JP2005338810A - Developing method and developing device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developing method with which coat defects such as streaks and unevenness are not caused to a developer layer on a developing sleeve and accumulation of external additives on a carrier surface and toner spent are suppressed, in a multistage developing system using a two-component developer. <P>SOLUTION: The developing method uses a developing device including at least: a first developer carrier arranged to be opposed to an image carrier; and a second developer carrier arranged on a downstream side of a rotation direction of the image carrier with respect to the first developer carrier, wherein a latent image formed on the image carrier is developed with a developer. The developer is a two-component developer having toner and a magnetic carrier; and the developer has a degree of compression C in the range of 20-32% and a shearing stress obtained by shearing stress measurement under a consolidation load of 4.0×10<SP>-4</SP>N/mm<SP>2</SP>in the range of 0.5×10<SP>-4</SP>to 2.5×10<SP>-4</SP>N/mm<SP>2</SP>. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  In the present invention, in an electrophotographic method, an electrostatic latent image formed on an electrostatic latent image carrier such as an electrophotographic photosensitive member or an electrostatic recording derivative is developed with a two-component developer to be visualized. The development method for this is related to.

  Conventionally, many methods are known as electrophotographic methods. Generally, a photoconductive material is used to form an electrostatic latent image on an electrostatic latent image carrier (photosensitive drum) by various means. Next, the electrostatic latent image is developed with a developer to be visualized, and the toner image is transferred to a transfer material such as paper as necessary, and then the toner image is fixed on the transfer material by heat and pressure. To obtain a copy. The development method in electrophotography is mainly divided into a one-component development method that does not require a carrier and a two-component development method that has a toner and a carrier, and is particularly used in a digital multi-function peripheral and a full-color copying machine that require high image quality. As the developing method, a two-component developing method is preferably used.

  As the two-component development method, the following method is known. A magnetic brush of a two-component developer having a non-magnetic toner and a magnetic carrier is formed on a developer carrier (developing sleeve) containing a magnet, and the magnetic brush has a predetermined layer thickness by a developer layer thickness regulating member. After coating, the film is transported to a development area facing the photosensitive drum. In the development area, the electrostatic latent image is used as a toner image by bringing the magnetic brush close to or in contact with the surface of the photosensitive drum while applying a predetermined developing bias between the photosensitive drum and the developing sleeve. It is a method of visualizing.

  In recent digital multi-function printers and full-color copiers that use two-component development methods, so-called multi-stage development methods have been widely proposed in which development is performed using a plurality of developer carriers as image quality and speed increase. Has been. This multi-stage development system is preferably used because there are many opportunities for rubbing between the magnetic brush and the surface of the photosensitive drum, and a wide development area can be secured, so that a high-definition and high-density image can be obtained. However, it is difficult to form a uniform developer layer on a plurality of developing sleeves. In particular, if the developer is not successfully transferred between the developing sleeves, the developer may be scattered or uneven coating may occur. In addition, the developer is likely to deteriorate due to the large stress applied to the developer between the developing sleeve and the developer layer thickness regulating member (between S and B) and between the developing sleeve and the developing sleeve (between SS). There is. Considering these problems, it seems important to control the fluidity of the developer.

Regarding the fluidity of the two-component developer, for example, in Patent Document 1 and Patent Document 2, the apparent density of the two-component developer is 1.2 to 2.0 g / cm ³ and the degree of compression is 5 to 19%. A two-component developer characterized in that it has been proposed. As a result, by suppressing the change in bulk density, the change in image density and color is suppressed in the image forming method that controls the toner density by detecting the change in permeability of the two-component developer using the inductance of the coil. Has the effect of

  However, in the above-described multi-stage development system, it is difficult to form a uniform developer layer on a plurality of developing sleeves when the two-component developer having such fluidity is used. The delivery of the developer is likely to be non-uniform, and a coating defect may occur.

As for the multi-stage development method using a two-component developer, for example, as proposed in Patent Document 3, Patent Document 4, and Patent Document 5, a uniform developer layer is formed on the developing sleeve, and In order to prevent the deterioration of the developer in the developing unit, the magnetic pole configuration, the stirring means, and the like have been improved. However, studies on the improvement of a developer having fluidity suitable for the multistage development method are still insufficient.
Japanese Patent Laid-Open No. 11-073005 Japanese Patent Laid-Open No. 11-147331 JP 2003-295602 A Japanese Patent Laid-Open No. 2003-323043 JP 2003-323052 A

  An object of the present invention is to prevent development of a coating layer such as streaks or unevenness in a developer layer on a developing sleeve in a developing method using a multistage developing system, and accumulation of external additives on a carrier surface or toner spent. It is to provide a developing method that has high solid uniformity over a long period of time even in different environments, and that has less image density fluctuation and tribo fluctuation.

  The above object is achieved by the following configurations of the present invention.

(1) The present invention provides a first developer carrier disposed opposite to an image carrier, and a developer layer thickness regulating member for forming a developer layer on the first developer carrier. And a second developer carrier disposed downstream of the first developer carrier in the rotation direction of the image carrier, the first developer carrier and the second developer carrier. The developer carrying member carries and conveys the developer to the development area where the first developer carrying member and the second developer carrying member and the image carrying member face each other, and the developer is carried on the image carrying member. A developing method using a developing device that develops the formed latent image with the developer,
The developing device transfers the developer supplied to the development area formed by the first developer carrier and the image carrier from the first developer carrier to the second developer carrier. The developed developer is provided to a development region formed by the second developer carrier and the image carrier,
The developer is a two-component developer having a toner having toner particles containing at least a binder resin and a colorant, and a magnetic carrier.
The developer is represented by the following formula (1)
Compression degree C (%) = 100 × (PA) / P (1)
[In the formula, A is a loose apparent density (g / cm ³ ), and P is a firm apparent density (g / cm ³ ). ]
The compression degree C obtained from is 20 to 32%,
Further, the developer has a shear stress of 0.5 × 10 ^{−4 to} 2.5 × 10 ⁻⁴ N / mm under a consolidation load of 4.0 × 10 ⁻⁴ N / mm ² according to shear stress measurement. ^The present invention relates to a developing method.

  (2) The present invention also relates to the developing method according to (1), wherein the magnetic carrier has a coating layer on the surface of a magnetic fine particle dispersed resin core containing at least magnetic fine particles and a binder resin.

  (3) In the present invention, the toner is obtained by externally adding inorganic fine particles to toner particles, and the aspect ratio (major axis / minor axis) of the inorganic fine particles on the toner particle surface is 1.0 to 1. And the number average particle diameter on the surface of the toner particles is 0.06 to 0.30 μm.

(4) Further, in the invention, the developing device is provided in a developing chamber for supplying the developer to the first developer carrier, and below the developing chamber, and the second developer And a stirring chamber for recovering the developer from the carrier, and the recovered developer is pushed up from the stirring chamber to the developing chamber by the pressure of the developer at the end of the stirring chamber. The present invention relates to the developing method described in (1).

(5) In the present invention, the first developer carrying member includes a first magnetic field generating unit provided so as not to rotate and the first magnetic field generating unit, and is provided rotatably. A first developing sleeve;
The first magnetic field generating means is provided so as to be adjacent to the first magnetic pole downstream of the developing region in the moving direction of the first developer carrier and downstream of the first magnetic pole in the moving direction. Having at least a first magnetic pole and a second magnetic pole of the same polarity;
The developer layer thickness regulating member is disposed in a region substantially opposite to the second magnetic pole;
The second developer carrying member includes a second magnetic field generating unit provided so as not to rotate, and a second developing sleeve including the second magnetic field generating unit and provided rotatably. And
The second magnetic field generating means includes a third magnetic pole opposite in polarity to the first magnetic pole provided in a region substantially opposite to the first magnetic pole, and the second developer carrier rotating direction of the third magnetic pole. The developing method according to (1), further comprising at least a fourth magnetic pole having the same polarity as the third magnetic pole provided adjacent to the upstream side.

  (6) Further, in the invention, the developing device has a developer discharging mechanism, and the developer discharging mechanism discharges excess developer, and the developing device includes the toner and the magnetic carrier. The developing method according to (1), wherein a replenishing developer containing at least is replenished.

(7) The present invention also provides a developer layer thickness regulation for forming a developer layer on the first developer carrier and the first developer carrier disposed opposite to the image carrier. A member and at least a second developer carrier disposed on the downstream side in the rotation direction of the image carrier relative to the first developer carrier, the first developer carrier and the second developer carrier. The developer carrier is used to carry and transport the developer to the development area where the first developer carrier and the second developer carrier and the image carrier are opposed to each other, on the image carrier. A developing device for developing the latent image formed in the developer with the developer,
The developing device transfers the developer supplied to the development area formed by the first developer carrier and the image carrier from the first developer carrier to the second developer carrier. The developed developer is provided to a development region formed by the second developer carrier and the image carrier,
The developer is a two-component developer having a toner having toner particles containing at least a binder resin and a colorant, and a magnetic carrier.
The developer is represented by the following formula (1)
Compression degree C (%) = 100 × (PA) / P (1)
[In the formula, A is a loose apparent density (g / cm ³ ), and P is a firm apparent density (g / cm ³ ). ]
The compression degree C obtained from is 20 to 32%,
Further, the developer has a shear stress of 0.5 × 10 ^{−4 to} 2.5 × 10 ⁻⁴ N / mm under a consolidation load of 4.0 × 10 ⁻⁴ N / mm ² according to shear stress measurement. ^The present invention relates to a developing device.

According to the present invention, the development method described in (1) above does not cause coating defects such as streaks or unevenness in the developer layer on the development sleeve in the development method using the multistage development method, In addition, accumulation of external additives on the carrier surface and toner spent can be prevented, and solid uniformity is high over a long period of time even in different environments, and image density fluctuation and tribo fluctuation can be suppressed.

  Further, according to the present invention, the development method described in (2) above, between the developing sleeve and the developer layer thickness regulating member by using a magnetic fine particle dispersed carrier having an appropriate true density and magnetic characteristics. In addition, the stress on the developer between the upstream developing sleeve and the downstream developing sleeve can be reduced, and toner spent can be further prevented.

  Further, according to the present invention, the development method described in the above (3) allows the spacer effect of the inorganic fine particles having an appropriate particle size and aspect ratio to be provided between the developing sleeve and the developer layer thickness regulating member or on the upstream side. The stress on the developer between the developing sleeve and the downstream developing sleeve can be reduced, and toner spent can be prevented.

  According to the present invention, the development method described in the above (4) separates the function into a developing chamber for supplying a fresh developer and a stirring chamber for collecting the developed developer. As a result, the developing device itself can be reduced in size, and the deterioration of the developer can be suppressed, and a good image can be obtained over a long period of time.

