JP6024323B2 - Electrostatic latent image developer carrier, developer, image forming method, replenishment developer, and process cartridge - Google Patents

Description

  The present invention relates to a carrier for an electrostatic latent image developer, a developer, an image forming method, a replenishment developer, and a process cartridge.

In electrophotographic image formation, an electrostatic latent image is formed on an electrostatic latent image carrier such as a photoconductive substance, and a charged toner is developed on the electrostatic latent image to form a toner image. After that, the toner image is transferred to a recording medium and fixed to form an output image. In recent years, the technology of copying machines and printers using an electrophotographic system is rapidly expanding from monochrome to full color, and the full color market tends to expand.
In color image formation by full-color electrophotography, generally, all colors are reproduced by laminating three color toners of yellow, magenta, and cyan, or four color toners including black.

Conventionally, as a developing method used in an image forming apparatus, a one-component developing method, a two-component developing method, a hybrid developing method, etc. are used, but in order to obtain a clear full-color image with excellent color reproducibility. Therefore, it is necessary to keep the toner amount on the electrostatic latent image carrier faithful to the electrostatic latent image.
When the amount of toner on the electrostatic latent image carrier fluctuates, the image density changes on the recording medium or the color tone of the image fluctuates.

The cause of the fluctuation of the toner amount on the electrostatic latent image carrier is, for example, the fluctuation of the toner charge amount. For example, the phenomenon that the next image takes over the previous image history (ghost phenomenon) in hybrid development is already known. It has been.
This ghost phenomenon is a problem peculiar to the hybrid developing system, and is a phenomenon in which the image density of the next image fluctuates because the toner amount on the toner carrier changes according to the toner consumption pattern of the immediately preceding image. This is because in the hybrid developing system, a constant amount of toner is always supplied to the toner carrier, and thus the amount of toner on the toner carrier varies depending on the number of times the toner is supplied.

  That is, when the previous image prints an image with low toner consumption, the amount of residual toner on the toner carrier is large, and after toner supply, the amount of toner on the toner carrier further increases and the image density becomes high. On the other hand, after printing an image with high toner consumption, the amount of residual toner on the toner carrier is small, and after toner supply, the amount of toner on the toner carrier is small and the image density becomes light.

  As described above, the ghost development in the hybrid development is such that when the toner is transferred from the two-component developer onto the toner carrier, the toner is developed and the toner is removed from the toner carrier, and the toner is not developed. It is difficult to re-apply the toner amount of the part where the toner on the toner carrier remains as it is, and the toner amount on the toner carrier at the time of printing the next image varies depending on the history of the previous image. It is caused by that.

  In order to solve these problems, for example, Patent Documents 1 to 3 propose that the remaining toner on the toner carrier is scraped off by a scraper or a toner collecting roll after development and before toner resupply. Patent Document 4 proposes a method of stabilizing the amount of toner on the toner carrier by collecting the residual toner on the toner carrier to a magnetic roll by a potential difference using between copies or between papers. Has been. Further, as a countermeasure against the hysteresis phenomenon using a magnetic brush, Patent Document 5 proposes to collect and supply toner on the developing roll by setting a wide half-value width region of the magnetic flux density of the magnetic roll. . Further, Patent Document 6 uses a non-spherical carrier as a carrier for a two-component developer, so that a charge is injected up to the carrier at the tip of the magnetic brush, and the substantial difference between the developer carrier and the toner carrier. By narrowing the interval, the amount of toner supplied to the toner carrier at one time is increased, and the toner is supplied up to the toner saturation amount on the toner carrier, so that the toner is carried without being affected by the history of the previous image. A method for keeping the amount of toner on the body constant has been proposed.

Further, as described in Patent Document 7, the ghost phenomenon has been reported in the two-component development method, but the inventors have developed the two-component development method for the reason why the ghost phenomenon occurs in the two-component development method. It is considered that poor drug withdrawal is the cause.
The two-component developer is peeled off by using an odd number of magnets in the developing sleeve and providing a pair of magnets with the same polarity at a position below the rotation axis of the developing sleeve to create a peeling region where the magnetic force is almost zero. In this method, the developer after the development is naturally dropped by using gravity and is peeled off.
However, a counter charge is generated in the carrier when the amount of toner consumed in the previous image is generated, so that a mirror image force is generated between the carrier and the developer carrying member, and the agent concentration is not normally removed at the agent separation pole. This is a phenomenon in which the developing ability is lowered and the image density is decreased by transporting the agent having decreased to the developing area again. That is, there is a problem that the density of the circumference of the sleeve is normal, whereas the density is reduced after the second round.

  In order to solve these problems, for example, Patent Document 7 describes a configuration in which a scooping roll having a magnet inside is arranged in the vicinity of a peeling region on the developing sleeve, and the developer is peeled off with the magnetic force. Has been. The peeled developer is further pumped up by another scooping roll and then conveyed to a developer agitating chamber having a screw to readjust the toner concentration and charge the toner.

  Patent Documents 8 and 9 propose a carrier in which the surface of magnetic core particles is coated with a specific copolymer resin. According to this, there is little change in carrier resistance and developer pumping amount, and the toner composition It is said that there is little fluctuation in charging due to spent, and that fluctuation in charging environment is suppressed.

An object of the present invention is to develop a stable amount of toner and obtain a clear image with excellent color reproducibility without being affected by the toner consumption history of the immediately preceding image in view of the current state of the prior art. In addition, it has stable charging ability over a long period of time, is excellent in both hardness and toughness (flexibility & elasticity) of the carrier coating film, excellent in wear resistance (scraping / peeling), and changes in carrier resistance. Fewer variations in electrification due to spent toner composition, less fluctuations in charging environment, and various characteristics such as image density fluctuations, background stains and in-machine contamination due to toner scattering in various usage environments. To provide a satisfactory career.
It is another object of the present invention to provide an electrostatic latent image developer, an image forming method, a replenishment developer, and a process cartridge using the electrostatic latent image developing carrier.

  The present inventors have described, "A carrier for an electrostatic latent image developer comprising a core material particle having magnetism and a coating layer covering the surface of the core material particle, the core material particle having an SF-2 of 120- 160, Ra is 0.5 to 1.0 μm, the carrier contains 50 to 500 parts by weight of filler in the coating layer with respect to 100 parts by weight of resin, and SF-2 is in the range of 115 to 150. The carrier fluid energy amount is in the range of 3000 to 4000 mJ in terms of the total energy amount at an approach distance of 70 mm when the tip speed of the rotor blade is 100 mm / sec and the approach angle of the rotor blade is -5 ° in the powder rheometer. The inventors have found that the various characteristics of the carrier for an electrostatic latent image developer are more fully satisfied, and have further studied to complete the present invention.

Thus, the above problem is solved by the present invention described below.
A carrier for an electrostatic latent image developer comprising a magnetic core material particle and a coating layer covering the surface of the core material particle, the core material particle having SF-2 of 120 to 160 and Ra of 0.5. The coating layer contains 50 to 500 parts by weight of filler selected from aluminum oxide and barium sulfate with respect to 100 parts by weight of the resin, and the carrier has SF-2 of 127 to The flow energy amount of the carrier is in the range of 3200 to 4000 mJ in the powder rheometer when the tip speed of the rotor blade is 100 mm / sec and the total energy amount is 70 mm when the rotor blade has an approach angle of -5 °. A carrier for an electrostatic latent image developer.

  According to the present invention, a stable toner amount can be developed and image defects can be prevented without being affected by the toner consumption history of the immediately preceding image.

(A) is a figure which shows a mode that a rotary blade rotates with the tip speed of a rotary blade 100 mm / s, moving in the particle | grains with which the container was filled from filling surface H1 to H2 at the approach angle of -5 degrees. b) A diagram showing a vertical load in the powder rheometer, and (c) a diagram showing a rotational torque in the powder rheometer. It is a figure which shows how to obtain | require the total energy with a powder rheometer. It is a figure which shows the rotary blade of a powder rheometer. It is a figure which shows another rotary blade of a powder rheometer. FIG. 2 is a schematic diagram for explaining an example of a developing unit of an image forming apparatus useful for carrying out the image forming method of the present invention. It is the schematic for demonstrating an example of the image development part of the other image forming apparatus useful for implementation of the image forming method of this invention. It is the schematic for demonstrating an example of the image development part of the further another image forming apparatus useful for implementation of the image forming method of this invention. It is a figure which shows an example of the process cartridge of this invention. It is a figure which shows the cell used when measuring the volume specific resistance of the carrier of this invention. It is a figure which shows the apparatus used when measuring the charged state of this invention carrier. (A) is a figure of the longitudinal belt chart used for evaluation of a ghost image, (b) is a figure which shows the density difference of (a) for one round of a sleeve when copied, and (b) after one round.

Hereinafter, the present invention will be described in more detail.
The ghost phenomenon that is the subject of the present invention differs from any of the above ghost phenomena in the generation mechanism. The generation mechanism of the ghost phenomenon in the present invention is considered as follows although the details are not clear. The toner adheres to the developer carrying member according to the immediately preceding image history, and the toner development amount of the next image varies depending on the potential of the toner attached on the developer carrying member. That is, it is considered that the toner development amount of the next image varies depending on the immediately preceding image history.
Specifically, toner adhesion to the developer carrying member occurs when the toner is supplied onto the developer carrying member because a bias is applied in the direction of the developing sleeve during non-image, and is supplied to the developer carrying member. Since the toner has a potential, the developing potential is increased by the potential of the toner on the developer carrying member during copying, and the toner development amount increases. Further, since the toner supplied onto the developer carrier is consumed during development, the amount of toner on the developer carrier is not constant but varies depending on the history of the previous image. That is, at the time of development when the immediately preceding image is a non-image or immediately after the interval between sheets, toner is supplied onto the developer carrier, and the toner adheres on the developer carrier, The image density increases. On the other hand, when the immediately preceding image is an image having a large image area, the toner is consumed on the developer carrying member, so that the image density decreases.
As described above, the phenomenon to be solved by the present invention is a phenomenon in which the toner development amount on the developer carrying member fluctuates in response to the history of the immediately preceding image, and the density fluctuation of the next image appears due to the fluctuation. .

  As a result of intensive studies on this problem, improvement was confirmed by adopting a carrier for an electrostatic latent image developer (hereinafter also simply referred to as a carrier) as a means for solving the above-described problems. Although details are not clear, the irregular shape of the core particles is within a specified range, and the coated core particles, that is, the carrier, forms a low resistance part that is close to the core material resistance, so that the developer is supported at the time of non-image. Since the toner supplied onto the body is less likely to be consumed at the time of copying, it is considered that the toner amount on the developer carrying body is stabilized regardless of the immediately preceding image, and the image uniformity is obtained.

  The core particle used in the present invention is not particularly limited as long as it is a magnetic substance; however, ferromagnetic metals such as iron and cobalt; iron oxides such as magnetite, hematite and ferrite; various alloys and compounds; Examples thereof include resin particles dispersed in the resin. Of these, Mn-based ferrite, Mn-Mg-based ferrite, Mn-Mg-Sr ferrite, and the like are preferable from the viewpoint of environmental considerations.

  The core particles of the present invention have a shape factor SF-2 in the range of 120 to 160, and an arithmetic average surface roughness Ra of 0.5 to 1.0 μm, preferably 0.6 to 0.9 μm. Here, the meaning of defining the arithmetic average surface roughness Ra of the core particles is that the arithmetic average surface roughness Ra is out of the range of 0.5 to 1.0 [mu] m, and the SF is only determined by atypification that is greatly deviated from the spherical shape. This is because core particles in which −2 is in the range of 120 to 160 are not subject to the present invention because carrier adhesion increases. A core material having a weight average particle diameter in the range of 10 to 80 μm is preferable.

  When SF-2 of the core material particles is smaller than 120, the convex portions of the core material particles are easily covered with the resin layer, and it becomes difficult to make a local low resistance. On the other hand, if SF-2 of the core material particles is larger than 160, voids in the core material particles are increased, and the strength of the core material particles is weakened. The carrier adhesion phenomenon that the carrier adheres to the photosensitive member is likely to occur. Further, when SF-2 is larger than 160, the core material is excessively exposed when used in a developing machine for a long time in actual use, and the change of the initial resistance value and the resistance value after use becomes large. There is a tendency that the amount of toner on the image carrier and how it is loaded change and the image quality is not stable.

  In the present invention, the arithmetic average surface roughness Ra means the following. Using OPTELICS C130 manufactured by LASERTEC, and capturing an image with a magnification of 50 times objective lens and Resolution 0.20 μm, the observation area is 10 μm × 10 μm centering on the apex of the core particles, and the number of core particles A value obtained by measuring 100 pieces was used.

