a rotatable mixing container, and heat-treated for 2 hours at 150°C in a nitrogen atmosphere while stirring at 10 revolutions per minute. The mixture was then separated into low magnetic particles by magnetic separation, passed through a sieve with 70μm openings, and then classified with an air classifier to obtain magnetic carrier 38 having a 50% particle size (D50) of 40.2μm based on volume distribution. The magnetic carrier 32 had an ST3 of 0.00, a silicon atom concentration of 0.0 atomic %, an ST3 / SX2 of 0.0, and an arithmetic mean surface roughness Ra of 15 nm.

[0155] <Production example of amorphous resin 1> Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane: 73.8 parts (0.19 moles; 100.0 mole% based on the total number of moles of polyhydric alcohol) Terephthalic acid: 12.5 parts (0.08 moles; 48.0 mole % based on the total number of moles of polycarboxylic acids) Adipic acid: 7.8 parts (0.05 moles; 34.0 mole % based on the total number of moles of polycarboxylic acids) Titanium tetrabutoxide (esterification catalyst): 0.5 parts The above materials were weighed and placed in a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. After the atmosphere in the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and the temperature was kept at 200°C. The mixture was allowed to react for 2 hours with stirring. Furthermore, the pressure inside the reaction vessel was reduced to 8.3 kPa and maintained for 1 hour, after which it was cooled to 160 and returned to atmospheric pressure (first reaction step). Trimellitic acid: 5.9 parts (0.03 moles; 18.0 mole % based on the total number of moles of polycarboxylic acids) tert-butylcatechol (polymerization inhibitor): 0.1 parts by mass The above materials were then added, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 200°C. Once it was confirmed that the softening point measured in accordance with ASTM D36-86 had reached 120°C, the temperature was reduced to stop the reaction (second reaction step), yielding Amorphous Resin 1. The resulting Amorphous Resin 1 had a peak molecular weight Mp of 10,000, a softening point Tm of 110°C, and a glass transition temperature Tg of 60°C.

[0156] <Toner 1 manufacturing example> 100 parts amorphous resin 1 Fischer-Tropsch wax (maximum endothermic peak temperature 90°C) 4 parts Carbon black 10 parts The above materials were mixed using a Henschel mixer (FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 1500 rpm for 5 minutes, and then kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Co., Ltd.) set at a temperature of 130° C. The resulting kneaded product was cooled and coarsely crushed to 1 mm or less using a hammer mill to obtain a coarsely crushed product. The obtained coarsely crushed material was finely crushed using a mechanical crusher (T-250, manufactured by Turbo Kogyo Co., Ltd.), and further classified using a Faculty (F-300, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions were a classifying rotor rotation speed of 11,000 rpm and a dispersing rotor rotation speed of 7,200 rpm. Toner particles 1: 100 parts Silica particle A: Fumed silica surface-treated with hexamethyldisilazane (Median diameter (D50) based on number is 120 nm) 4 parts Small inorganic particles: Titanium oxide particles surface-treated with isobutyltrimethoxysilane (Median diameter (D50) based on number is 10 nm) 1 part The above materials were mixed in a Henschel mixer (FM-75 model, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 1900 rpm for 10 minutes to obtain negatively charged toner 1. The coverage of toner 1 with inorganic fine particles was 30%.

[0157] <Toner 2 manufacturing example> The same procedure as in the production example of Toner 1 was carried out except that 2 parts of a quaternary ammonium salt (BONTRON "P-51" manufactured by Orient Chemical Industry Co., Ltd.) was added, thereby obtaining Toner 2 exhibiting positive charging properties. The coverage rate of Toner 2 with inorganic fine particles was 30%.

[0158] <Manufacturing example of two-component developer 1> 92.0 parts of magnetic carrier 1 and 8.0 parts of toner 1 were mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain two-component developer 1.

[0159] <Production examples of two-component developers 2 to 38> In the production example of two-component developer 1, the same operation was carried out except that the combination of toner and magnetic carrier was changed as shown in Table 6, to obtain two-component developers 2 to 38.