  Further, according to the present invention, the development method described in the above (5) reduces the stress on the developer between the developing sleeve and the developer layer thickness regulating member and between the upstream developing sleeve and the downstream developing sleeve. Further, the toner can be further reduced and toner spent can be prevented.

  According to the present invention, the developing method described in (6) above allows the deteriorated developer to be discharged including the carrier, and a good image can be obtained over a long period of time.

  According to the invention, since the developing device described in (7) above is used, in the developing device using the multistage developing system, the developer layer on the developing sleeve does not cause coating defects such as streaks and unevenness. Also, to provide a developing device that prevents accumulation of external additives on the carrier surface and toner spent, has high solid uniformity over a long period of time even in different environments, and can suppress fluctuations in image density and tribo. Can do.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  First, the developing method of the present invention will be described in detail.

  An example of a developing device using the developing method of the present invention is shown in FIG. The developer T accommodated in the developing container 2 in the developing device 1 is first arranged in the first developing sleeve including the first magnet roll 8 ′ disposed upstream of the rotation direction “a” of the image carrier 10. 8 is carried and conveyed. Then, a developer layer is formed on the surface of the developing sleeve by the developer layer thickness regulating member 9 disposed close to the developing sleeve 8. Thereafter, the developer T is conveyed by the developing sleeve 8 to a first developing area where the developing sleeve 8 and the image carrier 10 are opposed to each other, and is used for development. Thereafter, the developer remaining on the surface of the first developing sleeve is a region where the first developing sleeve 8 and the second developing sleeve 11 disposed on the downstream side in the rotation direction a of the image carrier 10 face each other. It is delivered to the second developing sleeve 11. The developer T transferred to the second developing sleeve 11 is carried and transported by the second developing sleeve 11 and transported to the second developing region where the second developing sleeve 11 and the image bearing member face each other. And subjected to development. Thereafter, the developer remaining on the surface of the second developing sleeve is collected in the developing container 2.

In the case of a developing method employing such a multi-stage developing system, between the developing sleeve 8 and the developer layer thickness regulating agent 9 (between S and B), between the first developing sleeve 8 and the second developing sleeve 11 (S- (Between S), a compressive force or a shearing force is applied to the developer. In particular, when the rotation direction of the first developing sleeve 8 is the b direction and the rotation direction of the second developing sleeve 11 is the c direction, The shearing force to the developer between S and S becomes very large, and the developer tends to deteriorate. Therefore, the present inventors have expressed the following formula (1) as a two-component developer in order to reduce the stress on the developer T between S-B and S-S.
Compression degree C (%) = 100 (PA) / P (1)
[Where A is the loose apparent density (g / cm ³ ) and P is the firm apparent density (g / cm ³ )]
The compression degree C obtained from is 20 to 32%,
In addition, a developer having a shear stress of 0.5 × 10 ^{−4 to} 2.5 × 10 ⁻⁴ N / mm ² under a consolidation load of 4.0 × 10 ⁻⁴ N / mm ² by shear stress measurement. The inventors have found that the above-mentioned problems can be solved by using, and have reached the present invention.

  In the present invention, the degree of compressibility C of the developer as measured by fluidity is 20 to 32%. By being in this range, the rising state of the developer layer on the developing sleeve becomes uniform, and the toner charge amount distribution on the developing sleeve becomes sharper. As a result, solid uniformity is improved, and stress on the developer is reduced, so that deterioration of the developer can be prevented.

  When the degree of compression is less than 20%, the stress on the developer is surely reduced, but since the rising state of the developer becomes non-uniform, the charge amount distribution on the developing sleeve becomes broad, and the solid image In some cases, the uniformity of the film decreases. Further, it may be difficult to control the particle behavior between S and B or between S and S, which may cause deterioration in image quality or developer scattering.

  On the other hand, when the degree of compression C is greater than 32%, the stress on the developer becomes too great, and the compressed developer stays between S-B and S-S or packs, thereby developing the developer. The layer is likely to cause streaks, unevenness, or the like, or the accumulation of external additives on the carrier surface and the toner spent are likely to occur, and the deterioration of the image quality due to the accelerated developer deterioration is likely to occur.

In the present invention, the shear stress of the developer by shearing stress measurement is consolidation load 4.0 × 10 ^-4 N / mm ² under, 0.5 × 10 ^-4 to 2.5 × 10 ^-4 N / mm ² It is. By being in this range, even when a large shearing force is applied between S-B and S-S, the developer is uniformly on the developing sleeve without staying between S-B and S-S. Coated. Thereby, uneven coating of the developer layer on the developing sleeve and deterioration of the developer are prevented, and a good image can be obtained over a long period of time.

When the shear stress under a consolidation load of 4.0 × 10 ⁻⁴ N / mm ² is smaller than 0.5 × 10 ⁻⁴ N / mm ² , the developer fluidity is too good, and the developing sleeve rotation direction When a shearing force is applied to the developing sleeve, a coating defect or the like may occur on the developing sleeve due to poor regulation between S and B, or developer scattering may occur during delivery of the developer between SS. It becomes easy to cause deterioration of image quality.

In addition, when the shear stress under a consolidation load of 4.0 × 10 ⁻⁴ N / mm ² is larger than 2.5 × 10 ⁻⁴ N / mm ² , the developing sleeve is moved between SB and SS. Even when a shearing force in the rotational direction is applied, the developer stays between S-B and SS, causing streaks and unevenness in the developer layer, and the developer on the developing sleeve. In some cases, the toner tends to accompany accumulation of external additives on the carrier surface and toner spent, and image quality deterioration due to accelerated developer deterioration is likely to occur.

Therefore, in the above developing method, the compressibility C of the developer is 20 to 32%, and the shear stress under a consolidation load of 4.0 × 10 ⁻⁴ N / mm ² is 0.5 × 10 ^{−4 to} 2.5 × 10 ^-4
By being in the range of N / mm ² , the coatability of the developer layer on the developing sleeve becomes more uniform,
The toner charge amount distribution is further sharpened, and even when the developer is compressed or sheared between S-B and S-S, the developer does not stay, and the developer remains in the developer. By reducing the stress, it is possible to provide a developing method that does not cause developer deterioration, improves solid uniformity over a long period of time, and can suppress image density fluctuation and tribo fluctuation. In the embodiment shown in FIG. 1, in order to facilitate the delivery of the developer between the developing sleeves, the second magnet roll 11 ′ included in the first magnet roll 8 ′ and the second developing sleeve 11 is used. It is preferable that the magnetic poles of the above have a reverse polarity.

  In the developing device 1, the inside of the developing container 2 is divided into a developing chamber 3 and a stirring chamber 4 by a partition wall 7. A toner storage chamber is provided above the stirring chamber 4. Is housed. An amount of toner t commensurate with the toner consumed by development is dropped and replenished from the replenishing port in the toner storage chamber into the stirring chamber 4. On the other hand, the developer T in which the toner and the magnetic carrier are mixed is accommodated in the developing chamber 3 and the stirring chamber 4.

  A conveying screw 5 is accommodated in the developing chamber 3 and conveys the developer along the longitudinal direction of the first developing sleeve 8 by rotational driving. The developer conveying direction by the screw 5 is opposite to that by the screw 6.

  The partition wall 7 is provided with openings on the front side and the back side, and the developer conveyed by the screw 5 is transferred to the screw 6 from one of the openings, and the developer conveyed by the screw 6 is The other one of the openings is transferred to the screw 5.

  Therefore, the toner t and the developer T replenished in the stirring chamber 4 are stirred and mixed by the screw 6, transported to the developing chamber 3 for development, and the developer after being used for development is put into the stirring chamber 4. A circulation method is adopted in which the toner T consumed by the development is replenished and replenished.

  When such a developer circulation method is applied to the above-described multi-stage development method in which the stress on the developer is large compared to the conventional development method, the developing chamber for supplying the developer to the developing sleeve has a development area. Since it also serves to collect the developer that has passed, as the developer moves in the axial direction of the developing sleeve, the charge amount distribution of the toner on the developing sleeve changes, and the solid uniformity in the axial direction is It may be damaged.

  Therefore, as shown in the developing device 100 of FIG. 2, the developer chamber 3 for supplying the developer to the first developing sleeve 8 and the developer that has passed through the developing region are collected from the second developing sleeve 11. For this purpose, a developing device in which the stirring chamber 4 is functionally separated by a partition wall 7 is preferably used. In FIG. 2, the image carrier 10 rotates clockwise, and the first developing sleeve 8 and the second developing sleeve 11 rotate counterclockwise.

  As a result, fresh developer is always supplied from the developing chamber 3 to the first developing sleeve 8, and the toner supplied from the replenishing port (not shown) and the developing area have passed through the agitating chamber 4. The developer is sufficiently agitated and mixed and supplied again to the developing chamber.

  In the developing device 100 of FIG. 2, the developing chamber 3 and the agitating chamber 4 in the developing container 2 are arranged in the vertical direction, but function separation such as supply and recovery of the developer is performed as described above. Is important and is not limited to the arrangement of FIG. In addition, when the developing chamber and the stirring chamber are arranged in the vertical direction, an advantage of downsizing the developing device itself can be obtained.

  FIG. 3 shows an example of the presence state (agent surface state) of the developer T accommodated in the developing container 2 shown in FIG. The circulation direction of the developer T is the d direction. In this case, the developer T is transported to the opening 71 by the screw 6 in the stirring chamber 4 together with the developer collected from the second developing sleeve 11 after passing through the developing region. Lifted and supplied. Further, the developer T that has been lifted is conveyed to the opening 72 by the screw 5 in the developing chamber 3 and dropped into the stirring chamber 4 while being supplied to the first developing sleeve 8 in the developing chamber 3.

  In the case of the developing method using such a circulation system, the developer surface of the developer T is lifted from the stirring chamber 4 to the developing chamber 3 in the opening 71 to facilitate supply, and the supplied developer T is supplied to the developing chamber. The point is to make it easy to be transported within 3.

In the present invention, the developer has a compressibility C of 20 to 32% and a shear stress under a compaction load of 4.0 × 10 ⁻⁴ N / mm ² is 0.5 × 10 ^{−4 to} 2. By being in the range of 5 × 10 ⁻⁴ N / mm ² , the developer surface is easily lifted by being compressed to some extent, and by having an appropriate shear stress, transportability by a screw is also improved. Excessive packing and poor circulation will not occur.