The carrier of the present invention comprises magnetic core particles and a resin layer covering the surface. However, when the core particles are coated with the resin coating layer, it is important to coat the core particles so as to leave irregularities. is there. The coating of the resin layer is preferably performed using a fluidized bed coating apparatus, and is preferably performed by post-coating heat treatment (heat treatment temperature: 100 to 350 ° C.).
If the thickness of the resin coating layer is too thin, the surface of the core material is easily exposed by stirring in the developing machine, and the change in resistance value becomes large. On the other hand, if the resin coating layer is too thick, the convex portion of the core material is not exposed, and it becomes difficult to create a local low resistance state. For this reason, in order to make a local low resistance state by the thickness of the resin coating layer, it can be controlled by the resin ratio of the coating layer to the core material, and the resin ratio to the core material is 0.5-3. It is desirable to be weight percent.

The SF-2 of the carrier of the present invention is in the range of 115 to 150, preferably in the range of 120 to 145.
If the SF-2 of the carrier is less than 115, there is no local low resistance. If it is greater than 150, the core surface is easily exposed by stirring in the developing machine during actual use, and the resistance value changes. There is a tendency to become larger.

The shape factors SF-1 and SF-2 of the carriers (and core material particles) mean the following.
SF-1 and SF-2 indicating shape factors are randomly sampled, for example, 100 carrier particle images (and core particle images) magnified 300 times using FE-SEM (S-800) manufactured by Hitachi, Ltd. The image information is introduced into, for example, an image analysis apparatus (Luzex AP) manufactured by Nireco Co., Ltd. via an interface and analyzed, and the values obtained from the following equations (1) and (2) are used as shape factor SF- 1, defined as SF-2.
SF-1 = (L ² / A) × (π / 4) × 100 (1)
SF-2 = (P ² / A) × (1 / 4π) × 100 (2)
In the formula, L is the absolute maximum length of the particle (the length of the circumscribed circle), P is the peripheral length of the particle, and A is the projected area of the particle.

The shape factor SF-1 indicates the degree of roundness of the carrier or core material particles, and the shape factor SF-2 indicates the degree of unevenness of the carrier or core material particles.
The value of SF-1 increases as it moves away from the circle (spherical shape).
When the unevenness of the surface irregularities becomes severe, the value of SF-2 also increases.

  The carrier of the present invention desirably has a fluid energy amount in the range of 3000 to 4000 mJ at a tip speed of 100 mm / sec in the powder rheometer and an approach distance of 70 mm when the approach angle of the rotor is -5 °. If the amount of fluid energy is lower than 3000 mJ, it is easily affected by the toner consumption history of the immediately preceding image, and if it is higher than 4000 mJ, the agitation stress in the developing machine increases and the change in resistance increases.

In addition, in this invention, it measures using FT4 made from freeman technology as a powder rheometer. This powder rheometer is a fluidity measuring device that directly measures fluidity by simultaneously measuring rotational torque and vertical load obtained by rotating a rotating blade spirally in filled particles.
FIG. 3 is a view for explaining the shape of a rotary blade used in a powder rheometer. As the rotor blade, a two-blade propeller type φ48 mm blade manufactured by freeman technology is used.

The fluidity energy amount indicating the fluidity of the carrier of the present invention is determined as follows.
First, a container to be measured is filled into a container. As the container, a 160 mL container having an inner diameter of 50 mm and a height of 88 mm is used. The container is filled with a carrier to a height of 88 mm.
The carrier before measurement is allowed to stand for 8 hours or more at a temperature of 22 ° C. and a humidity of 50% RH so that an error does not occur due to external environmental factors at the time of measurement. After leaving, the filled carrier is conditioned before measuring the fluidity in order to eliminate variations in measured values due to changes in filling conditions. In conditioning, the rotor blades are gently stirred in the rotational direction (the direction opposite to the rotational direction at the time of measurement) that does not receive resistance from the carrier so as not to stress the carrier in the filled state, so that excess air and parts Removes most of the stress and keeps the sample homogeneous. Specific conditioning conditions are agitation at a tip angle of 40 mm / s with an approach angle of + 5 °.

After the conditioning is completed, the rotor blades are rotated while entering the filled carrier. As shown in FIG. 1A, as shown in FIG. 1A, the tip of the rotor blade is moved from the filling surface H1 to H2 (70 mm) through the particles filled in the container at an entrance angle of −5 °. Rotational torque and vertical load when rotating at a speed of 100 mm / s are measured.
The reason why the approach angle is set to -5 ° is that the sensitivity and accuracy are the highest in measuring the flow state of the carrier, and that it has a high correlation with the flowability of the developer in the developing device. In addition, an approach angle means the angle which the axis | shaft of a measurement container and the rotating shaft of a rotary blade make.
FIG. 1B and FIG. 1C show the relationship between the vertical load and the rotational torque with respect to the depth H from the filling surface H1. FIG. 2 shows the energy gradient (mJ / mm) with respect to the depth H obtained from the rotational torque and the vertical load. The area obtained by integrating the energy gradient in FIG. 2 (shaded portion in FIG. 2) is the total energy amount (mJ).

  In the present invention, in order to reduce the influence of errors, the average value when this conditioning and energy measurement operation cycle is performed five times is defined as the total energy amount (mJ) defined in the present invention.

  Examples of the coating resin that can be used in the present invention include silanol groups and / or hydrolyzable functional groups (functional groups capable of generating silanol groups by hydrolysis (for example, alkoxy groups and halogeno groups bonded to Si atoms). And the like. A silicone resin having a negative group))), a polymerization catalyst, and if necessary, a resin other than a silicone resin having a silanol group and / or a hydrolyzable functional group, and a composition for a coating layer containing a solvent. be able to.

  Specifically, it may be formed by condensing silanol groups while coating the core particles with the coating layer composition, or after coating the core particles with the coating layer composition, It may be formed by condensation. The method of condensing silanol groups while coating the core material particles with the coating layer composition is not particularly limited, but the method of coating the core particles with the coating layer composition while applying heat, light, etc. Etc. Further, the method for condensing the silanol group after coating the core material particles with the coating layer composition is not particularly limited, and examples thereof include a method of heating after coating the core material particles with the coating layer composition. It is done.

  The silicone resin having a silanol group used in forming such a resin layer and / or a functional group capable of generating a silanol group by hydrolysis is represented by the following general formula (I). It preferably contains at least one of the units.

In the above formula (I), A ¹ is a hydrogen atom, a halogen atom, a hydroxy group, a methoxy group, a lower alkyl group having 1 to 4 carbon atoms, or an aryl group (such as a phenyl group or a tolyl group), and A ² is carbon. It is an alkylene group of formulas 1 to 4, or an arylene group (such as a phenylene group).

  In the aryl group of the above formula (I), the carbon number is 6-20, preferably 6-14. This aryl group includes an aryl group derived from benzene (phenyl group), an aryl group derived from a condensed polycyclic aromatic hydrocarbon such as naphthalene, phenanthrene and anthracene, and a chain polycyclic aromatic such as biphenyl and terphenyl. An aryl group derived from a group hydrocarbon is included. The aryl group may be substituted with various substituents.

  The carbon number of the arylene group is 6 to 20, preferably 6 to 14. The arylene group includes an arylene group derived from benzene (phenylene group), an arylene group derived from a condensed polycyclic aromatic hydrocarbon such as naphthalene, phenanthrene, and anthracene, and a chain polycyclic aromatic such as biphenyl and terphenyl. An arylene group derived from a group hydrocarbon is included. The arylene group may be substituted with various substituents.

Although it does not specifically limit as a commercial item of the silicone resin which can be used for this invention, KR251, KR271, KR272, KR282, KR252, KR255, KR152, KR155, KR211, KR216, KR213 (above, Shin-Etsu Silicone company make), AY42- 170, SR2510, SR2400, SR2406, SR2410, SR2405, SR2411 (manufactured by Toray Dow Corning, Toray Silicone).
As described above, various silicone resins can be used.

  The resin other than the silicone resin having a silanol group and / or a hydrolyzable functional group is not particularly limited, but acrylic resin, amino resin, polyvinyl resin, polystyrene resin, halogenated olefin resin, polyester, polycarbonate, Polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymers of vinylidene fluoride and vinyl fluoride, terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, etc. Fluoroterpolymers, silicone resins having no silanol groups or hydrolyzable functional groups, and the like may be used in combination. Among them, an acrylic resin is preferable because it has high adhesion to the core material particles and conductive fine particles and low brittleness.

  The acrylic resin preferably has a glass transition point of 20 to 100 ° C, more preferably 25 to 80 ° C. Since such an acrylic resin has an appropriate elasticity, when the developer is triboelectrically charged, a shock is applied to the resin layer due to the friction between the toner and the carrier or the friction between the carriers. It can be absorbed and deterioration of the resin layer and the conductive fine particles can be prevented.

The resin layer composition further preferably contains a cross-linked product of an acrylic resin and an amino resin. Thereby, fusion | melting of resin layers can be suppressed, maintaining moderate elasticity. The amino resin is not particularly limited, but a melamine resin and a benzoguanamine resin are preferable because the charge imparting ability of the carrier can be improved. In addition, when it is necessary to appropriately control the charge imparting ability of the carrier, another amino resin may be used in combination with the melamine resin and / or the benzoguanamine resin.
As the acrylic resin capable of crosslinking with the amino resin, those having a hydroxyl group and / or a carboxyl group are preferable, and those having a hydroxyl group are more preferable. Thereby, adhesiveness with core material particle | grains or electroconductive fine particles can further be improved, and the dispersion stability of electroconductive fine particles can also be improved. In this case, the acrylic resin preferably has a hydroxyl value of 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more.

  Examples of resins other than silicone resins having silanol groups and / or hydrolyzable functional groups include acrylic resins, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyesters, polycarbonates, polyethylenes, polyvinyl fluorides, polyvinyl fluorides. Fluoroterpolymers such as vinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymers of vinylidene fluoride and vinyl fluoride, terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silanol groups Or the silicone resin etc. which do not have a hydrolysable functional group are mentioned, You may use 2 or more types together.

  In addition, the resin contained in the coating layer of the present invention includes at least an A portion represented by the following structural formula 1 (and a monomer A component therefor; the same shall apply hereinafter) and a B portion represented by the following structural formula 2 (and Therefore, it is also possible to contain a crosslinked product obtained by hydrolyzing an acrylic copolymer obtained by radical copolymerization to produce a silanol group and condensing it.

  A part (and monomer A component therefor)

(In Structural Formulas 1 and 2 above, R ¹ , R ² , R ³ , X, Y, and m are as follows.)
R ¹ : hydrogen atom or methyl group R ² : alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group)
R ^3: an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, X: 10 to 90 mol%
Y: 10 to 90 mol%
m: an integer of 1 to 8. The values, - (CH ₂₎ m- is methylene group, ethylene group, propylene group, an alkylene group such as butylene group

In A part (and monomer A component), it is X = 10-90 mol%, Preferably it is 10-40 mol%, More preferably, it is 20-30 mol%.
The A portion (monomer A component) has an atomic group tris (trimethylsiloxy) silane having a large number of methyl groups in the side chain, and the ratio of the A portion (monomer A component) to the entire resin increases. The surface energy is reduced and adhesion of toner resin components, wax components, and the like is reduced. If the A portion (monomer A component) is less than 10 mol%, a sufficient effect cannot be obtained, and adhesion of the toner component increases rapidly. Moreover, when it exceeds 90 mol%, while B part (monomer B component) and toughness are insufficient, the adhesiveness of a core material and a resin layer falls, and durability of a carrier film worsens.

R ² is an alkyl group having 1 to 4 carbon atoms, and examples of the monomer A component generating such an A moiety include tris (trialkylsiloxy) silane compounds represented by the following formula. In the following formulae, Me is a methyl group, Et is an ethyl group, and Pr is a propyl group.
_{CH 2 = CMe-COO-C} 3 H 6 -Si (OSiMe 3) 3
_{CH 2 = CH-COO-C} 3 H 6 -Si (OSiMe 3) 3
_{CH 2 = CMe-COO-C} 4 H 8 -Si (OSiMe 3) 3
_{CH 2 = CMe-COO-C} 3 H 6 -Si (OSiEt 3) 3
_{CH 2 = CH-COO-C} 3 H 6 -Si (OSiEt 3) 3
_{CH 2 = CMe-COO-C} 4 H 8 -Si (OSiEt 3) 3
_{CH 2 = CMe-COO-C} 3 H 6 -Si (OSiPr 3) 3
_{CH 2 = CH-COO-C} 3 H 6 -Si (OSiPr 3) 3
_{CH 2 = CMe-COO-C} 4 H 8 -Si (OSiPr 3) 3

  The production method of the monomer component A for the A portion is not particularly limited, but a method of reacting tris (trialkylsiloxy) silane with allyl acrylate or allyl methacrylate in the presence of a platinum catalyst, or JP-A-11-217389. It can be obtained by a method of reacting methacryloxyalkyltrialkoxysilane and hexaalkyldisiloxane in the presence of a carboxylic acid and an acid catalyst.