[0160] [Table 6]

[0161] Example 1 The above two-component developer 1 was used for evaluation. The image forming apparatus used was a modified Canon imageRUNNER ADVANCE C5560, and two-component developer 1 was placed in the developing device for cyan. The modifications to the apparatus included the fixing temperature, process speed, and DC voltage V DC , the charging voltage V of the electrostatic latent image carrier D The image output evaluation was carried out by outputting a FFh image (solid image) with the desired image ratio, and adjusting V so that the amount of toner on the FFh image on the paper was the desired amount. DC , V D The temperature and laser power were adjusted and the evaluation described below was carried out. FFh is the hexadecimal value of 256 gradations, with 00h being the first gradation of the 256 gradations. FFh is the 256th gradation (solid area) of the 256 gradations. Each item was evaluated before and after the durability test. In the durability test, 10,000 copies of the following image were printed. Paper: GFC-081 (81.0g / m 2 ) (Canon Marketing Japan Inc.) Toner amount on paper before durability test: 0.35 mg / cm 2 (Before the durability test, the DC voltage V DC , the charging voltage V of the electrostatic latent image carrier D (Adjusted by laser power. Do not change during or after the durability test.) Evaluation image: A band chart image with an image ratio of 1% FFh is placed in the center of the A4 paper. Fixing test environment: High temperature and humidity environment: Temperature 30°C / Humidity 80%RH (hereinafter referred to as "H / H") Process speed: 377 mm / sec

[0162] The evaluation was carried out based on the following evaluation methods, and the results are shown in Table 7. [Charge stability] Paper: GFC-081 (81.0g / m 2 ) (Canon Marketing Japan Inc.) Toner amount on paper before durability test: 0.35 mg / cm 2 (Before the durability test, the DC voltage V DC , the charging voltage V of the electrostatic latent image carrier D (Adjusted by laser power. Do not change during or after the durability test.) Evaluation image: A 2cm x 5cm image of FFh is placed in the center of the A4 paper. Test environment: High temperature and humidity environment: Temperature 30°C / Humidity 80%RH (hereinafter referred to as "H / H") The amount of triboelectric charge of the toner on the electrostatic latent image carrier was calculated by suction-collecting the toner using a metal cylindrical tube and a cylindrical filter. Specifically, the amount of triboelectric charge of the toner on the electrostatic latent image carrier was measured using a Faraday cage. A Faraday cage is a coaxial double cylinder, with the inner and outer cylinders insulated. If a charged object with a charge Q is placed inside this inner cylinder, electrostatic induction will create the same effect as if a metal cylinder with a charge Q were present. This induced charge was measured with an electrometer (Kesley 6517A, manufactured by Kesley), and the charge Q (mC) divided by the toner mass M (kg) in the inner cylinder (Q / M) was determined as the toner's triboelectric charge. Toner triboelectric charge (mC / kg) = Q / M Before the durability test, the above-mentioned evaluation image was formed on the electrostatic latent image carrier, and before the image was transferred to the intermediate transfer member, the rotation of the electrostatic latent image carrier was stopped, and the toner on the electrostatic latent image carrier was sucked and collected using a metal cylindrical tube and a cylindrical filter, and [Q / M before test] was measured. Next, after the durability test, the same operation as before the durability test was carried out, and the charge amount per unit mass Q / M (mC / kg) on ​​the electrostatic latent image bearing member after the durability test was measured. Then, the charge fluctuation difference was calculated using the following formula. The obtained charge fluctuation difference was evaluated according to the following evaluation criteria. If the evaluation was A to D, it was judged to be good. Charge fluctuation difference=|{(Q / M per unit mass on the electrostatic latent image carrier before durability test) / (Q / M per unit mass on the electrostatic latent image carrier after durability test)} / 100|-100 (Evaluation criteria) A: Charge fluctuation difference is less than 5% B: Charge fluctuation difference is 5% or more and less than 10% C: Charge fluctuation difference is 10% or more and less than 15% D: Charge fluctuation difference is 15% or more and less than 20% E: Charge fluctuation difference is 20% or more

[0163] [Image density stability] Paper: GFC-081 (81.0g / m 2 ) (Canon Marketing Japan Inc.) Toner amount on paper before durability test: 0.35 mg / cm 2 (Before the durability test, the DC voltage V DC , the charging voltage V of the electrostatic latent image carrier D (Adjusted by laser power. Do not change during or after the durability test.) Evaluation image: A 2cm x 5cm image of FFh is placed in the center of the A4 paper. Test environment: High temperature and humidity environment: Temperature 30°C / Humidity 80%RH (hereinafter referred to as "H / H") Before the durability test, the above evaluation image was printed and the density of the image was measured with an optical densitometer to determine image density A. Next, after the durability test, the above evaluation image was printed and the density of the image was measured with an optical densitometer to determine image density B. An X-Rite color reflection densitometer (manufactured by X-Rite) was used as the optical densitometer. Then, the density fluctuation difference was calculated using the following formula. The obtained density fluctuation difference was evaluated according to the following evaluation criteria. If the evaluation was A to D, it was judged to be good. Density fluctuation difference = |Image density A - Image density B| (Evaluation criteria) A: Density fluctuation difference less than 0.05 B: Density fluctuation difference 0.05 or more and less than 0.10 C: Density fluctuation difference 0.10 or more and less than 0.15 D: Density fluctuation difference 0.15 or more and less than 0.20 E: Density fluctuation difference 0.20 or more