  Further, as shown in FIG. 2, the first magnet roll 8 ′ has an N3 pole on the downstream side of the developing region of the first developing sleeve 8, and is adjacent to the downstream side of the N3 pole in the same moving direction. It is preferable to arrange the developer layer thickness regulating member 9 so as to face the provided N1 pole and the N1 pole. This repulsive magnetic field due to the N1 pole and the N3 pole improves the delivery of the developer to the second developing sleeve 11 at the N3 pole and has no magnetic pole between the N1 pole and the N3 pole. Excessive incorporation is eliminated, and the stress on the developer between S and B can be reduced.

  The second magnet roll 11 ′ has an S3 pole of reverse polarity at a position substantially opposite to the N3 pole of the first magnet roll 8 ′, and the S3 pole on the upstream side in the rotation direction of the second developing sleeve 11. It is preferable to have S4 pole provided so that it may adjoin. The N3 pole of the first magnet roll 8 ′ and the S3 pole of the second magnet roll 11 ′ have opposite polarities, so that the rotation of the developer in the first developing sleeve 8 is suppressed, and the first developing sleeve As a result, the developer is better delivered from the second developing sleeve 11 to the second developing sleeve 11, and the developer from the second developing sleeve 11 to the stirring chamber 4 is generated by the repulsive magnetic field generated by the S3 pole and the S4 pole. Is more effectively recovered, and the developer re-entry between SSs due to the rotation of the developer in the second developing sleeve 11 is prevented, and the stress on the developer between SSs is further reduced. can do. Although it is particularly preferable to use a magnet roll having the magnetic pole configuration as described above, the present invention is not limited to this as long as the magnetic pole configuration of the magnet roll achieves the above object.

  In addition, the developing device of the present invention preferably has a developer discharge mechanism, and it is preferable that the developer discharge mechanism discharges excess developer and supplies a replenishment developer containing at least toner and a magnetic carrier. . By this replenishment method of simultaneously replenishing the magnetic carrier, it is possible to further suppress the deterioration of the charge imparting property of the magnetic carrier due to long-term durability, and to stably obtain a good image for a long period of time.

Further, the developing sleeve 8 and the developing sleeve 11 are made of at least a material such as aluminum or nonmagnetic stainless steel, and it is preferable to impart an appropriate surface roughness to the surfaces thereof. As the surface roughness, the arithmetic average roughness Ra of JIS-B-0601 is preferably 0.1 to 4.0 μm, and the ten-point average roughness is 1.0 to 40 μm. It is preferable to adjust appropriately in order to obtain As a method for imparting roughness to the surface of the developing sleeve, known techniques can be applied, but dry blasting using a glass bead or alundum abrasive, wet honing or the like is preferably used.

  Next, the magnetic carrier that can be used in the present invention will be described in detail.

  The magnetic carrier that can be used in the present invention is preferably a magnetic carrier having a coating layer formed on the surface of a known ferrite core particle or magnetic fine particle dispersed resin core, and particularly preferably a magnetic fine particle dispersed resin core (carrier core). Magnetic carrier having a coating layer formed on the surface thereof.

Magnetic carrier that can be used in the present invention is preferably a true density of 2.5 to 5.0 g / cm ^3, more preferably 2.5 to 4.2 g / cm ^3, particularly preferably 3.0 to 4.0g /
cm ³ . When the true density of the magnetic carrier is within this range, it is preferable that the developer is prevented from scattering and the toner spent on the carrier is suppressed. The magnetic carrier forms a coating layer on the surface of the magnetic fine particle dispersed resin core. The magnetic carrier is particularly preferable because the true density can be easily controlled within this range.

In the magnetic carrier that can be used in the present invention, the magnetic fine particles used in the magnetic fine particle dispersed resin core are preferably magnetite fine particles, and are nonmagnetic inorganic compounds for adjusting the true density and magnetic properties of the magnetic carrier. It is preferable to use certain hematite (α-Fe ₂ O ₃ ) fine particles in combination.

  As the binder resin constituting the magnetic fine particle dispersed resin core particles that can be used in the present invention, a thermosetting resin is preferable.

  Thermosetting resins include phenolic resins, epoxy resins, polyamide resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, xylene resins, acetoguanamine resins, furan resins, silicone resins, polyimide resins, urethane resins. Is mentioned. These resins may be used alone or in combination of two or more, but preferably contain at least a phenol resin.

  The ratio of the binder resin and the magnetic fine particles constituting the core particles in the present invention is preferably binder resin: magnetic fine particles = 1: 99 to 1:50 on a mass basis.

  In the present invention, the carrier coating material preferably contains at least a binder resin and conductive fine particles.

  Any known resin can be used as the binder resin for forming the coating material used for the magnetic carrier that can be used in the present invention. Preferably, the binder resin is a perfluoroethylene such as polytetrafluoroethylene or polyperfluoropropylene. Polymer, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyfluorochloroethylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and trifluorochloroethylene, tetrafluoro Examples thereof include a copolymer of ethylene and hexafluoropropylene, a copolymer of vinyl fluoride and vinylidene fluoride, and a copolymer of vinylidene fluoride and tetrafluoroethylene.

  In particular, as a binder resin for forming a coating material preferably used in the present invention,

〔式中、ｍは０乃至１０の整数を示す。〕
で示されるパーフルオロアルキルユニットを有する（メタ）アクリル酸エステルの重合体又は共重合体がよい。

[Wherein, m represents an integer of 0 to 10. ]
A polymer or copolymer of (meth) acrylic acid ester having a perfluoroalkyl unit represented by

  The above-mentioned resins can be used alone or in combination. In addition, a curing agent or the like can be mixed with a thermoplastic resin and cured for use.

  In the present invention, when m exceeds 10 in the above general formula, the resin is likely to precipitate from the solvent, and it is difficult to obtain a good coating film when coating. It is more preferable that m is 5 to 9 in order to have both good toner releasability and coat film formability.

  More preferably, it is excellent in adhesiveness with a core by using resin of the following general formula.

〔式中、ｍは０乃至１０の整数を示し、ｎは１乃至１０の整数を示す。〕

[Wherein, m represents an integer of 0 to 10, and n represents an integer of 1 to 10. ]

  Further, a resin having a unit represented by the following general formula (C) and an acrylate unit or a methacrylic acid ester unit represented by the following general formula (d) is preferable in order to improve toner releasability from the carrier.

〔式中、ｍは０乃至１０の整数を示し、ｎは１乃至１０の整数を示し、ｌは、１以上の整数を示す。〕

[Wherein, m represents an integer of 0 to 10, n represents an integer of 1 to 10, and l represents an integer of 1 or more. ]

〔式中、Ｒ₁は水素又はメチル基を有し、Ｒ₂は水素又は炭素数１乃至２０のアルキル基を示し、ｋは１以上の整数を示す。〕

[Wherein, R ₁ has hydrogen or a methyl group, R ₂ represents hydrogen or an alkyl group having 1 to 20 carbon atoms, and k represents an integer of 1 or more. ]

Further, even if a resin obtained by grafting a polymer having a unit represented by (d) on the copolymer unit of the above general formulas (c) and (d) is used for a long period of time, the toner releasability characteristics can be maintained
The coating material is also excellent in resistance to peeling from the carrier, and is particularly preferable.

  When a thermoplastic resin is used as the binder resin for forming the coating material, this thermoplastic resin has a weight average molecular weight of 10,000 in a gel permeation chromatograph (GPC) which is a soluble component of tetrahydrofuran (THF). It is preferable that it is thru | or 300,000 at the point which improves the intensity | strength of a coating material and the peeling resistance of a coating material and a core surface.

  The binder resin forming the coating material preferably has a main peak in the region of molecular weight 2,000 to 100,000 in the GPC chromatogram of the THF soluble component, and further has a molecular weight of 2,000 to 100,000. It is preferable to have a subpeak or shoulder in the region of 000. Most preferably, the resin forming the coating material has a main peak in the molecular weight range of 20,000 to 100,000 in the GPC chromatogram of the THF soluble component, and a molecular weight range of 2,000 to 19,000. It is preferable to have sub-peaks or shoulders. By satisfying the above molecular weight distribution, development durability capable of developing a large number of sheets even with a small particle size toner, charging stability to the toner, and prevention of adhesion of external additives to the carrier particle surface are further improved. improves.

  Further, when the resin forming the coating material is a graft polymer, the weight average molecular weight of the trunk of the graft polymer is 15,000 to 200,000, and the weight average molecular weight of the branch is 3,000 to 10,000. 000 is preferred. The weight average molecular weight can be adjusted by the polymerization conditions of the trunk portion of the graft polymer and the polymerization conditions of the branch portion of the graft polymer.

  In the present invention, a resin having a graft polymer is preferably used as a coating material, and when the carrier core is coated with the coating material, the coating material is particularly excellent in resistance to peeling from the core surface, which is particularly preferable.

  In the present invention, a silicone resin can also be used as the coating material resin from the viewpoint of adhesion to the core and prevention of spent. The silicone resin can be used alone, but is preferably used in combination with a coupling agent in order to increase the strength of the coating layer and control the charge to a preferable level. Furthermore, the aforementioned coupling agent is preferably used as a so-called primer agent in which a part of the coupling agent is treated on the surface of the carrier core before coating the resin. By using a coupling agent as a primer agent, the coating layer can be formed in a more adhesive state with a covalent bond.

  Aminosilane is preferably used as the coupling agent. As a result, an amino group having positive chargeability can be introduced on the surface of the carrier, and the toner can be favorably imparted with negative charge characteristics. Furthermore, in the case of a magnetic substance-dispersed resin carrier, the presence of an amino group activates both the lipophilic treatment agent that is preferably treated with the metal compound and the silicone resin. By further enhancing the properties and at the same time promoting the curing of the resin, a stronger coating layer can be formed.

  During the coating treatment of the coating layer, it is preferable to coat in a reduced pressure state at a temperature of 30 to 80 ° C.

The reason is not clear, but is expected to be described below.
(I) A moderate reaction proceeds at the coating stage, and the coating material is uniformly and smoothly coated on the surface of the carrier core.
(Ii) In the baking step, low temperature treatment at 160 ° C. or lower is possible, and excessive crosslinking of the resin can be prevented and the durability of the coating layer can be enhanced.

  The coating amount of the resin forming the coating material on the carrier core is preferably 0.3 to 4.0 parts by mass with respect to 100 parts by mass of the carrier core. Preferably it is 0.4 to 3.5 mass parts, More preferably, it is 0.5 mass part to 3.2 mass parts.

  When the amount is within the above range, good toner releasability can be obtained, and image defects such as white spots are unlikely to occur. If the coating amount is less than 0.3 parts by mass, the surface of the carrier core cannot be sufficiently coated, and the effects of the present invention cannot be expressed. If the coating amount exceeds 4.0 parts by mass, it is uniform during coating. There is a case where the coating cannot be performed, and the charge up or the core surface is exposed to cause toner spent in the portion. In addition, the specific resistance of the magnetic carrier increases, and image defects such as white spots may occur.