  B part (and monomer B component / precursor monomer B): (crosslinking component)

Where
R ¹ is a hydrogen atom or a methyl group,
R ² is an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group),
R ³ is an alkyl group having 1 to 8 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.) or an alkoxy group having 1 to 4 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group). ,
Y is 10 to 90 mol%,
m is an integer of 1 to 8, - (CH ₂₎ m- is methylene, ethylene, propylene, an alkylene group such as butylene.

That is, the monomer B component (including the precursor) for the B portion is a radically polymerizable bifunctional (when R ³ is an alkyl group) or a trifunctional (when R ³ is also an alkoxy group) silane compound Y = 10 to 90 mol%, preferably 10 to 80 mol%, more preferably 15 to 70 mol%.
If the B component is less than 10 mol%, sufficient toughness cannot be obtained. On the other hand, when it exceeds 90 mol%, the coating becomes hard and brittle, and film scraping tends to occur. Moreover, environmental characteristics deteriorate. It is also conceivable that a large number of hydrolyzed crosslinking components remain as silanol groups, deteriorating environmental characteristics (humidity dependency).

  Examples of the monomer B component include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, and 3-methacryloxypropyl. Examples include methyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri (isopropoxy) silane, and 3-acryloxypropyltri (isopropoxy) silane.

  The copolymer comprising the monomer A component and the monomer B component is represented by the following structural formula 3.

(In the structural formula 3, R ¹ , R ² , R ³ , X, Y, and m are the same as those described in the structural formulas 1 and 2.)

Japanese Patent No. 3691115 discloses a technique for improving durability by crosslinking a coating.
Japanese Patent No. 3691115 discloses a radical having at least one functional group selected from the group consisting of an organopolysiloxane having a vinyl group at the terminal and a hydroxyl group, an amino group, an amide group and an imide group on the surface of the magnetic particle. Although a carrier for developing an electrostatic charge image is described in which a copolymer with a copolymerizable monomer is coated with a thermosetting resin crosslinked with an isocyanate-based compound, it has sufficient durability in peeling and scraping of the film. The current situation is that it has not been obtained.

The reason for this is not clear enough, but in the case of a thermosetting resin obtained by crosslinking the above-mentioned copolymer with an isocyanate compound, the isocyanate in the copolymer resin is understood from the structural formula. There are few functional groups (active hydrogen-containing groups such as amino group, hydroxy group, carboxy group, mercapto group, etc.) per unit weight that react (crosslink) with the compound, and two-dimensional or three-dimensional dense crosslinking at the crosslinking point The structure cannot be formed, and therefore, when used for a long time, the film is easily peeled off or scraped off (the abrasion resistance of the film is small), and it is assumed that sufficient durability is not obtained.
When the film is peeled off or scraped off, the image quality changes due to a decrease in carrier resistance and carrier adhesion occurs. Also, peeling or scraping of the coating reduces the fluidity of the developer and causes a decrease in the amount of pumping, which causes a decrease in image density, contamination when toner is increased, and toner scattering.

The coating resin of the present invention is a copolymer resin having a large number of bifunctional or trifunctional crosslinkable functional groups (points) (2 to 3 times more per weight) than the resin unit weight. Since this is further cross-linked by condensation polymerization, it is considered that the coating is extremely tough and difficult to scrape, and high durability is achieved.
Further, it is presumed that the cross-linking by the siloxane bond of the present invention has higher binding energy and is more stable against heat stress than the cross-linking by the isocyanate compound, so that the stability over time of the coating is maintained.

In the present invention, C is further represented by the following structural formula 4 in order to impart sufficient flexibility and to improve the adhesion between the core material and the resin layer, and between the resin layer and the conductive fine particles. Ingredients can be included.
C part (and monomer C component): (acrylic component)

Where
R ¹ is a hydrogen atom or a methyl group,
R ² is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and is a radical polymerizable acrylic compound having an acryloyl group or a methacryloyl group which is a methyl group, an ethyl group, a propyl group, and a butyl group.

When the component C is included, the content of the component A, the component B, and the component C is X = 10 to 40 mol%, Y = 10 to 40 mol%, and Z = 30 to 80 mol. % (Preferably 35 to 75 mol%) and 60 mol% <Y + Z <90 mol%, more preferably 70 mol% <Y + Z <85 mol%.
If the C portion (monomer C component) is greater than 80 mol%, either X or Y will be 10 or less, making it difficult to achieve both water repellency, hardness and flexibility (film scraping) of the carrier coating. .

  As the acrylic compound (monomer) of the monomer C component for the C portion, acrylic acid ester and methacrylic acid ester are preferable. Specifically, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate 2- (dimethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, 3- (dimethylamino) propyl methacrylate, 3- (dimethylamino) propyl acrylate, 2- (diethylamino) ethyl methacrylate, 2- (diethylamino) Ethyl acrylate is exemplified. Of these, alkyl methacrylate is preferable, and methyl methacrylate is particularly preferable. One of these compounds may be used alone, or a mixture of two or more may be used.

  A copolymer comprising the monomer A component, the monomer B component, and the monomer C component is represented by the following structural formula 5.

(In the formula, R ¹ , R ² , R ³ , X, Y, Z and m are as follows.)
R ¹ : hydrogen atom or methyl group R ² : alkyl group having 1 to 4 carbon atoms R ³ :
An alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 4 carbon atoms m: an integer 1 to 8 X: 10 to 40 mol%
Y: 10 to 40 mol%
Z: 30 to 80 mol%
60 mol% <Y + Z <90 mol%

In the resin layer composition of the present invention, when the copolymer and the silicone resin component are contained at the same time, the toner spent property is further improved.
As a content ratio when the silicone resin and the copolymer coexist, the silicone resin is 5% by weight to 80% by weight, preferably 10% by weight to 60% by weight with respect to the copolymer. . When the amount is less than 5% by weight, the effect of improving the spent property or the like cannot be obtained. When the amount is more than 80% by weight, the toughness of the resin layer is insufficient and the film is easily scraped.

In order to accelerate the condensation reaction of the crosslinking component B, a titanium-based catalyst, a tin-based catalyst, a zirconium-based catalyst, and an aluminum-based catalyst can be used. Of these various catalysts, titanium alkoxides and titanium chelates are particularly preferred among the titanium-based catalysts that give excellent results.
This is considered to be because the effect of promoting the condensation reaction of the silanol group derived from the crosslinking component B is large and the catalyst is hardly deactivated. Examples of titanium alkoxide catalysts include titanium diisopropoxybis (ethyl acetoacetate) represented by the following structural formula (i), and examples of titanium chelate catalysts include the following structural formula (ii). And titanium diisopropoxybis (triethanolaminate) represented by

_{Ti (O-i-C 3} H 7) 2 (C 6 H 9 O 3) 2
(I)
Ti (Oi-C ₃ H ₇ ) ₂ (C ₆ H ₁₄ O ₃ N) ₂
(Ii)

In the present invention, it is desirable to use a silane coupling agent in order to improve the dispersibility of the conductive fine particles.
The silane coupling agent is not particularly limited, but r- (2-aminoethyl) aminopropyltrimethoxysilane, r- (2-aminoethyl) aminopropylmethyldimethoxysilane, r-methacryloxypropyltrimethoxysilane, N -Β- (N-vinylbenzylaminoethyl) -r-aminopropyltrimethoxysilane hydrochloride, r-glycidoxypropyltrimethoxysilane, r-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Vinyltriacetoxysilane, r-chloropropyltrimethoxysilane, hexamethyldisilazane, r-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium Chloride, r-chloropropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, allyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, dimethyldiethoxysilane, 1, Examples include 3-divinyltetramethyldisilazane and methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, and two or more of them may be used in combination.

  Commercially available silane coupling agents include AY43-059, SR6020, SZ6023, SH6020, SH6026, SZ6032, SZ6050, AY43-310M, SZ6030, SH6040, AY43-036, AY43-031, sh6062, Z-6911, sz6300, sz6075, sz6079, sz6083, sz6070, sz6072, Z-6721, AY43-004, Z-6187, AY43-021, AY43-043, AY43-040, AY43-047, Z-6265, AY43-204M, AY43-048, Z-6403, AY43-206M, AY43-206E, Z6341, AY43-210MC, AY43-083, AY43-101, AY43-013, AY43-158E Z-6920, Z-6940 (Toray Ltd. Silicone Co., Ltd.) and the like.

Particularly for silicone resins, it is effective to contain an appropriate amount of the aminosilane coupling agent shown below.
H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃
MW 179.3
H ₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃
MW 221.4
H ₂ NCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ (OC ₂ H ₅ )
MW 161.3
_{H 2 NCH 2 CH 2 CH 2} Si (CH 3) (OC 2 H 5) 2
MW 191.3
H ₂ NCH ₂ CH ₂ NHCH ₂ Si (OCH ₃ ) ₃
MW 194.3
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂
MW 206.4
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
MW 224.4
(CH ₃ ) ₂ NCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂
MW 219.4
(C ₄ H ₉ ) ₂ NC ₃ H ₆ Si (OCH ₃ ) ₃
MW 291.6

  It is preferable that the addition amount of a silane coupling agent is 0.1-10 mass% with respect to resin. When the addition amount of the silane coupling agent is less than 0.1% by mass, the adhesiveness between the core material particles or filler particles and the resin is lowered, and the coating layer may fall off during long-term use. When the content exceeds 50% by mass, toner filming may occur during long-term use.

The resin coating layer of the present invention needs to contain 50 to 500 parts by weight, preferably 100 to 300 parts by weight of filler with respect to 100 parts by weight of the resin.
By containing a certain amount of filler in the resin coating layer, it becomes possible to suppress the abrasion of the coating layer when used for a long time in a developing machine. When the amount of filler is less than 50 parts by weight with respect to 100 parts by weight of the resin, the effect of preventing the coating layer from being scraped is reduced. As a result, the toner tends to be spent on the carrier surface.

  Furthermore, the number average particle diameter of the filler is preferably in the range of 50 to 800 nm, more preferably 200 to 700 nm. By having a certain range of particle sizes, it is easy to make fillers from the surface of the resin coating layer, and it is easy to make partial low resistance, and furthermore, it is easy to scrape the spent matter on the carrier surface, and it has excellent wear resistance. It is.

As for the particle size of the filler, 100 filler particle images magnified 10,000 times using FE-SEM (S-800) manufactured by Hitachi, Ltd. were randomly sampled, and the number average particle size was used.
As for the resistance value of the filler, a powder resistance measurement system MCP-PD51 manufactured by Dia Instruments Co., Ltd. is used, and a four-terminal four-probe type Loresta GP is used. The volume resistance value measured at 20 kN was used.

As the filler, a conductive filler or a non-conductive filler can be used, and a conductive filler and a non-conductive filler can be used in combination.
The conductive fine particles can be made of a filler such as aluminum oxide, titanium dioxide, zinc oxide, silicon dioxide, barium sulfate, zirconium oxide, etc., formed of tin dioxide or indium oxide as a layer, carbon black, etc. Barium sulfate is preferred. Substrates such as aluminum oxide, titanium dioxide, zinc oxide, silicon dioxide, barium sulfate, and zirconium oxide can be used as the non-conductive filler. Here, the conductive filler is one having a volume resistivity of 100 Ω · cm or less, and the non-conductive filler is one having a volume resistivity greater than 100 Ω · cm.

The carrier of the present invention is mixed with toner and used as a two-component developer.
The developer of the present invention has an air flow rate of 0.8 mm / sec in the powder rheometer, a tip speed of the rotary blade of 100 mm / sec, and a fluid energy amount of 30 to 70 mJ at an entrance distance of 50 mm at an entrance angle of the rotary blade of -5 °. It is desirable to be in the range.
Here, the approach angle of the rotor blade is set to −5 ° because it is the most sensitive and accurate in measuring the flow state of the carrier. Further, if the amount of fluidity energy is lower than 30 mJ, the toner consumption history of the immediately preceding image is easily affected. As a result, the probability of contact between developers decreases, and sufficient chargeability cannot be obtained. In the operation for obtaining the fluid energy amount of the developer, it is preferable to perform the conditioning in the same manner as the operation for obtaining the fluid energy amount of the carrier.