[0164] [Leakage] Paper: GFC-081 (81.0g / m 2 ) (Canon Marketing Japan Inc.) High temperature and humidity environment: Temperature 30°C / Humidity 80%RH (hereinafter referred to as "H / H") Evaluation image: A full-page image of FFh, 19cm x 26cm, placed on the A4 paper mentioned above Test environment: High temperature and humidity environment: Temperature 30°C / Humidity 80%RH (hereinafter referred to as "H / H") Before the durability test, five of the above evaluation images were printed out, and the number of white dots with a diameter of 1 mm or more on the images was counted to determine the number of leaks A. Next, after the durability test, the above evaluation images were printed out, and the number of white dots with a diameter of 1 mm or more on the images was counted to determine the number of leaks B. Then, the leakage fluctuation difference was calculated using the following formula. The obtained leakage fluctuation difference was evaluated according to the following evaluation criteria. If the evaluation was A to D, it was judged to be good. Leak fluctuation difference = |Leak count B - Leak count A| A: Less than 5 B: 5 or more but less than 10 C: 10 or more but less than 15 D: 15 or more but less than 20 E: 20 or more

[0165] [Wear resistance] The toner and magnetic carrier were separated from the two-component developer before and after the durability test, and the amount of abrasion of the coating layer of the magnetic carrier was quantified using a fluorescent X-ray analyzer. The measurement conditions were as described above. The calculated amount of abrasion was evaluated according to the following evaluation criteria. A rating of A to D was considered to be good. A: Less than 0.5% by mass B: 0.5% by mass or more and less than 1.0% by mass C: 1.0% by mass or more and less than 1.5% by mass D: 1.5% by mass or more and less than 2.0% by mass E: 2.0% by mass or more

[0166] <Examples 2 to 31 and Comparative Examples 1 to 7> In the evaluation of Example 1, the same procedure was carried out except that the two-component developer used was changed as shown in Table 6, and Examples 2 to 31 and Comparative Examples 1 to 7 were evaluated. Incidentally, Example 31 was evaluated as a reference example. The evaluation results are shown in Table 7. Here, in order to evaluate the positively charged toner, a Kyocera Document Solutions TASKalfa406ci image forming apparatus was also modified so that it could be adjusted in the same way as the modified Canon imageRUNNER ADVANCE C5560.

[0167] [Table 7]

Claims

1. A magnetic carrier having magnetic core particles and magnetic carrier particles having a coating layer of an organosilicon polymer on the surface of the magnetic core particles, The organosilicon polymer has a structure represented by the following formula (T3): The organosilicon polymer is a condensation polymer selected from the group consisting of the following (1) to (8): (1) a condensation polymer of 3-aminopropyltriethoxysilane and methyltriethoxysilane, (2) condensation polymer of methyltriethoxysilane; (3) condensation polymer of phenyltriethoxysilane, (4) A condensation polymer of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and methyltriethoxysilane. (5) Condensation polymer of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and ethyltriethoxysilane, (6) Condensation polymer of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and n-propyltriethoxysilane, (7) Condensation polymer of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and hexyltriethoxysilane, (8) Condensation polymer of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and phenyltriethoxysilane, The tetrahydrofuran insoluble portion of the organosilicon polymer ２９ In Si-NMR analysis, the ratio ST3 of the peak area of ​​the structure represented by formula (T3) below to the total peak area of ​​the organosilicon polymer is 0.70 or more: In the roughness curve of the magnetic carrier particles measured by a scanning probe microscope, The magnetic carrier is characterized in that the average length (RSm) of the roughness curve elements of the magnetic carrier particles is 20 nm or more and 500 nm or less, and the ratio (σ / RSm) of the standard deviation σ of the length of the portion where one period of unevenness occurs to the RSm is 0.80 or less. R-Si(O １／２ ) ３ (T3) In the formula, R represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a 3-aminopropyl group, or an N-2-(aminoethyl)-3-aminopropyl group.