  The coating resin preferably contains fine particles in order to make the shape of the carrier surface more uniform and / or sharpen the charge distribution of the toner.

  As the fine particles, both organic and inorganic fine particles can be used. However, it is necessary to maintain the shape of the particles when the carrier core is coated. Preferably, crosslinked resin particles or inorganic fine particles are preferably used. be able to. Specifically, a crosslinked polymethyl methacrylate resin, a crosslinked polystyrene resin, a melamine resin, a phenol resin, a nylon resin, and inorganic fine particles can be used alone or in combination from silica, titanium oxide, alumina, and the like. Among these, a crosslinked polymethyl methacrylate resin, a crosslinked polystyrene resin, and a melamine resin are preferable from the viewpoint of charge stability.

  These fine particles are preferably used in an amount of 1 to 40 parts by mass with respect to 100 parts by mass of the coating resin. By using it in the above range, charging stability and toner separation can be improved, and image defects such as white spots can be prevented. When the amount of the fine particles is less than 1 part by mass, the effect of addition of the fine particles cannot be obtained. When the amount exceeds 40 parts by mass, the coating layer is likely to be lost during durability, and the durability is poor.

  The particle diameter of the fine particles preferably has a peak value in the range of 0.08 to 0.70 μm (more preferably 0.10 to 0.50 μm) on the basis of the number in order to improve the toner separation. When the peak value is less than 0.08 μm, it is difficult to disperse the fine particles in the coating material. When the peak value exceeds 0.70 μm, the coating layer lacks during durability, resulting in poor durability.

  The coating resin preferably contains conductive fine particles so as not to reduce the specific resistance of the carrier excessively and to remove residual charges on the surface of the carrier.

As the conductive fine particles, those having a specific resistance of 1 × 10 ⁸ Ω · cm or less are preferable, and those having a specific resistance of 1 × 10 ⁶ Ω · cm or less are more preferable. Specifically, carbon black,
Particles containing at least one kind of particles selected from magnetite, graphite, titanium oxide, alumina, zinc oxide, and tin oxide are preferable. In particular, as a conductive particle, carbon black is preferably used without being able to remove residual charges on the carrier surface with a small addition amount, and having a small particle size and not inhibiting irregularities caused by fine particles on the carrier surface. be able to. The particle size of the carbon black has a peak value in the range of 10 to 60 nm (more preferably 15 to 50 nm) on the basis of the number so that residual charges on the carrier surface can be removed well and desorption from the carrier can be prevented. It is preferable for preventing it well.

Further, the DBP oil absorption amount of carbon black used as the conductive fine particles is preferably 20 to 500 ml, more preferably 25 to 300 ml, particularly preferably 30 to 200 ml, with respect to 100 g of carbon black.

  When the DBP oil absorption is in the above range, the residual charge on the carrier surface is efficiently removed, which is preferable for controlling the charging of the carrier. When the amount is less than 20 ml / 100 g, the structure of carbon black is short, so that efficient charge removal is not performed and the effect of addition is hardly exhibited.

  These conductive fine particles are preferably used in an amount of 1 to 15 parts by mass with respect to 100 parts by mass of the coating resin in order to reduce the specific resistance of the carrier and to remove residual charges on the carrier surface. When the amount is less than 1 part by mass, the effect of removing the residual charge on the carrier surface is hardly exhibited. When the amount exceeds 15 parts by mass, the dispersion in the coating material becomes unstable, and an excessive charge removing effect is obtained. Therefore, the charge imparting ability of the carrier itself may be reduced.

  The magnetic carrier that can be used in the present invention preferably has a number-based average particle diameter (D1) of 10 to 80 μm. Particles having an average particle size of less than 10 μm are likely to adhere to the carrier, and particles having an average particle size of more than 80 μm may not be able to be imparted with good charge due to a small specific surface area relative to the toner. In particular, in order to improve image quality and prevent carrier adhesion, the thickness is 15 to 60 μm, preferably 20 to 45 μm.

  The number average particle diameter of the magnetic carrier is measured as a carrier particle diameter by randomly extracting 300 or more carrier particles having a particle diameter of 0.1 μm or more with a scanning electron microscope (100 to 5000 times) and using a digitizer with a horizontal ferret diameter. The number average particle diameter of the carrier is calculated.

The magnetic carrier that can be used in the present invention has a magnetization intensity (σ1000) of 15 to 75 Am ² / kg (emu) measured under a magnetic field of (10 ³ / 4π) kA / m (1000 oersted).
/ G) and the residual magnetization (σr) is preferably 7.5 Am ² / kg or less. When the strength of magnetization (σ1000) exceeds 75 Am ² / kg, the stress on the toner in the developer magnetic brush increases, the toner deteriorates, and the spent on the carrier is likely to occur. . Further, when the magnetization intensity (σ1000) is less than 15 Am ² / kg, the magnetic binding force to the sleeve is lost, and the carrier adheres and adheres to the surface of the photoconductor to cause a defect in the image. Further, when the remanent magnetization (σr) exceeds 7.5 Am ² / kg, poor fluidity may occur due to magnetic aggregation.

  As a method for producing magnetic fine particle-dispersed resin core particles, there is a method in which a monomer of binder resin and magnetic fine particles are mixed and the monomer is polymerized to obtain magnetic fine particle-dispersed core particles. At this time, as monomers used for polymerization, vinyl monomers, bisphenols and epichlorohydrin for forming epoxy resins; phenols and aldehydes for forming phenol resins; urea and aldehydes for forming urea resins Melamine and aldehydes are used. For example, as a method of producing magnetic fine particle dispersed core particles using a curable phenolic resin, magnetic fine particles are placed in an aqueous medium, and phenols and aldehydes are polymerized in the presence of a basic catalyst in the aqueous medium. There is a method of obtaining fine particle dispersed resin core particles.

As another method for producing magnetic fine particle dispersed resin core particles, a vinyl or non-vinyl thermoplastic resin, a magnetic material, and other additives are thoroughly mixed by a mixer, and then heated rolls, kneaders, extensibles. There is a method in which a magnetic fine particle-dispersed core particle is obtained by melting and kneading using a kneader such as a ruder, cooling it, and then pulverizing and classifying it. At this time, it is preferable that the obtained magnetic fine particle dispersed core particles are thermally or mechanically spheroidized and used as magnetic fine particle dispersed core particles for the resin carrier. As the binder resin, a thermosetting resin such as a phenol resin, a melamine resin, or an epoxy resin is preferable in terms of excellent durability, impact resistance, and heat resistance. The binder resin is more preferably a phenol resin in order to more suitably express the characteristics of the present invention.

  As phenols for producing a phenol resin, in addition to phenol itself, alkylphenols such as m-cresol, p-tert-butylphenol, o-propylphenol, resorcinol, bisphenol A and a part of benzene nucleus or alkyl group or Examples thereof include compounds having a phenolic hydroxyl group such as halogenated phenols, all of which are substituted with chlorine atoms or bromine atoms. Of these, phenol (hydroxybenzene) is more preferable.

  Examples of aldehydes for producing a phenol resin include formaldehyde and furfural in the form of either formalin or paraaldehyde. Of these, formaldehyde is particularly preferable.

  The molar ratio of aldehydes to phenols is preferably 1 to 4, particularly preferably 1.2 to 3. If the molar ratio of aldehydes to phenols is less than 1, particles are difficult to produce, and even if they are produced, the resin is hard to progress, so the strength of the particles produced tends to be weak. On the other hand, when the molar ratio of aldehydes to phenols is larger than 4, unreacted aldehydes remaining in the aqueous medium after the reaction tend to increase.

  Examples of the basic catalyst used in the condensation polymerization of phenols and aldehydes include those used in the production of ordinary resol type resins. Examples of such a basic catalyst include aqueous ammonia, hexamethylenetetramine and alkylamines such as dimethylamine, diethyltriamine, and polyethyleneimine. The molar ratio of these basic catalysts to phenols is preferably 0.02 to 0.3.

  Next, the toner used in the present invention will be described in detail.

  First, the binder resin that can be used in the present invention will be described.

  As the binder resin that can be used in the present invention, known resins can be used, but (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, (c) ) A mixture of a hybrid resin and a vinyl copolymer, (d) a mixture of a polyester resin and a vinyl copolymer, (e) a mixture of a hybrid resin and a polyester resin, and (f) a polyester resin and a hybrid resin. It is a resin selected from a mixture with a vinyl copolymer.

  When a polyester resin is used as the binder resin, a polyhydric alcohol, a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or the like can be used as a raw material monomer. The same applies to the monomers used for producing the polyester unit in the hybrid resin.

Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

  The divalent acid component includes aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides; Succinic acid substituted with 6 to 12 alkyl groups or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof.

  Examples of the trivalent or higher polyvalent carboxylic acid component for forming a polyester resin having a crosslinking site include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2 , 4-Naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof.

  Among them, in particular, a bisphenol derivative represented by the following general formula (e) is used as a diol component, and a carboxylic acid component (for example, fumaric acid) composed of a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof. A polyester resin obtained by polycondensation using acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component is preferable because it has good charging characteristics as a color toner. .

In the binder resin contained in the toner that can be used in the present invention, the “hybrid resin” means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, it is a resin formed by a transesterification reaction between a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester, preferably a vinyl polymer. A graft copolymer (or block copolymer) having a trunk polymer and a polyester unit as a branch polymer. In the present invention, “polyester unit” refers to a portion derived from polyester, and “vinyl polymer unit” refers to a portion derived from a vinyl polymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component, and the vinyl polymer unit is a monomer component having a vinyl group.

  Examples of vinyl monomers for producing vinyl copolymers or vinyl polymer units include styrene; o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-phenyl styrene, p. -Ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn- Styrene such as decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene and derivatives thereof; ethylene , Unsaturated monoolefins such as propylene, butylene, isobutylene; butadiene, Unsaturated polyenes such as soprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, methacrylic acid Ethyl, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid Α-methylene aliphatic monocarboxylic esters such as diethylaminoethyl; methyl acrylate, ethyl acrylate, propyl acrylate, -n-butyl acrylate, isobutyl acrylate, -n-octyl acrylate, Acrylic esters such as dodecyl crylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl Vinyl ketones such as ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; Vinyl naphthalenes; Acrylonitrile, methacrylonitrile And acrylic acid or methacrylic acid derivatives such as acrylamide.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

In the toner that can be used in the present invention, the vinyl copolymer or vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate and 1,3-butylene glycol. Examples include diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylate. The diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, poly Examples include tylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylates; diacrylates linked by a chain containing an aromatic group and an ether bond. Examples of the compounds include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and the like The thing which replaced the acrylate of the compound of this with the methacrylate is mentioned.

  Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples include nurate and triallyl trimellitate.

  When producing the hybrid resin, it is preferable that a monomer component capable of reacting with the components of both resin units is contained in one or both of the vinyl polymer unit and the polyester unit. Examples of monomers that can react with the components of the vinyl polymer unit among the monomers constituting the polyester resin unit include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. It is done. Among the monomers constituting the vinyl polymer unit, those capable of reacting with the components of the polyester unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method of obtaining a reaction product of a vinyl polymer unit and a polyester unit, there is a polymer containing a monomer component capable of reacting with each of the vinyl polymer unit and the polyester unit listed above. A method obtained by carrying out the polymerization reaction of one or both resins is preferred.

Examples of the polymerization initiator used for producing the vinyl copolymer or vinyl polymer unit usable in the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis ( 4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2 '-Azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetyl Ketone peroxides such as seton peroxide and cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethyl Butyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide Decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl Ruperoxy dicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetyl Cyclohexylsulfonyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate T-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, -t- butyl peroxy hexahydro terephthalate, di -t- butyl peroxy azelate and the like.

  Examples of the production method for preparing the hybrid resin used in the toner that can be used in the present invention include the production methods shown in the following (1) to (5).

  (1) After separately producing a vinyl polymer and a polyester resin, dissolve and swell in a small amount of an organic solvent, add an esterification catalyst and an alcohol, and heat to synthesize a hybrid resin. Method.

  (2) A method for producing a polyester unit and a hybrid resin component in the presence of a vinyl polymer after the production thereof. The hybrid resin component is added as necessary to the reaction of a vinyl polymer unit (a vinyl monomer can be added if necessary) and a polyester monomer (polyhydric alcohol, polycarboxylic acid), and the unit and monomer as necessary. Produced by reaction with polyester. Also in this case, an organic solvent can be appropriately used.

  (3) A method for producing a vinyl polymer unit and a hybrid resin component in the presence of a polyester resin after the production. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer, and a reaction between the unit and the monomer and a vinyl polymer unit added as necessary. . Also in this case, an organic solvent can be appropriately used.

  (4) After the vinyl polymer and the polyester resin are produced, either or both of a vinyl monomer and a polyester monomer (polyhydric alcohol, polycarboxylic acid) are added in the presence of these polymer units, and the added monomer. The hybrid resin component can be produced by carrying out a polymerization reaction under conditions according to the conditions. Also in this case, an organic solvent can be appropriately used.

  (5) By mixing a vinyl monomer and a polyester monomer (polyhydric alcohol, polycarboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction, a vinyl polymer unit, a polyester unit, and a hybrid resin component are obtained. Manufactured. Furthermore, an organic solvent can be used as appropriate.

  In the production methods (1) to (5), a plurality of polymer units having different molecular weights and different degrees of crosslinking can be used for the vinyl polymer unit and the polyester unit.

  The vinyl polymer or vinyl polymer unit in the present invention means a vinyl homopolymer or vinyl copolymer, a vinyl monopolymer unit or a vinyl copolymer unit.

  Furthermore, the molecular weight distribution measured by gel permeation chromatography (GPC) of a resin having a polyester unit that can be used in the present invention has a main peak in the region of molecular weight 3,500 to 15,000, Preferably, it has a molecular weight of 4,000 to 13,000, and Mw / Mn is preferably 3.0 or more, more preferably 5.0 or more. When the main peak is in a region having a molecular weight of less than 3,500, the high temperature offset resistance of the toner decreases. On the other hand, when the main peak is in a region having a molecular weight of more than 15000, sufficient low-temperature fixability of the toner and OHP permeability are deteriorated. Moreover, when Mw / Mn is less than 3.0, good offset resistance is reduced.

  The toner that can be used in the present invention preferably contains a wax as a release agent from the viewpoint of improving the fixability.

  Examples of the wax that can be used in the present invention include the following. Oxides of aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or the like Block copolymers of these: waxes mainly composed of fatty acid esters such as carnauba wax, behenyl behenate, and montanic acid ester wax, and those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax Is mentioned. In addition, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, Esters of alcohols such as merisyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid Saturated fatty acid bisamides such as amide, ethylenebislauric acid amide and hexamethylene bisstearic acid amide; Unsaturated fatty acid amides such as sebacic acid amides; Aromatic bisamides such as m-xylene bisstearic acid amide and N, N ′ distearyl isophthalic acid amides; Calcium stearate, calcium laurate, zinc stearate, magnesium stearate, etc. Aliphatic metal salts (generally referred to as metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides and many others Price Lumpur partial ester; methyl ester compounds having hydroxyl groups obtained by and hydrogenated vegetable oils and the like.

Examples of the wax that can be particularly preferably used in the present invention include aliphatic hydrocarbon waxes and esterified products that are esters of fatty acids and alcohols. For example, low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure with Ziegler catalyst or metallocene catalyst under low pressure; alkylene polymer obtained by thermally decomposing high molecular weight alkylene polymer; synthesis containing carbon monoxide and hydrogen A synthetic hydrocarbon wax obtained from the distillation residue of hydrocarbons obtained from the gas by the age method or by hydrogenating them is preferred. Furthermore, what carried out the fractionation of the hydrocarbon wax by the use of the press perspiration method, the solvent method, the vacuum distillation, or the fractional crystallization method is more preferably used. The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems) [for example, the Jintol method, the Hydrocol method (the fluidized catalyst bed Hydrocarbon compounds synthesized by use); hydrocarbons with up to several hundred carbon atoms obtained by the age method (using the identified catalyst bed) from which a large amount of wax-like hydrocarbons can be obtained; alkylene such as ethylene by Ziegler catalyst Polymerized hydrocarbons are preferred because they are linear hydrocarbons with little branching, small and long saturation. In particular, a wax synthesized by a method that does not rely on polymerization of alkylene is also preferred from its molecular weight distribution. Paraffin wax is also preferably used.

  The wax that can be used in the present invention preferably has a peak temperature of the maximum endothermic peak in the range of 30 to 200 ° C. in the endothermic curve in differential scanning calorimetry (DSC). . More preferably, it is in the range of 65 to 125 ° C, and particularly preferably in the range of 65 to 110 ° C.

  When the maximum endothermic peak temperature of the wax is in the range of 60 to 130 ° C., moderate fine dispersibility in the toner particles can be achieved, which is preferable in order to exhibit the effects of the present invention. On the other hand, when the maximum endothermic peak is less than 60 ° C., the blocking resistance of the toner deteriorates. Conversely, when the maximum endothermic peak exceeds 130 ° C., the fixability tends to deteriorate.

  As the colorant used in the toner that can be used in the present invention, known dyes and / or pigments are used. Although the pigment alone may be used, it is more preferable from the viewpoint of the image quality of the full-color image that the combination of the dye and the pigment improves the sharpness.

  Examples of the color pigment for magenta toner include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, and thioindigo compounds. Specifically, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 254, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the magenta toner dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28 may be mentioned.

  Examples of the color pigment for cyan toner include C.I. I. Pigment Blue 1, 2, 3, 7, 15: 2, 15: 3, 15: 4, 16, 17, 60, 62, 66; I. Bat Blue 6, C.I. I. Examples include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula (f).

  Examples of the colored pigment for yellow include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal compounds, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 155, 168, 174, 180, 181, 185, 191, C.I. I. Bat yellow 1, 3, 20 and the like. In addition, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6 and Solvent Yellow 162 can also be used.

  As the black colorant that can be used in the present invention, carbon black, iron oxide particles, and those that are toned in black using the yellow / magenta / cyan colorant shown above can be used.

  In addition, in the toner that can be used in the present invention, it is preferable to use a toner obtained by mixing a colorant in advance with the binder resin of the present invention into a master batch. Then, the colorant can be favorably dispersed in the toner by melt-kneading the colorant master batch and other raw materials (binder resin, wax, etc.).

  When a masterbatch is formed using a resin and a colorant that can be used in the present invention, the dispersibility of the colorant does not deteriorate even when a large amount of the colorant is used, and the colorant is dispersed in the toner particles. And the color reproducibility such as color mixing and transparency when fixing a plurality of color toners to form an image is excellent. Further, a toner having a large covering power on the transfer material can be obtained by making a master batch. Further, by improving the dispersibility of the colorant by making the master batch, it is possible to obtain an image having excellent durability and stability of toner chargeability and maintaining high image quality.

  The amount of the colorant used in the toner is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 12 parts by mass, and most preferably 2 to 10 parts by mass with respect to 100 parts by mass of the binder resin. This is preferable in terms of color reproducibility and developability.

A known charge control agent can be used for the toner that can be used in the present invention in order to stabilize the chargeability. The charge control agent varies depending on the type of charge control agent and the physical properties of other toner particle constituent materials, but generally 0.1 to 10 parts by mass per 100 parts by mass of the binder resin is preferably contained in the toner particles. More preferably, 0.1 to 5 parts by mass are contained. As such a charge control agent, there are known one that controls the toner to be negatively charged and one that controls the toner to be positively charged. One or two kinds of various kinds of charge control agents are used depending on the kind and use of the toner. The above can be used.

  Negatively chargeable charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, calixarene Etc. are available. As the positively chargeable charge control agent, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, an imidazole compound, or the like can be used. The charge control agent may be added internally or externally to the toner particles.

  In particular, the color toner that can be used in the present invention is preferably an aromatic carboxylic acid metal compound that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount.

  The toner that can be used in the present invention is preferably used after adjusting the fluidity of the toner by mixing inorganic fine particles with a mixer such as a Henschel mixer after pulverization and classification or after surface modification.

  The inorganic fine particles that can be used in the present invention have an aspect ratio (major axis / minor axis) in the range of 1.0 to 1.5 on the toner particle surface, and a number average particle diameter of 0.06 to 0.30 μm. It is preferable that

  When the aspect ratio of the inorganic fine particles is within the above range, the fluidity of the toner after the addition of the inorganic fine particles is easily improved, and the fluidity of the toner can be easily controlled by the addition amount of the inorganic fine particles. When the aspect ratio of the inorganic fine particles is larger than 1.5, the adhesion to the surface of the toner particles is also lowered, and it becomes difficult to control the fluidity of the toner by the addition amount of the inorganic fine particles.