The amount of fluidity energy of the developer is measured by a powder rheometer as in the case of the carrier, and the measuring method is as follows.
First, a two-component developer to be measured is filled into a container.
As the container, a 25 mL split container having an inner diameter of 25 mm is used (a 25 mL container having a height of 59 mm). A cylinder having a height of 22 mm is placed on the container so that it can be separated vertically, and the developer having a height exceeding 59 mm is filled. At this time, since the bulk becomes small by the next conditioning, it is important to fill the container as much as possible.

After filling the developer, conditioning is performed in which the sample is homogenized by gently stirring the filled developer. This conditioning is necessary in order to always make the flow state of the toner to be measured uniform, and thus it is possible to control the variation in the measured value with little. During conditioning, the rotor blades are gently agitated in the direction of rotation (clockwise as viewed from above) so that the developer in the filled state is not stressed, causing excessive air or partial stress. Most of the sample is removed to make the sample homogeneous.
Specific conditioning conditions are agitation at a tip angle of 40 mm / s with an approach angle of + 5 °. At this time, the propeller-type rotor blades move downward simultaneously with the rotation, so that the tip draws a spiral, and the angle of the spiral path drawn by the propeller tip at this time is called an approach angle.
After repeating the conditioning operation 4 times, the upper end of the split container is gently moved, and the developer inside the vessel is worn at a height of 59 mm to obtain a developer that fills the 25 mL container. The conditioning operation is performed because it is important to always obtain a powder having a constant volume in order to stably obtain the total energy amount of the developer.

The developer obtained as described above is transferred to a 35 mL container having an inner diameter of 25 mm and a height of 80 mm. After transferring the developer to a 35 mL container, conditioning is performed once at a tip angle of 40 mm / s with an approach angle of + 5 °.
Next, after installing a ventilation measurement kit and performing air conditioning at a tip speed of 40 mm / s at a tip angle of 40 mm / s with an approach angle of + 5 ° while flowing air at a ventilation rate of 0.8 mm / sec, The tip speed of the rotor blade is 100 mm / sec while moving at an entrance angle of -5 ° from the filling surface H1 to H2 (50 mm) through the particles filled in the container while air is introduced at an air velocity of 0.8 mm / sec. Measure the rotational torque and vertical load when rotating at.
In the present invention, the total energy amount is obtained by integrating a section from 5 mm to 55 mm in height from the bottom surface.
At the time of measurement, the rotor blade is agitated in the rotational direction (counterclockwise as viewed from above) that receives resistance from the developer.

Here, the measurement is performed at an air velocity of 0.8 mm / sec and an entrance angle of -5 ° because the developer fluidity energy measured under these conditions has a strong correlation with the influence of the toner consumption history of the immediately preceding image and the chargeability. Because there is.
Further, in the present invention, in order to reduce the influence of errors, the average value when this conditioning and energy measurement operation cycle is performed five times is defined as the total energy amount (mJ) of the developer defined in the present invention.
FIG. 4 is a diagram for explaining the shape of a rotor blade used when measuring developer with a powder rheometer. The rotor blade is a two-blade propeller type φ23.5 mm diameter blade manufactured by freemanology. .

  The toner in the present invention preferably has a weight average particle diameter of 2 to 7 μm. By using the toner having such a particle size, the toner is easily uniformly charged by stirring in the developing device, and it becomes difficult to generate weakly and reversely charged toner, so that the clouded toner is not scattered. It can be attached to the image portion of the body 11. Further, since the dots can be faithfully reproduced, a high-resolution and high-quality image can be obtained, and particularly when used in a full-color copying machine, a high-quality image excellent in color reproducibility can be obtained. When the weight average particle diameter is larger than the range in the present invention, the toner is less likely to be uniformly charged by stirring in the developing device, and weakly and reversely charged toner is likely to be generated. When flying, it becomes easy to cause soiling. In addition, it is difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the particle size of the toner often increases. Conversely, a toner having a weight average particle size smaller than this range is substantially difficult to produce. The weakly and reversely charged toner is a toner that has a charge amount close to 0 and is hardly charged. The weakly charged toner is called a weakly charged toner. If the toner is positively charged, the toner is called reversely charged toner.

  The toner contains a colorant, fine particles, a charge control agent, a release agent, and the like in a binder resin mainly composed of a thermoplastic resin, and various conventionally known toners can be used. This toner can be an amorphous or spherical toner prepared by various toner production methods such as a polymerization method and a granulation method. Either magnetic toner or non-magnetic toner can be used.

As the binder resin for the toner, the following can be used alone or in combination.
Styrene binder resins such as polystyrene, polyvinyltoluene and other styrene and substituted homopolymers, styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-acrylic Acid methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate Copolymer, styrene-α-chloromethacrylic acid methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene -Isoprene copolymer, styrene- Styrene copolymers such as oleic acid copolymers and styrene-maleic acid ester copolymers; examples of acrylic binders include polymethyl methacrylate and polybutyl methacrylate. In addition, polyvinyl chloride, polyvinyl acetate, polyethylene, Polypropylene, polyester, polyurethane, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or aliphatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. Is mentioned.

A polyester resin is preferable because it can further reduce the melt viscosity while ensuring the stability of the toner during storage.
Polyester resins can be preferably used because they can lower the melt viscosity while ensuring the stability during storage of the toner, as compared with styrene and acrylic resins. Such a polyester resin can be obtained, for example, by a polycondensation reaction between an alcohol component and a carboxylic acid component.

  Examples of the alcohol component include diols such as polyethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-propylene glycol, neopentyl glycol, 1,4-butenediol, Etherified bisphenols such as 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A, and the like. Divalent alcohol units substituted with saturated hydrocarbon groups, other divalent alcohol units, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaesitol, dipenta Thritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, tri Mention may be made of trihydric or higher alcohol monomers such as methylolethane, trimethylolpropane and 1,3,5-trihydroxymethylbenzene.

  Examples of the carboxylic acid component used to obtain the polyester resin include monocarboxylic acids such as palmitic acid, stearic acid, and oleic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, terephthalic acid, cyclohexanedicarboxylic acid, Succinic acid, adipic acid, sebacic acid, malonic acid, divalent organic acid monomers in which these are substituted with saturated or unsaturated hydrocarbon groups having 3 to 22 carbon atoms, anhydrides of these acids, lower alkyl esters And dimer acid from linolenic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl- -Trivalent or higher polyvalent carboxylic acids such as methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid embol trimer acid, anhydrides of these acids, etc. A polymer can be mentioned.

  When a crystalline polyester resin is used in combination, fixing at a lower temperature becomes possible and the glossiness of the image can be further improved even at a low temperature. The polyester resin having crystallinity undergoes a crystal transition at the glass transition temperature, and at the same time, the melt viscosity suddenly decreases from the solid state, and exhibits a fixing function to a recording medium such as paper. The crystalline polyester here is represented by the ratio between the softening point and the highest endothermic peak temperature in the differential scanning calorimeter (DSC), that is, the crystallinity index defined by the softening point / the highest endothermic peak temperature. The index is 0.6 to 1.5, preferably 0.8 to 1.2. The content of the polyester crystalline polyester resin is 1 to 35 parts, preferably 1 to 25 parts with respect to 100 parts of the polyester resin. When the ratio of the crystalline polyester resin is increased, filming is likely to occur on the surface of the image carrier such as a photoconductor, and the storage stability is deteriorated.

  Epoxy resins include polycondensates of bisphenol A and epochrohydrin, such as epomic R362, R364, R365, R366, R367, R369 (above, Mitsui Petrochemical Co., Ltd.), Epototo Commercially available products such as YD-011, YD-012, YD-014, YD-904, YD-017 (manufactured by Tohto Kasei Co., Ltd.), Epcot 1002, 1004, 1007 (manufactured by Shell Chemical Co., Ltd.) Things.

Examples of the colorant used in the toner of the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue, Hansa Yellow G, rhodamine 6G lake, calco oil blue, chrome yellow, quinacridone, Conventionally known dyes and pigments such as benzidine yellow, rose bengal, triallylmethane dyes, monoazo dyes, disazo dyes, dyes and pigments can be used alone or in combination to produce the desired color tone. In a color toner other than black, a white or transparent material such as a metal salt of a white salicylic acid derivative is preferable.
In the case of a transparent toner, the toner can be obtained without containing a colorant.
Further, the black toner can be made into a magnetic toner by containing a magnetic material. As the magnetic material, ferromagnetic powders such as iron and cobalt, fine powders such as magnetite, hematite, Li-based ferrite, Mn-Zn-based ferrite, Cu-Zn-based ferrite, Ni-Zn ferrite, and Ba ferrite can be used.

  For the purpose of sufficiently controlling the triboelectric chargeability of the toner, so-called charge control agents such as metal complex salts of monoazo dyes, nitrohumic acid and its salts, salicylic acid, naphthoic salts, dicarboxylic acid Co, Cr, Fe, etc. , A quaternary ammonium compound, an organic dye, and the like can be contained.

Furthermore, a release agent may be added to the toner used in the present invention as necessary.
As the release agent material, low molecular weight polypropylene, low molecular weight polyethylene, carnauba wax, microcrystalline wax, jojoba wax, rice wax, montanic acid wax and the like can be used alone or in combination, but are not limited thereto. It is not a thing.

Additives other than those described above can be added to the toner. In order to obtain a good image, it is important to impart sufficient fluidity to the toner. For this purpose, it is generally effective to externally add hydrophobized metal oxide fine particles and fine particles such as lubricants as fluidity improvers, and metal oxides, organic resin fine particles, metal soaps and the like as additives. It is possible to use.
Specific examples of these additives include fluororesins such as polytetrafluoroethylene, lubricants such as zinc stearate, abrasives such as cerium oxide and silicon carbide; inorganic such as SiO ₂ and TiO ₂ having a hydrophobic surface Examples thereof include fluidity-imparting agents such as oxides; those known as anti-caking agents, and surface-treated products thereof. In order to improve the fluidity of the toner, hydrophobic silica is particularly preferably used.

The toner used in the electrostatic latent image developer comprising the toner of the present invention and the carrier has a weight average particle size of 3.0 to 9.0 μm, more preferably 3.0 to 6.0 μm.
The toner particle size was measured using Coulter Multisizer III (manufactured by Beckman Coulter, Inc.).

Further, the carrier of the present invention can be used as a replenishment developer composed of a carrier and a toner, and can be applied to an image forming apparatus that forms an image while discharging excess developer in the developing device. A developing device using a replenishment developer composed of a carrier and a toner can obtain a stable image quality for a very long time.
That is, the deteriorated carrier in the developing device and the non-deteriorated carrier in the replenishing developer are replaced, and the charge amount is kept stable over a long period of time, so that a stable image can be obtained. This method is particularly effective when printing a large image area. Deterioration at the time of printing a large image area is mainly due to a decrease in carrier charging ability due to toner spent on the carrier. However, using this method, the amount of carrier replenishment increases when the image area is large. The frequency with which the changed carriers are replaced increases. Thereby, a stable image can be obtained for an extremely long period of time.

  The mixing ratio of the replenishment developer is preferably 2 to 50 parts by weight, preferably 5 to 15 parts by weight of the toner with respect to 1 part by weight of the carrier. When the amount of toner is less than 2 parts by mass with respect to 1 part by weight of the carrier, the amount of replenishment carrier is excessive, the carrier is excessively supplied and the carrier concentration in the developing device becomes too high, and the toner charge amount is likely to increase. Further, as the toner charge amount increases, the developing ability decreases and the image density decreases. On the other hand, if the amount of toner exceeds 50 parts by mass with respect to 1 part by weight of the carrier, the carrier ratio in the replenishment developer is reduced, so that the replacement of the carrier in the image forming apparatus is reduced, and an effect on carrier deterioration can be expected. Disappear.

In the present invention, the weight average particle diameter Dw referred to for the core material particles, the carrier, and the toner is calculated based on the particle diameter distribution (relationship between the number frequency and the particle diameter) of the particles measured on the basis of the number. is there.
The weight average particle diameter Dw in this case is expressed by the following formula (3).

(Equation 1)
Dw = {1 / Σ (nD ³ )} × {Σ (nD ⁴ )} (3)

In formula (3), D represents the representative particle size (μm) of the particles present in each channel, and n represents the total number of particles present in each channel.
The channel indicates a length for dividing the particle size range in the particle size distribution diagram into measurement width units, and in the case of the present invention, an equal length (particle size distribution width) of 2 μm is adopted. .
Further, as the representative particle size of the particles existing in each channel, the lower limit value of the particle size stored in each channel was adopted.