2. 2. The magnetic carrier according to claim 1, wherein, in an X-ray photoelectron spectroscopy analysis of the magnetic carrier, the ratio of the silicon atom concentration dSi to the sum (dSi + dO + dC) of the silicon atom concentration dSi, the oxygen atom concentration dO, and the carbon atom concentration dC in the surface layer of the magnetic carrier (dSi / [dSi + dO + dC]) is 2.5 atomic % or more.

3. The tetrahydrofuran insoluble portion of the organosilicon polymer ２９ In the Si-NMR measurement, the ratio of the silicon-bonded O to the total peak area of ​​the organosilicon polymer is １／２ 3. The magnetic carrier according to claim 1, wherein when the ratio of the peak area of ​​a structure in which the number of units is 2.0 is defined as SX2, the ratio of ST3 to SX2, ST3 / SX2, is 1.0 or more.

4. the surface of the magnetic carrier has irregularities, 4. The magnetic carrier according to claim 1, wherein the arithmetic mean surface roughness Ra of the surface of the magnetic carrier satisfies 10 nm≦Ra≦2000 nm.

5. the surface of the magnetic carrier has irregularities, 5. The magnetic carrier according to claim 1, wherein the arithmetic mean surface roughness Ra of the surface of the magnetic carrier satisfies 10 nm≦Ra≦200 nm.

6. the magnetic carrier has a primer layer having a vinyl polymer between the magnetic core particle and the coating layer of the organosilicon polymer, 6. The magnetic carrier according to claim 1, wherein the vinyl polymer has a structure represented by the following formula (1): R Ｖ１ is H, CH ３ or C ２ H ５ indicates R Ｖ２ is H or CH ３ Shows.

7. the magnetic carrier has a primer layer having a vinyl polymer between the magnetic core particle and the coating layer of the organosilicon polymer, 7. The magnetic carrier according to claim 1, wherein the content of the vinyl polymer in the primer layer is 0.1 to 2.0 parts by mass with respect to 100.0 parts by mass of the magnetic core particles.

8. When a deterioration test was carried out using a two-component developer in which 92.0 parts of the magnetic carrier and 8.0 parts of the toner were mixed, and 10,000 images with an image ratio of 1% were output at a process speed of 377 mm / sec, 8. The magnetic carrier according to claim 1, wherein the amount of scraping of the organosilicon polymer that constitutes the coating layer is less than 2.0% by mass of the amount of organosilicon polymer before testing.

9. A two-component developer containing a toner and a magnetic carrier, the toner has toner particles containing a binder resin, A two-component developer, wherein the magnetic carrier is the magnetic carrier according to any one of claims 1 to 8.

10. the toner has the toner particles and inorganic fine particles on the surfaces of the toner particles, The two-component developer according to claim 9, wherein a coverage rate of the toner with the inorganic fine particles is 10% or more and 80% or less.

11. A method for producing the magnetic carrier according to any one of claims 1 to 8, Dispersing the magnetic core particles in an aqueous medium; and A method for producing a magnetic carrier, comprising the step of coating the surfaces of the magnetic core particles with the organosilicon polymer.

12. In the step of dispersing the magnetic core particles in an aqueous medium, compound A is added, 12. The method for producing a magnetic carrier according to claim 11, wherein the compound A is represented by at least one selected from the group consisting of formulas (3-1) to (3-5): In formula (3-1), R' is a hydrocarbon group having 3 to 30 carbon atoms. D is a single bond, an ether bond (-O-), an ester bond (-COO-), an amide group (-CONR Ｃ７ -), or an amino group (-NR Ｃ７ -) (R Ｃ７ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. E is a hydrogen atom or an acyl group having 2 to 31 carbon atoms, and n is an integer of 1 to 60. In formula (3-2), G is a single bond or —(CH ２ -CH ２ -O) ｑ -, and m, n, and q each independently represent an integer of 1 to 60. In formula (3-3), R' is a hydrocarbon group having 3 to 30 carbon atoms, and E is a hydrogen atom or an acyl group having 2 to 31 carbon atoms. In formula (3-4), R' is a hydrocarbon group having 3 to 30 carbon atoms. ６ , B ７ , B ８ , B ９ are each independently a single bond, -(CH ２ CH ２ O) ｎ - or - (CH ２ CH ２ O) ｎ -CH ２ - is. １ , E ２ , E ３ are each independently a hydrogen atom or an acyl group having 2 to 31 carbon atoms, and n is an integer of 1 to 60. In formula (3-5), R' is a hydrocarbon group having 3 to 30 carbon atoms. J is a single bond or a carbonyl bond (>C=O). n is an integer of 1 to 60, and p is an integer of 0 to 60.

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