  Further, since the number average particle diameter of the inorganic fine particles is in the range of 0.06 to 0.30 μm, the spacer effect between the toner and the toner of the inorganic fine particles is more exerted, so that the fluidity of the toner is easily improved. . When the number average particle diameter of the inorganic fine particles is smaller than 0.06 μm, it is difficult to obtain the spacer effect, and a large amount of addition is required, which may lead to deterioration of developability and fixability. On the other hand, when the number average particle diameter of the inorganic fine particles is larger than 0.30 μm, the adhesion to the toner particle surface is lowered and the spacer effect is hardly obtained.

  Examples of inorganic fine particles having such a shape and particle size include fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, titanium oxide fine powder, alumina fine powder, wet process silica, and dry process silica. Examples thereof include finely-powdered silica, and treated silica obtained by subjecting them to surface treatment with a silane compound, an organosilicon compound, a titanium coupling agent, silicone oil, and the like.

  In the present invention, wet-process silica is particularly preferred. As a wet process silica, in particular, a sol-gel method in which a solvent is removed from a silica sol suspension obtained by hydrolysis and condensation reaction with a catalyst in an organic solvent in which water is present, and then dried to form particles. There are silica particles that are produced. The silica particles produced by the sol-gel method have a sharp particle size distribution of the obtained particles, and approximately spherical particles can be obtained, and particles having a desired particle size distribution can be obtained by changing the reaction time. It is particularly preferably used in the invention.

Moreover, a dry process silica can also be used suitably. Dry process silica is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is called so-called dry process silica or fumed silica, and is manufactured by a conventionally known technique. For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

  In this production process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. .

  In addition, as the titanium oxide fine powder, sulfuric acid method, chlorine method or volatile titanium compound (for example, titanium oxide fine particles obtained by low-temperature oxidation (thermal decomposition, hydrolysis) of titanium alkoxide, titanium halide, titanium acetylacetonate). Can be used. As the crystal system, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.

  And as alumina fine powder, buyer method, improved buyer method, ethylene chlorohydrin method, underwater spark discharge method, organoaluminum hydrolysis method, aluminum alum pyrolysis method, ammonium aluminum carbonate pyrolysis method or flame decomposition of aluminum chloride Alumina fine powder obtained by the method can be used. As the crystal system, α, β, γ, δ, ξ, η, θ, κ, χ, ρ type, mixed crystal type or amorphous can be used, and α, δ, γ, θ, mixed type can be used. Crystalline or amorphous materials are preferably used.

  As a method for hydrophobizing the inorganic fine powder, it is applied by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with the inorganic fine powder.

  As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound. Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane. , Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyl Dimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si at each terminal unit. These are used alone or in a mixture of two or more.

  As inorganic fine particles that can be used in the present invention, the above-described wet process silica or dry process silica treated with a coupling agent having an amino group or silicone oil is used as necessary to achieve the object of the present invention. It doesn't matter. The added amount is 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass of inorganic fine particles with respect to 100 parts by mass of the toner.

  Next, a procedure for manufacturing toner will be described.

  The toner that can be used in the present invention is obtained by melt-kneading a binder resin, a colorant, wax, and an arbitrary material, cooling and pulverizing, and performing spheroidizing treatment and classification treatment of the pulverized product as necessary, It is particularly preferable to produce the mixture by mixing the inorganic fine particles as necessary.

First, in the raw material mixing step, as a toner internal additive, at least a resin and a colorant are weighed and mixed in a predetermined amount and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.

  Further, the toner raw materials blended and mixed as described above are melt-kneaded to melt the resins, and the colorant and the like are dispersed therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. A twin screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, etc. are generally used. Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.

  In general, the cooled colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed with a crusher, a hammer mill, a feather mill or the like, and further, pulverization is performed with a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nisshin Engineering Co., Ltd. or the like. Then, if necessary, classification is performed using a classifier such as an inertia classification type elbow jet (manufactured by Nippon Steel Mining Co., Ltd.) or a centrifugal classification type turboplex (manufactured by Hosokawa Micron Co., Ltd.) to obtain a classified product. .

  In the present invention, the surface modification apparatus shown in FIG. 4 that can perform classification and surface modification treatment at the same time is preferably used.

  The surface modification apparatus shown in FIG. 4 includes a casing 55, a jacket (not shown) through which cooling water or antifreeze liquid can be passed, a classification rotor 41 that is a classification means for separating fine particles having a predetermined particle size or less, and a machine for separating particles. A dispersion rotor 46, which is a surface treatment means for treating the surface of the particles with a specific impact, a liner 44 provided around the outer periphery of the dispersion rotor 46 with a predetermined interval, and a classification rotor 41. Among the divided particles, fine particles having a predetermined particle size or less among the particles divided by the guide ring 49 and the classification rotor 41 that guide the particles including the predetermined particle size to the dispersion rotor 46 of the apparatus. A fine powder collecting discharge port 42 which is a discharge means for discharging outside, a cold air introduction port 45 which is a particle circulation means for sending particles whose surface is processed by the dispersion rotor 46 to the classification rotor 41, It has a raw material supply port 43 for introducing the particles into the casing 55 within a closable powder outlet 47 and the discharge valve 48 for discharging the treated surface particles from the casing 55 inside.

  The classification rotor 41 is a cylindrical rotor and is provided at one upper end portion in the casing 55. The fine powder collection outlet 42 is provided at one end of the casing 55 so as to discharge particles inside the classification rotor 41. The raw material supply port 43 is provided at the center of the peripheral surface of the casing 55. The cold air inlet 45 is provided on the other end surface side of the peripheral surface of the casing 55. The powder discharge port 47 is provided at a position facing the raw material supply port 43 on the peripheral surface of the casing 55. The discharge valve 48 is a valve that freely opens and closes the powder discharge port 47.

A dispersion rotor 46 and a liner 44 are provided between the cold air introduction port 45 and the raw material supply port 43 and the powder discharge port 47. The liner 44 is provided along the inner peripheral surface of the casing 55. As shown in FIG. 5, the dispersion rotor 46 includes a disk and a plurality of square disks 50 arranged along the normal line of the disk at the periphery of the disk. The dispersion rotor 46 is provided on the lower upper surface of the casing 55, and is provided at a position where a predetermined interval is formed between the liner 44 and the square disk 50. A guide ring 49 is provided at the center of the casing 55. The guide ring 49 is a cylindrical body, and is provided so as to extend from a position covering a part of the outer peripheral surface of the classification rotor 41 to the vicinity of the dispersion rotor 46. The guide ring 49 includes a first space 51 that is a space between the outer peripheral surface of the guide ring 49 and an inner peripheral surface of the casing 55 in the casing 55, and a second space that is a space inside the guide ring 49. A space 52 is formed.

  The dispersion rotor 46 may have a cylindrical pin instead of the square disk 50. In the present embodiment, the liner 44 is provided with a large number of grooves on the surface facing the rectangular disk 50, but may have no grooves on the surface. Further, the installation direction of the classification rotor 41 may be a vertical type as shown in FIG. 4 or a horizontal type. Further, the number of classification rotors 41 may be single as shown in FIG. 4 or plural.

  Further, if necessary, surface modification and spheronization may be further performed using, for example, a hybridization system manufactured by Nara Machinery Co., Ltd. or a mechano-fusion system manufactured by Hosokawa Micron. In such a case, if necessary, a sieving machine such as a wind-type sieve high voltor (manufactured by Shin Tokyo Machine Co., Ltd.) may be used. Furthermore, as a method of externally adding the external additive, a predetermined amount of classified toner and various known external additives are blended, and a high-speed stirrer that gives a shearing force to the powder such as a Henschel mixer or a super mixer is removed. A method of stirring and mixing can be used as an accessory.

  Other methods for producing a toner usable in the present invention include a method of directly producing toner particles using a suspension polymerization method, and an aqueous system that is soluble in the monomer and insoluble in the obtained polymer. Toner particles are produced using an emulsion polymerization method represented by a dispersion polymerization method in which toner particles are directly generated using an organic solvent, or a soap-free polymerization method in which toner particles are generated by direct polymerization in the presence of a water-soluble polar polymerization initiator. Methods and the like. In addition, a production method such as an interfacial polymerization method such as a microcapsule production method, an in situ polymerization method, or a coacervation method can also be used.

  When toner particles are produced using the suspension polymerization method, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, Azo polymerization initiators such as 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide Peroxide-based polymerization initiators such as methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide are used.

  Although the addition amount of a polymerization initiator changes with the target degree of polymerization, generally 0.5-20 mass% is added and used with respect to a monomer. The kind of the polymerization initiator varies slightly depending on the polymerization method, but can be used alone or in combination with reference to the 10-hour half-life temperature. A known crosslinking agent, chain transfer agent, polymerization inhibitor and the like for controlling the degree of polymerization can be further added and used.

  When suspension polymerization is used as a toner production method, an inorganic oxide can be used as a dispersant. Inorganic oxides include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, sulfuric acid Examples include barium, bentonite, silica, and alumina. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. These are used by being dispersed in an aqueous phase. These dispersants are preferably used in an amount of 0.2 to 10.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

As these dispersants, commercially available ones may be used as they are, but in order to obtain dispersed particles having a fine uniform particle size, the inorganic oxide can also be produced in a dispersion medium under high-speed stirring. . For example, in the case of tricalcium phosphate, a preferred dispersant for the suspension polymerization method can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution under high-speed stirring. Moreover, you may use together 0.001-0.1 mass part surfactant for refinement | miniaturization of these dispersing agents. Specifically, commercially available nonionic, anionic or cationic surfactants can be used, for example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pendadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate. Calcium oleate is preferably used.

  When a direct polymerization method is used as a toner production method, the toner can be produced specifically by the following production method. Monomer composition in which a release agent, a colorant, a charge control agent, a polymerization initiator and other additives composed of a low softening substance are added to the monomer and dissolved or dispersed uniformly by a homogenizer, ultrasonic disperser, etc. The product is dispersed in an aqueous phase containing a dispersion stabilizer by a usual stirrer, homomixer, homogenizer or the like. Preferably, the droplets composed of the monomer composition are granulated by adjusting the stirring speed and time so as to obtain a desired toner particle size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. Polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. The temperature may be raised in the latter half of the polymerization reaction, and for the purpose of improving the durability, a part of the aqueous medium is retained after the latter half of the reaction or after the completion of the reaction in order to remove unreacted polymerizable monomers and byproducts. You may leave. After completion of the reaction, the produced toner particles are recovered by washing and filtration and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer composition.

  Next, the wettability of the toner that can be used in the present invention to a 45% aqueous methanol solution will be described in detail.

  As the wettability of the toner that can be used in the present invention, it is preferable that the transmittance is 10 to 80% in the measurement of UV transmittance in a 45% by volume aqueous solution of methanol. By being in this range, it becomes easy to obtain the compressibility and shear stress of the developer of the present invention.