As a particle size analyzer for measuring the particle size distribution in the present invention, a Microtrac particle size analyzer (model HRA9320-X100: manufactured by Honeywell) was used. The measurement conditions are as follows.
[1] Particle size range: 100 to 8 [mu] m [2] Channel length (channel width): 2 [mu] m [3] Number of channels: 46 [4] Refractive index: 2.42

  Next, the image forming method of the present invention will be described in detail with reference to the drawings based on an image forming apparatus useful for the implementation thereof, but these are for explaining the present invention and for limiting the present invention. It is not a thing.

FIG. 5 is a schematic diagram for explaining the developing unit of the image forming apparatus, and the following modifications also belong to the category of the image forming apparatus.
In FIG. 5, a developing device (40) disposed opposite to a photosensitive drum (20) as a latent image carrier includes a developing sleeve (41) as a developer carrier and a developer accommodating member (42). It is mainly composed of a doctor blade (43) as a regulating member, a support case (44) and the like.
To a support case (44) having an opening on the side of the photosensitive drum (20), a toner hopper (45) as a toner storage portion for storing the toner (21) is joined. In the developer accommodating portion (46) that accommodates the developer composed of toner (21) and carrier particles (23) adjacent to the toner hopper (45), the toner particles (21) and carrier particles (23) are agitated. In addition, a developer stirring mechanism (47) is provided for imparting friction / release charges to the toner particles.

Inside the toner hopper (45), a toner agitator (48) and a toner replenishing mechanism (49) are disposed as toner supplying means rotated by a driving means (not shown).
The toner agitator (48) and the toner replenishing mechanism (49) send out the toner (21) in the toner hopper (45) toward the developer container (46) while stirring.
A developing sleeve (41) is disposed in a space between the photosensitive drum (20) and the toner hopper (45). The developing sleeve (41), which is driven to rotate in the direction of the arrow by a driving means (not shown), has a relative position relative to the developing device (40) in order to form a magnetic brush by carrier particles (23). A magnet (not shown) is provided as magnetic field generating means. At the time of development, the magnetic brush contains not only carrier particles (23) but also toner particles (21).
A regulating member (doctor blade) (43) is integrally attached to the side of the developer accommodating member (42) facing the side attached to the support case (44). In this example, the regulating member (doctor blade) (43) is disposed in a state where a certain gap is maintained between the tip thereof and the outer peripheral surface of the developing sleeve (41).

  Using such an apparatus without limitation, the developing method of the present invention is performed as follows. That is, with the above configuration, the toner (21) sent out from the toner hopper (45) by the toner agitator (48) and the toner replenishing mechanism (49) is transported to the developer accommodating portion (46), where the developer agitation is performed. By stirring by the mechanism (47), a desired friction / peeling charge is imparted, and it is carried on the developing sleeve (41) in the form of a magnetic brush as a developer together with the carrier particles (23), and the photosensitive drum (20 ) To the position opposed to the outer peripheral surface, and only the toner (21) is electrostatically coupled to the electrostatic latent image formed on the photosensitive drum (20), so that the photosensitive drum (20) A toner image is formed.

  FIG. 6 is a cross-sectional view illustrating an example of an image forming apparatus. Around the drum-shaped image carrier, that is, the photosensitive drum (20), an image carrier charging member (32), an image exposure system (33), a development (device) mechanism (40), a transfer mechanism (50), and a cleaning mechanism. (60), a static elimination lamp (70) is arranged. In this example, the surface of the image carrier charging member (32) is not spaced apart from the surface of the photoreceptor (20) by about 0.2 mm. When the photosensitive member (20) is charged by the charging member (32) in the contact state, the photosensitive member (32) is applied to the photosensitive member by an electric field obtained by superimposing the alternating current component on the direct current component by a voltage applying means (not shown). By applying charging, it is possible and effective to reduce charging unevenness. The image forming method including the developing method is performed by the following operation.

  A series of image forming processes can be described by a negative-positive process. An image carrier (20) represented by a photoconductor (OPC) having an organic photoconductive layer is neutralized by a static elimination lamp (70), and is uniformly negatively charged by a charging member (32) such as a charging charger or a charging roller. A latent image is formed by laser light emitted from the laser optical system (33) (in this example, the absolute value of the exposed portion potential is lower than the absolute value of the non-exposed portion potential).

  Laser light is emitted from a semiconductor laser and scans the surface of the image carrier, that is, the photoreceptor (20) in the direction of the rotation axis of the image carrier (20) by a polygonal polygon mirror (polygon) that rotates at high speed. . The latent image formed in this way is developed from a mixture of toner particles and carrier particles supplied on a developing sleeve (41) which is a developer carrying member in the developing device, developing means or developing device (40). The toner is developed to form a visible toner image. At the time of developing the latent image, a voltage of an appropriate magnitude or AC is applied to the developing sleeve (41) from a voltage application mechanism (not shown) between the exposed portion and the non-exposed portion of the image carrier (20). A developing bias with a superimposed voltage is applied.

  On the other hand, a transfer medium (for example, paper) (80) is fed from a paper feed mechanism (not shown), and is synchronized with the leading edge of the image by a pair of upper and lower registration rollers (not shown). And the transfer member (50) to transfer the toner image. At this time, it is preferable that a potential opposite to the polarity of toner charging is applied to the transfer member (50) as a transfer bias. Thereafter, the transfer medium or intermediate transfer medium (80) is separated from the image carrier (20) to obtain a transfer image.

Further, the toner particles remaining on the image carrier are collected into a toner collection chamber (62) in the cleaning mechanism (60) by a cleaning blade (61) as a cleaning member.
The collected toner particles may be transported to a developing unit and / or a toner replenishing unit by a toner recycling unit (not shown) and reused.

  The image forming apparatus may be a device in which a plurality of the developing devices described above are arranged and the toner images are sequentially transferred onto the transfer medium, then sent to the fixing mechanism, and the toner is fixed by heat or the like. It is also possible to use a device that transfers a plurality of toner images to the transfer medium and transfers them all together onto a transfer medium and performs the same fixing.

  FIG. 7 shows another process example using the electrophotographic developing method according to the present invention. The photosensitive member (20) is provided with at least a photosensitive layer on a conductive support and is driven by driving rollers (24a) and (24b) to be charged by a charging roller (32), image exposure by a light source (33), and development. Development with the apparatus (40), transfer with the charger (50), exposure before cleaning with the light source (26), cleaning with the brush-like cleaning means (64) and the cleaning blade (61), and static elimination with the static elimination light source (70) are repeated. Done. In FIG. 5, the photoconductor (20) (of course, the support is translucent in this case) is irradiated with pre-cleaning exposure light from the support side.

  FIG. 8 shows an example of the process cartridge of the present invention. This process cartridge uses the carrier of the present invention, the photoconductor (20), the proximity brush-like contact charging means (32), the developing means (40) containing the developer of the present invention, and the cleaning means. This is a process cartridge that integrally supports a cleaning unit having at least a cleaning blade (61) and is detachable from the main body of the image forming apparatus. In the present invention, the above-described components can be integrally combined as a process cartridge, and the process cartridge can be configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these. “Parts” represents parts by weight , and Examples 6, 10 and 14 are used as reference examples .

(Core production method 1)
MnCO ₃ powder, Mg (OH) ₂ powder, and Fe ₂ O ₃ powder were weighed and mixed to obtain a mixed powder.
This mixed powder was calcined at 900 ° C. for 3 hours in an air atmosphere in a heating furnace, and the obtained calcined product was cooled and pulverized to obtain a powder having a weight average particle diameter of 7 μm.
This powder was added to an aqueous solution of 1 wt% dispersant to form a slurry, and this slurry was supplied to a spray dryer and granulated to obtain a granulated product having a weight average particle size of 45 μm. This granulated product was loaded into a firing furnace and fired at 1250 ° C. for 5 hours in a nitrogen atmosphere.
The obtained fired product was pulverized by a pulverizer, and then the particle size was adjusted by sieving to obtain spherical ferrite particles having a weight average particle diameter of 40 μm. Of these spherical ferrite particles, SF-1 was 140, SF-2 was 145, and Ra was 0.7 μm. When it was component analysis of the granulated _{material, MnO 46.2 mol%, MgO 0.7} mol%, were Fe 2 O 3 53 mol%.

(Core production method 2)
The mixed powder was calcined similarly to the core material manufacturing method 1, and the obtained calcined product was cooled and pulverized to obtain a powder having a particle diameter of approximately 3 μm.
This powder was added to an aqueous solution of 1 wt% dispersant to form a slurry, and this slurry was supplied to a spray dryer and granulated to obtain a granulated product having a weight average particle size of 45 μm. This granulated product was loaded into a firing furnace and fired at 1200 ° C. for 5 hours in a nitrogen atmosphere.
The obtained fired product was pulverized by a pulverizer, and then the particle size was adjusted by sieving to obtain spherical ferrite particles having a weight average particle diameter of 40 μm. The spherical ferrite particles had SF-1 of 130, SF-2 of 152, and Ra of 0.93 μm.

(Core production method 3)
The mixed powder was calcined similarly to the core material manufacturing method 1, and the calcined product obtained was cooled and pulverized to obtain a powder having a weight average particle diameter of 1 μm. This powder was added to an aqueous solution of 1 wt% dispersant to form a slurry, and this slurry was supplied to a spray dryer and granulated to obtain a granulated product having a weight average particle size of 40 μm. This granulated product was loaded into a firing furnace and fired at 1300 ° C. for 5 hours in a nitrogen atmosphere.
The obtained fired product was pulverized by a pulverizer, and then the particle size was adjusted by sieving to obtain spherical ferrite particles having a weight average particle diameter of 40 μm. The spherical ferrite particles had SF-1 of 125, SF-2 of 119, and Ra of 0.45 μm.

(Core production method 4)
The mixed powder was calcined similarly to the core material manufacturing method 1, and the calcined product obtained was cooled and pulverized to obtain a powder having a weight average particle diameter of 1 μm. This powder was added to an aqueous solution of 1 wt% dispersant to form a slurry, and this slurry was supplied to a spray dryer and granulated to obtain a granulated product having a weight average particle size of 45 μm. This granulated product was loaded into a firing furnace and fired at 1050 ° C. for 5 hours in a nitrogen atmosphere.
The obtained fired product was pulverized by a pulverizer, and then the particle size was adjusted by sieving to obtain spherical ferrite particles having a weight average particle diameter of 40 μm. The spherical ferrite particles had SF-1 of 130, SF-2 of 125, and Ra of 0.75 μm.

(Core production method 5)
MnCO ₃ powder, Mg (OH) ₂ powder, Fe ₂ O ₃ powder and SrCO ₃ powder were weighed and mixed to obtain a mixed powder.
This mixed powder was calcined in a heating furnace at 850 ° C. for 1 hour in an air atmosphere, and the obtained calcined product was cooled and pulverized to obtain a powder having a weight average particle size of 3 μm or less.
This powder was added to an aqueous solution of 1 wt% dispersant to form a slurry, and this slurry was supplied to a spray dryer and granulated to obtain a granulated product having a weight average particle size of 45 μm. This granulated product was loaded into a firing furnace and fired at 1120 ° C. for 4 hours in a nitrogen atmosphere.
The obtained fired product was pulverized by a pulverizer, and then the particle size was adjusted by sieving to obtain spherical ferrite particles having a weight average particle diameter of 40 μm. The spherical ferrite particles had SF-1 of 145, SF-2 of 155, and Ra of 0.85 μm. When it was component analysis of the granulated _{material, MnO 40.0 mol%, MgO 10.0} mol%, Fe 2 O 3 50 mol%, were SrO 0.4 mol%.

(Core production method 6)
The mixed powder was calcined and granulated in the same manner as in the core material production method 4 to obtain a granulated product having a weight average particle size of 45 μm, and the granulated product was loaded into a calcining furnace and 1180 ° C. in a nitrogen atmosphere. Baked for 4 hours. The obtained fired product was pulverized by a pulverizer, and then the particle size was adjusted by sieving to obtain spherical ferrite particles having a weight average particle diameter of 40 μm. Of these spherical ferrite particles, SF-1 was 135, SF-2 was 122, and Ra was 0.63 μm.

(Core manufacturing method 7)
The mixed powder was calcined and granulated in the same manner as in the core material production method 4 to obtain a granulated product having a weight average particle size of 45 μm, and the granulated product was loaded into a calcining furnace and was subjected to 1080 ° C. in a nitrogen atmosphere. Baked for 4 hours. The obtained fired product was pulverized by a pulverizer, and then the particle size was adjusted by sieving to obtain spherical ferrite particles having a weight average particle diameter of 40 μm. The spherical ferrite particles had SF-1 of 150, SF-2 of 165, and Ra of 1.03 μm.