  When the transmittance is less than 10%, the fluidity as a toner is deteriorated, so that the shear stress of the developer tends to increase, and the stress on the developer may increase.

  If the transmittance is greater than 80%, the fluidity of the toner is too good, and the degree of compression of the developer tends to be small, and uneven coating on the developing sleeve and scattering of the developer are likely to occur. is there.

  Therefore, the wettability of the toner is preferably within the above range. However, in the present invention, this range can be achieved by changing the particle size and aspect ratio of the external additive.

  Next, the shape of the toner that can be used in the present invention will be described in detail.

  As the shape of the toner that can be used in the present invention, the average circularity measured by FPIA2100 (manufactured by Sysmex Corporation) is preferably 0.920 to 0.970.

  When the average circularity is smaller than 0.920, the fluidity as a toner is deteriorated, so that the shear stress of the developer tends to increase, and the stress on the developer may increase.

If the average circularity is greater than 0.970, the fluidity of the toner is too good.
There is a tendency that the degree of compression of the developer tends to be small, and uneven coating on the developing sleeve and scattering of the developer are likely to occur.

Therefore, the shape of the toner is preferably within the above range, but in the present invention, this range can be achieved by adjusting the pulverization condition and surface treatment modification condition of the toner.
The average particle diameter of the toner is preferably a weight average particle diameter (D4) of 4.0 to 10 μm. When the average particle size is less than 4.0 μm, developer scattering tends to occur. If the average particle size is larger than 10 μm, dot reproducibility during development deteriorates, and it may be difficult to obtain a high-quality image. The average particle diameter of the toner is preferably in the above range, but in the present invention, this range can be achieved by adjusting the pulverization conditions and surface treatment modification conditions of the toner.

  The physical property analysis / measurement method according to the present invention will be described below.

<Measurement of developer compressibility>
First, a loose apparent density A (g / cm ³ ) was measured using a powder tester PT-R (manufactured by Hosokawa Micron Corporation). The measurement environment was 23 ° C. and 50% RH. In the measurement, the developer was collected in a metal cup having a volume of 100 ml using a sieve having an opening of 75 μm and vibrating at an amplitude of 1 mm until it reached 100 ml. The loose apparent density A (g / cm ³ ) was calculated from the developer amount collected in the metal cup.

Next, the apparent apparent density P (g / cm ³ ) was measured. Using a sieve with an opening of 75 μm, the developer is vibrated with an amplitude of 1 mm, and the developer is replenished until it reaches 100 ml, and the metallic cup is tapped 180 times up and down at an amplitude of 18 mm, and after tapping The apparent apparent density P (g / cm ³ ) was calculated from the developer amount.

And the compression degree C was calculated | required by following formula (1).
Compression degree C (%) = 100 × (PA) / P (1)

<Measurement of developer shear stress>
The shear stress of the developer was measured using a powder bed tester PTHN-13BA type (manufactured by Sankyo Piotech Co., Ltd.). The measurement environment was 23 ° C. and 50% RH. For the measurement, a parallel plate type shear strength measurement cell was used. First, a powder layer of a developer was formed on a fixed plate, a movable plate (W50 mm × D70 mm × H4 mm) was horizontally placed on the powder, and a preconsolidation load was applied from the movable plate. The preconsolidation load was performed for 5 minutes under 1.3 × 10 ⁻² N / mm ² . Then, shear strength measurement was performed in a state where a vertical load was applied on the movable plate so that the consolidation load on the powder layer was 4.0 × 10 ⁻⁴ N / mm ^2, and this was repeated six times. The average value was taken as the shear stress of the developer.

<Molecular weight distribution of binder resin, toner, and coating resin by GPC measurement>
The molecular weight of the chromatogram by gel permeation chromatography (GPC) is measured under the following conditions. For the measurement, HLC-8120GPC (manufactured by Tosoh Corporation) was used.

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. About 50 to 200 μl of THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts (retention time). Examples of standard polystyrene samples for preparing a calibration curve include those manufactured by Tosoh Corporation or Pressure Chemical Co. The molecular weights manufactured are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8 .6
It is appropriate to use × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As a column, in order to accurately measure a molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, shodex GPC KF-801, 802, 803 manufactured by Showa Denko KK , 804, 805, 806, and 807, and combinations of μ-styragel 500, 10 ³ , 10 ⁴ , and 10 ⁵ manufactured by Waters.

<Measurement of maximum endothermic peak in DSC of toner and wax>
The maximum endothermic peak of toner and wax can be measured according to ASTM D3418-82 using a differential thermal analyzer (DSC measuring device) and DSC2920 (TA Instruments Japan).
Temperature curve: Temperature increase I (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (200 ° C-30 ° C, temperature drop rate 10 ° C / min)
Temperature increase II (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)

  As a measuring method, 5 to 20 mg, preferably 10 mg of a measurement sample is accurately weighed. This is put into an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min and normal temperature and humidity in a measurement temperature range of 30 to 200 ° C. The maximum endothermic peak of the toner is determined in the process of temperature increase II, the one having the highest height from the baseline in the region above the endothermic peak of the resin Tg, or the endothermic peak of the resin Tg overlaps with another endothermic peak. If this is difficult, the maximum endothermic peak of the toner of the present invention is defined as the highest peak from the maximum peak of the overlapping peaks.

<Measurement of toner particle size distribution>
As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Inc.) is used. As the electrolytic solution, an about 1% NaCl aqueous solution is used. As the electrolytic solution, an electrolytic solution prepared using primary sodium chloride or, for example, ISOTON (registered trademark) -II (manufactured by Coulter Scientific Japan) can be used.

  As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzenesulfone hydrochloride) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of the sample are measured for each channel by the measuring apparatus using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From these obtained distributions, the weight average particle diameter (D4) of the sample is determined. As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00-40.30 μm are used.

<Measurement of average circularity of toner>
The average circularity of the toner is measured using a flow type particle image measuring device “FPIA-2100 type” (manufactured by Sysmex Corporation), and is calculated using the following equation.

  Here, “particle projection area” is the area of the binarized particle image, and “perimeter of the particle projection image” is defined as the length of the contour line obtained by connecting the edge points of the particle image. . The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm).

  In the present invention, the circularity is an index indicating the degree of unevenness of the particles, and is 1.000 when the particles are perfectly spherical. The more complicated the surface shape, the smaller the circularity.

  The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of measured particles.

  In addition, “FPIA-2100”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity. 1.00 is divided into classes equally divided every 0.01, and the average circularity is calculated using the center value of the division points and the number of measured particles.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, and then further measurement is performed. Add 0.02 g of sample (toner) and disperse uniformly. As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the temperature inside the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocus is performed using 2 μm latex particles every 2 hours.

  For the measurement of the circularity of the toner, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 / μl, and 1000 or more toners are added. measure. After the measurement, using this data, data having an equivalent circle diameter of less than 2 μm is cut to determine the average circularity of the toner particles.

Furthermore, “FPIA-2100”, which is a measuring apparatus used in the present invention, improves the magnification of the processed particle image as compared with “FPIA-1000” conventionally used for calculating the shape of the toner. Furthermore, the processing resolution of the captured image is improved (256 × 256 → 512 ×
512) improves the accuracy of toner shape measurement, thereby achieving more reliable capture of fine particles. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA-2100 that can obtain information on the shape more accurately is more useful.

<Measurement of UV transmittance in 45% by volume of methanol in toner>
-Preparation of toner dispersion First, an aqueous solution having a volume mixing ratio of methanol: water of 45:55 is prepared. 10 ml of this aqueous solution is placed in a 30 ml sample bottle (Nippon Denka Glass: SV-30), and 20 mg of toner is impregnated on the liquid surface to cover the bottle. Thereafter, the mixture is shaken for 10 seconds at 2.5 S ⁻¹ with a Yayoi type shaker (model: YS-LD). At this time, the angle of shaking is such that the shaking column moves 15 degrees forward and 20 degrees backward, assuming that the vertical (vertical) of the shaker is 0 degree. The sample bottle is fixed to a fixing holder (with the sample bottle lid fixed on the extension at the center of the column) attached to the tip of the column. After removing the sample bottle, the dispersion after 30 seconds is used as a dispersion for measurement.

-Measurement of transmittance The dispersion is put into a 1 cm square quartz cell, and the transmittance (%) at a wavelength of 600 nm of the dispersion after 10 minutes is measured using a spectrophotometer MPS2000 (manufactured by Shimadzu Corporation).
Transmittance (%) = I / I ₀ × 100 (I ₀ : incident light beam, I: transmitted light beam)

<Analysis of composition of resin for carrier coating>
About 50 mg of a sample is put in a sample tube having a diameter of 5 mm, and CDCl ₃ is added as a solvent to dissolve it to obtain a measurement sample. The measurement conditions are shown below.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 6.9 μs
Data points: 32768
Frequency range: 10500Hz
Integration count: 16 times Measurement temperature: 25 ° C

  Further, the carrier coating resin may be separated from the carrier particles as necessary. As a method for separating the coating material from the carrier particles, a solvent soluble in the coating material (for example, acetone, toluene, etc.) is used, ultrasonic separation is performed with an ultrasonic disperser, and then the core particles are separated using a magnet. I do. Thereafter, using a centrifugal separator, the fine particles added to the coating material are separated, and the supernatant liquid (resin solution component) is separated and evaporated to dryness to obtain a resin component for carrier coating.

<Measurement of resistivity of magnetic carrier>
The specific resistance value of the magnetic carrier is measured using the measuring apparatus shown in FIG. If necessary, the sample is prepared by separating the toner and the magnetic carrier.