(Core production method 8)
MnCO ₃ powder, Mg (OH) 2 powder, Fe 2 O ₃ powder, and CaCO ₃ powder were weighed and mixed to obtain a mixed powder.
This mixed powder was calcined in a heating furnace at 850 ° C. for 1 hour in an air atmosphere, and the obtained calcined product was cooled and pulverized to obtain a powder having a weight average particle size of 3 μm or less. This powder was added to an aqueous solution of 1 wt% dispersant to form a slurry, and this slurry was supplied to a spray dryer and granulated to obtain a granulated product having a weight average particle size of 45 μm. This granulated product was loaded into a firing furnace and fired at 1200 ° C. for 5 hours in a nitrogen atmosphere.
The obtained fired product was pulverized by a pulverizer, and then the particle size was adjusted by sieving to obtain spherical ferrite particles having a weight average particle diameter of 40 μm. The spherical ferrite particles had SF-1 of 130, SF-2 of 140, and Ra of 0.68 μm. Moreover, when the component analysis of the said granulated material was conducted, they were MnO 44.3 mol%, MgO 0.7 mol%, Fe2O3 53 mol%, CaO 2.0 mol%.

(Conductive fine particle production example 1)
100 g of aluminum oxide (manufactured by Sumitomo Chemical Co., Ltd., AKP-30) was dispersed in 1 liter of water to form a suspension, and this liquid was heated to 70 ° C. To this suspension, a solution of 100 g of stannic chloride and 3 g of phosphorus pentoxide dissolved in 1 liter of 2N hydrochloric acid and 12 wt% aqueous ammonia was added dropwise over 2 hours so that the pH of the suspension was 7-8. did. After dropping, the cake obtained by filtering and washing the suspension was dried at 110 ° C. Next, this dry powder was treated in a nitrogen stream at 500 ° C. for 1 hour to obtain conductive fine particles 1.
The obtained conductive fine particles had a weight average particle diameter of 400 nm and a volume resistivity of 50 Ω · cm.

(Conductive fine particle production example 2)
100 g of aluminum oxide (manufactured by Sumitomo Chemical Co., Ltd., AKP-30) was dispersed in 1 liter of water to form a suspension, and this liquid was heated to 70 ° C. To this suspension, a solution of 10 g of stannic chloride and 0.30 g of phosphorus pentoxide in 100 ml of 2N hydrochloric acid and 12% by weight aqueous ammonia are applied for 12 minutes so that the pH of the suspension is 7-8. And dripped. After dropping, the cake obtained by filtering and washing the suspension was dried at 110 ° C. Next, this dry powder was treated in a nitrogen stream at 500 ° C. for 1 hour to obtain conductive fine particles 2.
The obtained conductive fine particles had a weight average particle diameter of 300 nm and a volume resistivity of 1200 Ω · cm.

(Conductive fine particle production example 3)
100 g of aluminum oxide (manufactured by Sumitomo Chemical Co., Ltd., AKP-30) was dispersed in 1 liter of water to form a suspension, and this liquid was heated to 70 ° C. A suspension of 200 g of stannic chloride and 6 g of phosphorus pentoxide in 1.5 liters of 2N hydrochloric acid and 12 wt% aqueous ammonia was added to the suspension over 3 hours so that the pH of the suspension was 7-8. And dripped. After dropping, the cake obtained by filtering and washing the suspension was dried at 110 ° C. Next, this dry powder was treated in a nitrogen stream at 500 ° C. for 1 hour to obtain conductive fine particles 3.
The obtained conductive fine particles had a weight average particle diameter of 600 nm and a volume resistivity of 10 Ω · cm.

(Conductive fine particle production example 4)
100 g of aluminum oxide (manufactured by Sumitomo Chemical Co., Ltd., AKP-30) was dispersed in 1 liter of water to form a suspension, and this liquid was heated to 70 ° C. A solution prepared by dissolving 11.6 g of stannic chloride in 1 liter of 2N hydrochloric acid and 12 wt% aqueous ammonia were added dropwise to the suspension over 40 minutes so that the pH of the suspension was 7-8. Subsequently, a solution obtained by dissolving 36.7 g of indium chloride and 5.4 g of stannic chloride in 450 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia were added dropwise over 1 hour so that the pH of the suspension was 7-8. . After dropping, the cake obtained by filtering and washing the suspension was dried at 110 ° C. Next, this dried powder was treated in a nitrogen stream at 500 ° C. for 1 hour to obtain conductive particles 7.
The obtained conductive fine particles had a weight average particle diameter of 300 nm and a volume resistivity of 4 Ω · cm.

(Conductive fine particle production example 5)
100 g of rutile titanium oxide (manufactured by Titanium Industry, KR-310) was dispersed in 1 liter of water to form a suspension, and this liquid was heated to 70 ° C. To this suspension, a solution of 100 g of stannic chloride and 3 g of phosphorus pentoxide dissolved in 1 liter of 2N hydrochloric acid and 12 wt% aqueous ammonia was added dropwise over 2 hours so that the pH of the suspension was 7-8. did. After dropping, the cake obtained by filtering and washing the suspension was dried at 110 ° C. Next, this dry powder was treated in a nitrogen stream at 500 ° C. for 1 hour to obtain conductive particles 8.
The obtained conductive fine particles had a weight average particle diameter of 450 nm and a volume resistivity of 40 Ω · cm.

(Resin synthesis example 1)
300 g of toluene was charged into a flask equipped with a stirrer, and the temperature was raised to 90 ° C. under a nitrogen gas stream. Then this
_{CH 2 = CMe-COO-C} 3 H 6 -Si (OSiMe 3) 3 ( wherein, Me is a methyl group.)
3-methacryloxypropyltris (trimethylsiloxy) silane 84.4 g (200 mmol: Silaplane TM-0701T / manufactured by Chisso Corporation), 3-methacryloxypropylmethyldiethoxysilane 39 g (150 mmol), methacrylic acid A mixture of 65.0 g (650 mmol) of methyl and 0.58 g (3 mmol) of 2,2′-azobis-2-methylbutyronitrile was added dropwise over 1 hour. After completion of the dropwise addition, a solution prepared by dissolving 0.06 g (0.3 mmol) of 2,2′-azobis-2-methylbutyronitrile in 15 g of toluene was further added (2,2′-azobis-2-methylbutyrate). A total amount of ronitrile (0.64 g = 3.3 mmol) was mixed at 90 to 100 ° C. for 3 hours and radical copolymerized to obtain a methacrylic copolymer.
The resulting methacrylic copolymer had a weight average molecular weight (converted to standard polystyrene using gel permeation chromatography) of 33,000. Subsequently, it diluted with toluene so that the non volatile matter of this methacrylic copolymer solution might be 25 weight%. The viscosity of the copolymer solution thus obtained was 8.8 mm ² / s, and the specific gravity was 0.91.

(Resin synthesis example 2)
Radical copolymerization was carried out in exactly the same manner as in Resin Synthesis Example 1 except that 39 g (150 mmol) of 3-methacryloxypropylmethyldiethoxysilane was replaced with 37.2 g (150 mmol) of 3-methacryloxypropyltrimethoxysilane. As a result, a methacrylic copolymer was obtained.
The resulting methacrylic copolymer had a weight average molecular weight of 34,000 (converted to standard polystyrene using gel permeation chromatography). Subsequently, it diluted with toluene so that the non volatile matter of this methacrylic copolymer solution might be 25 weight%. The viscosity of the copolymer solution thus obtained was 8.7 mm ² / s, and the specific gravity was 0.91.

  In addition, the said viscosity was measured according to JIS-K2283 at 25 degreeC. The non-volatile content was measured by weighing 1 g of the coating agent composition in an aluminum dish and heating it at 150 ° C. for 1 hour. The formula “non-volatile content (%) = (weight before heating−weight after heating)” ) × 100 / weight before heating ”.

<Toner Production Example 1>
-Production example of inorganic fine particles Liquid SiCl4 as a core raw material is used as a carrier gas using a liquid raw material supply device.
The gas was blown at a flow rate of 300 SCCM (standard volume flow rate (CC) per minute) and a flow rate of 250 SCCM of SiCl4 Vapor was sent to a core burner together with H2 gas 20 SLM (standard volume flow rate (L)) and O2 gas 20 SLM to cause flame hydrolysis and fusion to produce SiO2 fine particles.
The fine particles were grown to a predetermined primary particle size, and the obtained fine particles were hydrophobized with hexamethyldisilazane to obtain [Inorganic fine particles 1] having an average primary particle size of 5 nm.

Synthesis of organic fine particle emulsion In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 80 parts of styrene Then, 83 parts of methacrylic acid, 110 parts of butyl acrylate, 12 parts of butyl thioglycolate and 1 part of ammonium persulfate were charged and stirred for 15 minutes at 400 rpm, and a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) A dispersion was obtained. This is designated as [fine particle dispersion 1]. The volume average particle size of the [fine particle dispersion 1] measured by a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corporation) was 120 nm.
A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 42 ° C., and the weight average molecular weight was 30,000.

-Preparation of aqueous phase 990 parts of water, 65 parts of [fine particle dispersion 1], 37 parts of 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: Sanyo Chemical Industries), 90 parts of ethyl acetate Were mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].

Synthesis of low molecular weight polyester In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2 mol adduct, 529 parts of bisphenol A propylene oxide 3 mol adduct, 208 parts terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Then, 44 parts of trimellitic anhydride was added to the reaction vessel, The mixture was reacted at 180 ° C. and normal pressure for 2 hours to obtain [Low molecular weight polyester 1]. [Low molecular weight polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25 mgKOH / g. The acid value can be measured, for example, by the method specified in JIS K0070 (the same applies hereinafter).

Synthesis of intermediate polyester In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mol adduct, 81 parts of bisphenol A propylene oxide 2-mol adduct, 283 parts terephthalic acid Then, 22 parts of trimellitic anhydride and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a Tg of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g. The hydroxyl value can be measured, for example, by a method specified in JIS K0070 (the same applies hereinafter).

Synthesis of a modified polyester resin (referred to as prepolymer 1) capable of reacting with a compound having at least an active hydrogen group In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, the above [intermediate polyester 1] 410 parts, 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate were added and reacted at 100 ° C. for 5 hours to obtain [Prepolymer 1]. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

-Synthesis of ketimine In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418 mgKOH / g. It can be measured by the method defined in JIS K 0070 (the same applies hereinafter).

・ Synthesis of masterbatch 1200 parts of water, 40 parts of carbon black (manufactured by Cabot, Regal 400R), 60 parts of polyester resin (manufactured by Sanyo Kasei, RS801) and 30 parts of water are further added, and Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). ), The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

Preparation of toner composition containing oil phase, that is, inorganic fine particles In a container equipped with a stir bar and a thermometer, 400 parts of [low molecular weight polyester 1], 110 parts of carnauba wax and 947 parts of ethyl acetate are charged and stirred. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].

  [Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed is 1 kg / hr, a disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The wax was dispersed under the conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] and 34 parts of the above [inorganic fine particles 1] were added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. The solid content concentration of [Pigment / Wax Dispersion 1] (130 ° C., 30 minutes) was 50%.

Emulsification [Pigment / Wax Dispersion 1] 648 parts, [Prepolymer 1] 154 parts, [Ketimine Compound 1] 8.5 parts in a container, 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika) After mixing for 1 minute, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at a rotational speed of 10,000 rpm for 20 minutes to obtain [Emulsion Slurry 1].
That is, it is dispersed in an aqueous medium containing resin fine particles and an elongation reaction is performed.

-Solvent removal [Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C for 8 hours, aging was carried out at 45 ° C for 4 hours to obtain [Dispersion slurry 1]. .

-After washing, drying and fluorine treatment [dispersion slurry 1] 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice to obtain a cake. . This is designated as [Filter cake 1].
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer.
Thereafter, 15 parts of [Filter cake 1] is added to 90 parts of water, and a fluorine compound (C ₉ F ₁₇ O—Ph—SO ₂ NH— (CH ₂ ) ₃ —N ⁺ (CH ₃ ) _3. The fluorine compound was adhered to the surface of the toner particles by dispersing 0.005 part of I ⁻ : Ph is a phenylene group, and then dried at 45 ° C. for 48 hours with a circulating dryer. Thereafter, the mixture was sieved with a 75 μm mesh to obtain toner base particles. This is designated as [toner base particle 1].

External additive treatment For 100 parts of the [ner base particles 1] obtained above, 0.7 parts of hydrophobic silica and 0.3 parts of hydrophobized titanium oxide as external additives are mixed in a Henschel mixer. The toner was obtained. This is referred to as [Toner 1]. The fluorine atom content at this time was 2.2 atomic percent.

<Carrier Production Example 1>
80 parts of a 15,000 weight molecular weight methyl silicone resin (solid content 25%) made from a bifunctional or trifunctional monomer, 56 parts of the conductive fine particle production example 1 filler, titanium diisopropoxybis (ethyl) as a catalyst Acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) 4 parts, and silane coupling agent SH6020 (manufactured by Toray Silicone Co., Ltd.) 0.6 parts were diluted with toluene to obtain a resin solution having a solid content of 10 wt%. . This resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 1 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier a having a weight average particle size of 40 μm. The SF-2 of this carrier a was measured and found to be 128, and the carrier fluidity energy amount was 3300 mJ.

<Carrier Production Example 2>
44 parts of a methylsilicone resin (solid content 25%) made of bifunctional or trifunctional monomers with a weight molecular weight of 15,000, 22 parts of filler in Production Example 4 of conductive fine particles, titanium diisopropoxybis (ethyl) as a catalyst Acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) 2 parts and SH6020 (manufactured by Toray Silicone Co., Ltd.) 0.3 part as a silane coupling agent were diluted with toluene to obtain a resin solution having a solid content of 10 wt%. . This resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 1 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier b having a weight average particle size of 40 μm. The SF-2 of this carrier b was measured and found to be 134, and the carrier fluidity energy amount was 3600 mJ.

<Carrier Production Example 3>
30 parts of methyl silicone resin (solid content 25%) having a weight molecular weight of 15,000 made from a bifunctional or trifunctional monomer, 30 parts of the resin obtained in Resin Synthesis Example 1, and the filler of Production Example 4 for conductive fine particles 15 parts, 3 parts of titanium diisopropoxybis (ethyl acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) as a catalyst and 0.5 part of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent are diluted with toluene. Thus, a resin solution having a solid content of 10 wt% was obtained. This resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 1 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier c having a weight average particle size of 40 μm. The SF-2 of this carrier c was measured and found to be 130, and the carrier fluidity energy amount was 3400 mJ.

<Carrier Production Example 4>
64 parts of methyl silicone resin (solid content: 25%) having a weight molecular weight of 15,000 made from a bifunctional or trifunctional monomer, 16 parts of the resin obtained in Resin Synthesis Example 2, and the filler of Conductive Fine Particle Production Example 4 56 parts, 4 parts of titanium diisopropoxybis (ethyl acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) as a catalyst and 0.6 part of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent are diluted with toluene. Thus, a resin solution having a solid content of 10 wt% was obtained. This resin solution was applied and dried on 1000 parts by weight of the core material particles prepared by the core material manufacturing method 1 by using a fluidized bed type coating apparatus and controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier d having a weight average particle size of 40 μm. The SF-2 of this carrier d was measured to be 127, and the carrier fluidity energy amount was 3200 mJ.

<Carrier Production Example 5>
42 parts of a methyl silicone resin (solid content 25%) having a weight molecular weight of 15,000 made from a bifunctional or trifunctional monomer, 2 parts of the resin obtained in Resin Synthesis Example 1, and the filler of Conductive Fine Particle Production Example 3 30 parts, 3 parts of titanium diisopropoxybis (ethyl acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) as a catalyst and 0.3 part of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent are diluted with toluene. Thus, a resin solution having a solid content of 10 wt% was obtained. This resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 1 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier e having a weight average particle size of 40 μm. The SF-2 of this carrier e was measured and found to be 136, and the carrier fluidity energy amount was 3600 mJ.

<Carrier Production Example 6>
74 parts of methyl silicone resin (solid content 25%) 15,000 weight molecular weight made from bifunctional or trifunctional monomers, 18 parts of resin obtained in Resin Synthesis Example 1, and filler of conductive fine particle production example 4 50 parts, 46.6 parts of oxygen deficient tin oxide-coated barium sulfate powder (Pastran 4310, Mitsui Mining & Mining Co., Ltd., weight average particle size: 150 nm, volume resistivity: 12 Ω · cm), titanium diisopropoxybis ( Ethyl acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co.) 4 parts, SH6020 (manufactured by Toray Silicone Co., Ltd.) 0.7 parts as a silane coupling agent is diluted with toluene to obtain a resin solution having a solid content of 10 wt%. It was. This resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 1 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier f having a weight average particle size of 40 μm. The SF-2 of this carrier f was measured to be 117, and the carrier fluidity energy amount was 3100 mJ.

<Carrier Production Example 7>
48 parts of the resin obtained in Resin Synthesis Example 2, 18 parts of the filler in Production Example 1 of conductive fine particles, 1 carbon black REGAL 330 (number average particle diameter: 25 nm, volume resistivity: 0.1 Ω · cm) manufactured by Cabot Corporation 2 parts of titanium diisopropoxybis (ethyl acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co.) as a catalyst and 0.4 part of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent were diluted with toluene. A resin solution having a solid content of 10 wt% was obtained. This resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 1 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier g having a weight average particle size of 40 μm. The SF-2 of this carrier g was measured and found to be 132, and the carrier fluidity energy amount was 3400 mJ.

<Carrier Production Comparative Example 1>
16 parts of methylsilicone resin (solid content 25%) made of bifunctional or trifunctional monomer having a weight molecular weight of 15,000, 2 parts of filler of Production Example 3 of conductive fine particles, titanium diisopropoxybis (ethyl) as a catalyst Acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) 1 part, SH6020 (manufactured by Toray Silicone Co., Ltd.) 0.2 part as a silane coupling agent was diluted with toluene to obtain a resin solution having a solid content of 10 wt%. . This resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 1 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier h having a weight average particle size of 40 μm. The SF-2 of this carrier h was measured and found to be 140. The carrier fluidity energy amount was 4200 mJ and the carrier bulk density was 2.10.

<Carrier Production Comparative Example 2>
120 parts of a methyl silicone resin (solid content 25%) made of a bifunctional or trifunctional monomer having a weight molecular weight of 15,000, 120 parts of the conductive fine particle production example 1, and titanium diisopropoxybis (ethyl) as a catalyst Acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) 6 parts and SH6020 (manufactured by Toray Silicone Co., Ltd.) 1.2 parts as a silane coupling agent were diluted with toluene to obtain a resin solution having a solid content of 10 wt%. . The resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material production method 4 using a fluidized bed type coating apparatus, controlling the temperature in the fluidized tank to 70 ° C., respectively. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain Carrier I having a weight average particle size of 40 μm. The SF-2 of this carrier i was measured and found to be 114, and the carrier fluidity energy amount was 2800 mJ.

<Carrier Production Example 8>
60 parts of methylsilicone resin (solid content 25%) having a weight molecular weight of 15,000 made from a bifunctional or trifunctional monomer, 38 parts of the filler of Production Example 4 of conductive fine particles, titanium diisopropoxybis (ethyl) as a catalyst Acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co.) 3 parts and SH6020 (manufactured by Toray Silicone Co., Ltd.) 0.5 part as a silane coupling agent were diluted with toluene to obtain a resin solution having a solid content of 10 wt%. . The resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material production method 2 using a fluidized bed coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier j having a weight average particle size of 40 μm. The SF-2 of this carrier j was measured and found to be 137, and the carrier fluidity energy amount was 3700 mJ.

<Carrier Production Comparative Example 3>
40 parts of methylsilicone resin (solid content 25%) having a weight molecular weight of 15,000 made from a bifunctional or trifunctional monomer, oxygen-deficient tin oxide-coated barium sulfate powder (Pastran 4310, Mitsui Kinzoku Mining Co., Ltd., weight average particle) Diameter: 150 nm, volume resistivity: 12 Ω · cm) 20 parts, titanium diisopropoxybis (ethyl acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co.) as catalyst, SH6020 (Toray Silicone) as silane coupling agent 0.3 parts) was diluted with toluene to obtain a resin solution having a solid content of 10 wt%. This resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 3 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier k having a weight average particle size of 40 μm. The SF-2 of this carrier k was measured and found to be 116, and the carrier fluidity energy amount was 2600 mJ.

<Carrier Production Example 9>
24 parts of a methyl silicone resin (solid content 25%) made of a bifunctional or trifunctional monomer having a weight molecular weight of 15,000, 24 parts of oxygen-deficient tin oxide-coated barium sulfate powder (Pastlan 4310 manufactured by Mitsui Mining & Smelting Co., Ltd.) 7 parts of particle size: 150 nm, volume resistivity: 12 Ω · cm), 1 part of titanium diisopropoxybis (ethylacetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co.) as a catalyst, SH6020 (Toray Silicone Co., Ltd. (0.2 parts) was diluted with toluene to obtain a resin solution having a solid content of 10 wt% .The resin solution was added to 1000 parts of the core material particles prepared by the core material manufacturing method 5 and fluidized bed type coating apparatus. Was applied and dried while controlling the temperature in the fluidized tank at 70 ° C. The obtained carrier was 180 ° C. in an electric furnace. After baking for 2 hours, the particle size was adjusted by sieving to obtain a carrier l having a weight average particle diameter of 40 μm, and SF-2 of this carrier l was measured to be 148 and the carrier fluidity energy was 3900 mJ. there were.

<Carrier Production Example 10>
112 parts of methyl silicone resin having a weight molecular weight of 15,000 (solid content 25%) made from a bifunctional or trifunctional monomer, 100 parts of the filler of Conductive Fine Particle Production Example 4, and the filler of Conductive Fine Particle Production Example 2 34.4 parts, 6 parts of titanium diisopropoxybis (ethylacetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co.) as a catalyst, 1.0 part of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent with toluene Dilution was performed to obtain a resin solution having a solid content of 10 wt%. The resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 5 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier m having a weight average particle size of 40 μm. The SF-2 of this carrier m was measured and found to be 126, and the carrier fluidity energy amount was 3400 mJ.

<Carrier Production Example 11>
12 parts of methylsilicone resin (solid content 25%) having a weight molecular weight of 15,000 made from a bifunctional or trifunctional monomer, 48 parts of the resin obtained in Resin Synthesis Example 2, and the filler of Conductive Fine Particle Production Example 4 38 parts, 1 part of titanium diisopropoxybis (ethyl acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) as a catalyst, and 0.5 part of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent are diluted with toluene. Thus, a resin solution having a solid content of 10 wt% was obtained. The resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 5 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier n having a weight average particle size of 40 μm. The SF-2 of this carrier n was measured to be 139, and the carrier fluidity energy amount was 3700 mJ.

<Carrier Production Example 12>
22 parts of methyl silicone resin (solid content 25%) having a weight molecular weight of 15,000 made from a bifunctional or trifunctional monomer, 22 parts of the resin obtained in Resin Synthesis Example 1, and the filler of Production Example 3 for conductive fine particles 22 parts, 2 parts of titanium diisopropoxybis (ethyl acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) as a catalyst, and 0.3 part of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent are diluted with toluene. Thus, a resin solution having a solid content of 10 wt% was obtained. The resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 5 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier o having a weight average particle size of 40 μm. The SF-2 of this carrier o was measured and found to be 137, and the carrier fluidity energy amount was 3600 mJ.

<Carrier Production Example 13>
28 parts of methyl silicone resin (solid content 25%) having a weight molecular weight of 15,000 prepared from a bifunctional or trifunctional monomer, 28 parts of the resin obtained in Resin Synthesis Example 2, and the filler of Conductive Fine Particle Production Example 5 15 parts, 1 part of titanium diisopropoxybis (ethyl acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co.) as a catalyst, 0.5 part of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent are diluted with toluene. Thus, a resin solution having a solid content of 10 wt% was obtained. The resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 5 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier p having a weight average particle size of 40 μm. The SF-2 of this carrier p was measured and found to be 143, and the carrier fluidity energy amount was 3800 mJ.

<Carrier Production Example 14>
35 parts of a methylsilicone resin (solid content 25%) having a weight molecular weight of 15,000 made from a bifunctional or trifunctional monomer, 9 parts of the resin obtained in Resin Synthesis Example 2, and the filler of Conductive Fine Particle Production Example 1 7 parts, 1 part of titanium diisopropoxybis (ethyl acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co.) as a catalyst, and 0.3 part of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent are diluted with toluene. Thus, a resin solution having a solid content of 10 wt% was obtained. This resin solution was applied and dried on 1000 parts of core material particles prepared by the core material production method 6 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier q having a weight average particle size of 40 μm. The SF-2 of this carrier q was measured to be 117, and the carrier fluidity energy amount was 3300 mJ.

<Carrier Production Comparative Example 4>
64 parts of methyl silicone resin having a weight molecular weight of 15,000 (solid content 25%) made from a bifunctional or trifunctional monomer, 56 parts of the filler of Production Example 3 of conductive fine particles, titanium diisopropoxybis (ethyl) as a catalyst Acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) 6 parts and SH6020 (manufactured by Toray Silicone Co., Ltd.) 0.6 parts as a silane coupling agent were diluted with toluene to obtain a resin solution having a solid content of 10 wt%. . This resin solution was applied and dried on 1000 parts of core material particles prepared by the core material production method 6 using a fluidized bed type coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier r having a weight average particle size of 40 μm. The SF-2 of this carrier r was measured and found to be 114, and the carrier fluidity energy amount was 3200 mJ.

<Carrier Production Comparative Example 5>
80 parts of methyl silicone resin (solid content 25%) having a weight molecular weight of 15,000 made from a bifunctional or trifunctional monomer, carbon black REGAL 330 (number average particle size: 25 nm, volume resistivity: 0.1Ω) manufactured by Cabot Corporation 2 parts of cm), 4 parts of titanium diisopropoxybis (ethylacetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co.) as a catalyst, and 0.6 parts of SH6020 (manufactured by Toray Silicone Co., Ltd.) as a silane coupling agent, Dilution with toluene gave a resin solution with a solid content of 10 wt%. The resin solution was applied and dried on 1000 parts of the core material particles prepared by the core material manufacturing method 7 using a fluidized bed coating apparatus while controlling the temperature in the fluidized tank at 70 ° C. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier s having a weight average particle size of 40 μm. The SF-2 of this carrier s was measured to be 145, and the carrier fluidity energy amount was 4400 mJ.

<Carrier Production Example 15>
1. 26 parts of a methylsilicone resin (solid content 25%) having a weight molecular weight of 15,000 and a guanamine resin (Hitaloid 3001, manufactured by Hitachi Chemical Co., Ltd., solid content: 50% by weight) prepared from a bifunctional or trifunctional monomer 5 parts, 5 parts of acrylic resin (My Coat 106 manufactured by Mitsui Cytec Co., Ltd., solid content: 77% by weight), 10 parts of the filler of Production Example 1 of conductive fine particles, titanium diisopropoxybis (ethylacetoacetate) TC as a catalyst -750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) 2 parts and SH6020 (manufactured by Toray Silicone Co., Ltd.) 0.3 part as a silane coupling agent were diluted with toluene to obtain a resin solution having a solid content of 10 wt%. The resin solution was coated on 1000 parts of core material particles prepared by the core material manufacturing method 8 by a dipping method using a multifunctional mixer. At this time, the carrier core temperature was set to 100 ° C., the resin solution was put into the mixing mixer, the mixing stirring blade was rotated until the coating solution evaporated, the coating / stirring / drying process was performed, and the carrier was taken out. After the obtained carrier was baked in an electric furnace at 180 ° C./2 hours, the particle size was adjusted by sieving to obtain a carrier t having a weight average particle size of 40 μm. The SF-2 of this carrier t was measured and found to be 136, and the carrier fluidity energy amount was 3700 mJ.

<Developing developer>
70 parts of the toner obtained in Toner Production Example 1 were mixed with 930 parts of each of carriers a to t obtained in the carrier production example and carrier production comparative example, and stirred at 81 rpm for 5 minutes using a turbuler mixer. T was obtained from developer A.
The fluidity energy amount of the developer for evaluation was measured by the above method.
In addition, for the replenishment developer composed of carrier and toner, a replenishment developer is prepared so that the carrier concentration becomes 10%, and printing is performed by the following method, and the ghost image, resistance value change, and spent toner amount are adjusted. It was measured.

<Printing method>
Set each developer and replenishment developer on a commercially available digital full-color printer (RICOH Pro C901, manufactured by Ricoh Co., Ltd.), and 100 kp of a character chart (size of one character: 2 mm × 2 mm) with an image area of 8% ( After printing (100,000 sheets), another 200 kp sheets were printed.

<Ghost image evaluation method>
For the ghost, after outputting 100 kp sheets, the longitudinal band chart shown in FIG. 11A is printed, and the density difference between the sleeve one round (a) and one round after (b) is measured by the X-Rite 938 spectrocolorimetric densitometer (X -Made by Rite), the average density difference between the three measurements at the center, the rear, and the front was taken as ΔID, and the ranking was performed below.
◎: Very good, ○: Good, Δ: Acceptable level, ×: Unusable level for practical use ◎, ○, △ were accepted and x was rejected.
A: 0.01 ≧ ΔID
○: 0.01 <ΔID ≦ 0.03
Δ: 0.03 <ΔID ≦ 0.06
×: 0.06 <ΔID

<Change in resistance value after 300 kp>
A carrier resistance value (volume resistivity) was measured using a 0 kp developer and a 300 kp printed developer. It measured using the apparatus (cell) of FIG. At this time, the toner was separated and removed using 795 mesh as the developer using the apparatus shown in FIG. 10, and only the carrier was measured. The resistance value of the carrier was measured using the apparatus (cell) shown in FIG.
Incidentally, a method for obtaining the volume resistivity of the carrier using the cell shown in FIG. 9 will be described as follows. First, a carrier 13 is filled in a cell made of a fluororesin container in which electrodes 12a and 12b having a surface area of 2.5 cm × 4 cm are accommodated at a distance of 0.2 cm, the drop height is 1 cm, and the tapping speed is 30 times. Tapping was performed 10 times per minute. Next, a resistance r [Ω] 30 seconds after applying a DC voltage of 1000 V between the electrodes 12a and 12b was measured using a high resistance meter 4329A (manufactured by Yokogawa Hewlett-Packard Company), and the formula “r × The volume resistivity [Ωcm] was calculated from (2.5 × 4) /0.2 ”.
Further, the apparatus shown in FIG. 10 indicates that “a certain amount of developer is put into a conductor container (cage) having a metal mesh at both ends. The mesh (stainless steel) has an opening between the toner and the carrier particle size. Select one (opening 20 μm) and set so that the toner passes between the meshes.When compressed nitrogen gas (1 kgf / cm ² ) is blown from the nozzle for 60 seconds and the toner is ejected from the gauge, The carrier having the opposite polarity to the charge of the toner is left.
A difference ΔLogR between the resistance value of the carrier at 300 kp printing and the resistance value of the carrier at 0 kp was calculated and judged as follows.
◎: Very good, ○: Good, △: Acceptable level, ×: Unusable level for practical use ◎ ΔLogR ≦ 0.5
○ 0.5 <ΔLogR ≦ 1
△ 1 <ΔLogR ≦ 2
× 2 <ΔLogR

<Spent toner amount>
The toner component is extracted with methyl ethyl ketone for the carrier running 300 kp sheets and the initial carrier, and the difference is expressed as the amount of spent toner (expressed in wt% with respect to the carrier weight).
◎: Very good, ○: Good, △: Acceptable level, ×: Unusable level ◎ 0 or more and less than 0.03 wt% ○ 0.03 or more and less than 0.07 wt% △ 0.07 or more ~ Less than 0.15wt% x 0.15wt% or more

The developer using the carrier shown in Examples 1 to 155 has a small and good ΔID of the ghost image carried out after 100 kp printing, the resistance change at 0 kp and 300 kp is small, the toner spent amount is also small, and the image changes. There were few.
On the other hand, the developer using the carrier shown in Comparative Examples 2, 3, and 4 had a large ghost image ΔID, and the image density difference could be visually confirmed. In the carriers shown in Comparative Examples 1 and 5, the resistance value after 300 kp greatly decreased, the toner amount to the fine line decreased, the image density increased, and a change in image quality was observed. Further, in Comparative Example 2, the amount of toner spent was large, the resistance value increased, and it was confirmed that background stains, in-machine toner scattering, and image density increase accompanying a decrease in charge were confirmed.

11 Cell 12a Electrode 12b Electrode 13 Carrier 20 Photosensitive drum 21 Toner 23 Carrier 24a Drive roller 24b Drive roller 26 Exposure light source 32 before cleaning Image carrier charging member 33 Image exposure system 40 Developing device 41 Developing sleeve 42 Developer containing member 43 Developing Agent supply restriction member (doctor blade)
44 Support case 45 Toner hopper 46 Developer container 47 Developer agitation mechanism 48 Toner agitator 49 Toner supply mechanism 50 Transfer mechanism 60 Cleaning mechanism 61 Cleaning blade 62 Toner recovery chamber 64 Brush-like cleaning means 70 Static elimination lamp 80 Intermediate transfer medium

Japanese Patent No. 3356948 JP 2005-157002 A JP 11-231652 A Japanese Unexamined Patent Publication No. 7-72733 Japanese Patent Laid-Open No. 7-128983 Japanese Patent Laid-Open No. 7-92913 Japanese Patent Laid-Open No. 11-65247 JP 2012-47971 A JP 2012-58637 A

Claims (8)

A carrier for an electrostatic latent image developer comprising a magnetic core material particle and a coating layer covering the surface of the core material particle, the core material particle having SF-2 of 120 to 160 and Ra of 0.5. The coating layer contains 50 to 500 parts by weight of a filler selected from aluminum oxide and barium sulfate with respect to 100 parts by weight of the resin, and the carrier has SF-2 of 127 to The flow energy amount of the carrier is in the range of 3200 to 4000 mJ in the powder rheometer when the tip speed of the rotary blade is 100 mm / sec and the total energy amount is 70 mm when the rotary blade has an approach angle of -5 °. A carrier for an electrostatic latent image developer.   The carrier for an electrostatic latent image developer according to claim 1, wherein the filler has a number average particle diameter of 50 to 800 nm. Electrostatic latent image developer carrier according to claim 1 or 2, wherein the resin percentage of the coating layer to the core material particles is 0.5 to 3 wt%. A method for producing a carrier for an electrostatic latent image developer comprising a core material particle having magnetism and a coating layer covering the surface of the core material particle, wherein the core material particle has SF-2 of 120 to 160, Ra 0.5 to 1.0 μm is used, and the core particle surface is a copolymer containing at least a monomer component represented by the following structural formula 1 and a monomer component represented by the following structural formula 2. It is coated with a coating layer containing a filler selected from 50 to 500 parts by weight of aluminum oxide and barium sulfate with respect to 100 parts by weight of a resin containing a resin obtained by heat treatment, and SF-2 is 127 to 150. The amount of fluid energy of the carrier is within the range, and the total energy amount when the tip speed of the rotor blade is 100 mm / sec in the powder rheometer and the approach distance is 70 mm at the rotor blade approach angle of -5 °. To obtain a carrier in the range of 3200 to 4000 mJ.
(In Structural Formulas 1 and 2 above, R ¹ , R ² , R ³ , X, Y, and m are as follows.)
R ¹ : hydrogen atom or methyl group R ² : alkyl group having 1 to 4 carbon atoms R ³ : alkyl group having 1 to 8 carbon atoms or alkoxy group having 1 to 4 carbon atoms X: 10 to 90 mol%
Y: 10 to 90 mol%
m: an integer from 1 to 8 The copolymer, an electrostatic latent image producing method of the career developer according to claim 4, characterized in that it comprises a copolymer represented by the following structural formula 3.
(In the above structural formula 3, R ¹ , R ² , R ³ , X, Y, and m are as follows.)
R ¹ : hydrogen atom or methyl group R ² : alkyl group having 1 to 4 carbon atoms R ³ : alkyl group having 1 to 8 carbon atoms or alkoxy group having 1 to 4 carbon atoms X: 10 to 90 mol% Y : 10 to 90 mol%
m: an integer from 1 to 8 It said resin layer by coating, an electrostatic latent image producing method of the career developer according to claim 4 or 5, characterized in that it is obtained by heat treatment thereafter. Forming an electrostatic latent image on the electrostatic latent image carrier;
The electrostatic latent image formed on the electrostatic latent image carrier is developed using the developer having the electrostatic latent image developer carrier and the toner according to any one of claims 1 to 3 to form a toner image. Forming a step;
Transferring the toner image formed on the electrostatic latent image carrier to a recording medium;
Fixing the toner image transferred to the recording medium;
An image forming method comprising: A replenishing developer containing the proportions of 2 to 50 parts by weight of toner to carrier 1 part by weight, the carrier for electrostatic latent image developer of the carrier according to any one of claims 1 to 3 A developer for replenishment characterized by the above.