The specific resistance is measured by filling the cell E with sample particles 67, placing a lower electrode 61 and an upper electrode 62 in contact with the filled sample particles, and applying a voltage between these electrodes by a constant voltage device 66. Then, a method is used in which the specific resistance is obtained by measuring the current flowing at that time with an ammeter 64. The measurement conditions of the specific resistance in the present invention are as follows: the contact area S between the filled sample particles and the electrode is about 2.4 cm ² , the sample thickness d is about 0.2 cm, and the load of the upper electrode is 240 g. The voltage is applied in the order of application conditions I, II, and III, and the current at the applied voltage in application condition III is measured. Thereafter, the thickness d of the sample was accurately measured, the specific resistance (Ω · cm) at each electric field strength (V / cm) was obtained by calculation, and the specific resistance at the electric field strength of 3000 V / cm was taken as the specific resistance of the sample. . In addition, 63 shows an insulator, 65 shows a voltmeter, 68 shows a guide ring, E shows a resistance measurement cell.
Application condition I: (0V → 1000V: Increase in steps of 200V every 30 seconds)
II: (Hold for 30 seconds at 1000V)
III: (1000V → 0V: Decrease in steps of 200V every 30 seconds)
Sample resistivity (Ω · cm) =
(Applied voltage (V) / measured current (A)) × S (cm ² ) / d (cm)
Electric field strength (V / cm) = applied voltage (V) / d (cm)

<Measurement of particle size of magnetic fine particles, nonmagnetic inorganic compounds, etc. in carrier core>
Regarding the particle size of the magnetic fine particles, a cross section obtained by cutting the carrier with a microtome or the like is observed with a scanning electron microscope (50,000 times), and 500 or more particles having a particle size of 5 nm or more are randomly extracted from the microscope image. The major and minor axes of the extracted particles are measured with a digitizer, and the average is used as the particle size. The particle size distribution of 500 or more particles (column width is 5-15, 15-25, 25-35, 35 -45, 45-55, 55-65, 65-75, 75-85, 85-95 (unit: nm), etc. (the column histogram divided every 10 nm is used). The maximum peak particle size is calculated with the median particle size of. In addition, as a method for measuring the particle size of the magnetic substance or nonmagnetic inorganic compound, the maximum peak particle size is determined in the same manner as the above method from a 50,000 times photograph obtained by a transmission electron microscope (TEM) of the raw material. You can ask for it.
<Measurement of particle size of fine particles in carrier coating resin>
The particle size of the fine particles is 500 or more random particles having a particle size of 5 nm or more by scanning electron microscope (50,000 times) obtained by dissolving a coating material from a carrier in a solvent such as toluene. Extract and measure the major and minor axes with a digitizer. The average is the particle size, with the mode diameter that becomes the peak of the particle size distribution of 500 or more particles (from the column histogram separated every 10 nm). The average particle size is calculated.

<Measurement of particle size of carbon black in carrier coating resin>
The particle size of the carbon black was determined by randomly scanning 500 particles having a particle size of 5 nm or more with a scanning electron microscope (50,000 times) by dissolving a coating material from a carrier in a solvent such as toluene. Extract the above, measure the major and minor axes with a digitizer, and use the average value as the particle size, and the mode diameter that becomes the peak of the particle size distribution of 500 or more particles (from the histogram of the column separated every 10 nm) To calculate the average particle size.

<Measurement of DBP oil absorption of carbon black in resin for carrier coating>
The DBP oil absorption of carbon black is JIS-K 6221-1982 6.1.2.
It is calculated from the DBP oil absorption (dibutyl phthalate oil absorption) by the A method (mechanical kneading method).

<Measurement of magnetization strength of magnetic carrier and magnetic fine particles>
The magnetization strength of the magnetic carrier is determined from the magnetic properties of the magnetic carrier and the true density of the magnetic carrier. The magnetic characteristics of the magnetic carrier can be measured by using an oscillating magnetic field type magnetic characteristic automatic recording apparatus BHV-30 manufactured by Riken Denshi Co., Ltd. As a measuring method, a cylindrical plastic container is filled with a magnetic carrier so as to be sufficiently dense, while an external magnetic field of (10 ³ / 4π) kA / m (1 kilo-Oersted) is created, and in this state, the container The magnetization moment of the magnetic carrier filled in is measured. Further, the actual mass of the magnetic carrier filled in the container is measured to determine the magnetization strength (Am ² / kg) of the magnetic carrier. Further, the strength of magnetization of the magnetic fine particles in the carrier core can be obtained in the same manner.

<Measurement of true density of magnetic carrier and magnetic fine particles>
The true density of the magnetic carrier particles and magnetic fine particles can be measured, for example, by a dry automatic densimeter 1330 (manufactured by Shimadzu Corporation). The apparent density of the carrier particles and magnetic fine particles can be measured according to JIS Z2504.

  Hereinafter, the present invention will be described in more detail with reference to specific production examples and examples, but the present invention is not limited thereto.

<Production example of hybrid resin>
As a material for the vinyl copolymer unit, dicumyl peroxide is placed in a dropping funnel in 10 parts by mass of styrene, 5 parts by mass of 2-ethylhexyl acrylate, 2 parts by mass of fumaric acid, and 5 parts by mass of a dimer of α-methylstyrene. It was. Moreover, as a material of the polyester resin unit, 25 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4 -Hydroxyphenyl) propane 15 parts by mass, terephthalic acid 9 parts by mass, trimellitic anhydride 5 parts by mass, fumaric acid 24 parts by mass and dibutyltin oxide are put into a glass 4-liter four-necked flask, a thermometer and a stirring rod A condenser and a nitrogen inlet tube were attached to a four-necked flask, and this four-necked flask was placed in a mantle heater. Next, after the inside of the four-necked flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and while stirring at a temperature of 130 ° C., the monomer and the polymerization of the vinyl copolymer from the previous dropping funnel The initiator was added dropwise over about 4 hours. Next, the temperature was raised to 200 ° C. and reacted for about 4 hours to obtain a hybrid resin.

The molecular weight measurement result of THF-soluble matter by GPC of the obtained hybrid resin was Mw of 8.9 × 10 ⁴ and Mn of 3.8 × 10 ³ . The glass transition point was 62 ° C.

<Production example of polyester resin>
30 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 10 parts by mass of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Put 20 parts by mass of terephthalic acid, 3 parts by mass of trimellitic anhydride, 27 parts by mass of fumaric acid and dibutyltin oxide into a 4 liter glass four-necked flask, and add four thermometers, stirring rods, condensers and nitrogen inlet tubes. The flask was attached to a neck flask, and this four-neck flask was placed in a mantle heater. Under a nitrogen atmosphere, reaction was carried out at 210 ° C. for about 5.5 hours to obtain a polyester resin. The molecular weight measurement result by GPC of THF-soluble matter of the obtained polyester resin was Mw of 8.7 × 10 ⁴ and Mn of 3.7 × 10 ³ . The glass transition point was 59 ° C.

<Toner Production Example 1>
Toner (B-1) was produced using the following materials and production method.

-100 parts by mass of the above hybrid resin-C.I. I. Pigment Blue 15: 3 4.5 parts by mass, paraffin wax (W-1; maximum endothermic peak 69 ° C., Mw 600, Mn 400) 5 parts by mass The above materials were mixed with a Henschel mixer (FM-75 type, Mitsui Miike Chemical Co., Ltd.) The mixture was melt kneaded in a twin screw extruder set at a temperature of 150 ° C. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized toner. The obtained coarsely pulverized toner was finely pulverized using a collision-type airflow pulverizer using a high-pressure gas.

Next, the obtained finely pulverized product was treated using a surface modification treatment apparatus as shown in FIGS. Specifically, toner particles were obtained by performing surface treatment for 45 seconds at a dispersion rotor rotation speed of 100 s ⁻¹ (rotational peripheral speed of 130 m / sec) while removing fine particles at a classification rotor rotation speed of 120 s ⁻¹ (raw material) The finely pulverized product was supplied from the supply port 43, and after processing for 45 seconds, the discharge valve 48 was opened and taken out as a processed product). At that time, 10 square hammers were installed on the top of the dispersion rotor 46, the distance between the guide ring 49 and the top square hammer on the dispersion rotor 46 was 30 mm, and the distance between the dispersion rotor 46 and the liner 44 was 3.5 mm. . The blower air volume was 20 m ³ / min, the temperature of the refrigerant passed through the jacket and the cold air temperature T1 were set to −20 ° C. This surface modification process is referred to as process A.

Then, to 100 parts by mass of the obtained toner particles, 1.0 part by mass of titanium oxide (T-1) having a primary average particle diameter of 55 nm surface-treated with isobutyltrimethoxysilane, and the number average particle diameter and aspect shown in Table 1 were used. 1.0 part by mass of hydrophobic silica (Z-1) having a ratio is mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) for 10 minutes at a rotation speed of 30 s ^-1 . Toner (B-1) was obtained. The toner (B-1) obtained had a weight average particle diameter of 6.5 μm, an average circularity of 0.942, and a UV transmittance of 45% when stirred and mixed in a 45% methanol solution.

<Toner Production Example 2>
In Toner Production Example 1, the rotation speed of the dispersion rotor during the surface modification treatment was changed from 100 s ⁻¹ to 50 s ⁻¹ , and the silica (Z-1) mixed with the obtained toner particles was shown in Table 1. Toner (B-2) was obtained in the same manner as in Toner Production Example 1 except that the mixing time was changed to 8 minutes as (Z-2). The toner (B-2) obtained had a weight average particle diameter of 6.7 μm, an average circularity of 0.932, and a UV transmittance of 32% when stirred and mixed in a 45% methanol solution.

<Toner Production Example 3>
In Toner Production Example 1, the obtained toner particles are further spheroidized using a hybridization system (manufactured by Nara Machinery Co., Ltd.), and silica (Z-1) mixed with the toner particles is shown in Table 1. A toner (B-3) was obtained in the same manner as in Toner Production Example 1 except that the composition was changed to (Z-3). The toner (B-3) obtained had a weight average particle diameter of 6.3 μm, an average circularity of 0.955, and a UV transmittance of 62% when stirred and mixed in a 45% methanol solution.

<Toner Production Example 4>
In Toner Production Example 1, the same procedure as in Toner Production Example 1 was carried out except that the silica (Z-1) mixed with the toner particles was changed to silica (Z-4) shown in Table 1 and the mixing time was changed to 20 minutes. A toner (B-4) was obtained. The toner (B-4) obtained had a weight average particle diameter of 6.6 μm, an average circularity of 0.956, and a UV transmittance of 71% when stirred and mixed in a 45% methanol solution.

<Toner Production Example 5>
In Toner Production Example 1, the hybrid resin is changed to the above polyester resin, the blower air volume during the surface modification treatment is adjusted, and the silica (Z-1) mixed with the obtained toner particles is shown in Table 1 Toner (B-5) was obtained in the same manner as in Toner Production Example 1, except that the procedure was changed to Z-5). The obtained toner (B-5) had a weight average particle diameter of 4.5 μm, an average circularity of 0.940, and a UV transmittance of 79% when stirred and mixed in a 45% methanol solution.

<Toner Production Example 6>
450 parts by mass of 0.1 mol / l-Na ₃ PO ₄ aqueous solution is put into 710 parts by mass of ion-exchanged water, heated to 60 ° C., and then rotated using a TK homomixer (manufactured by Special Machine Industries). The mixture was stirred at several 2000 s ⁻¹ . To this, 68 parts by mass of 1.0 mol / l-CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing a calcium phosphate salt.

on the other hand,
Monomer styrene 165 parts by mass
35 parts by mass of n-butyl acrylate / colorant C.I. I. Pigment Blue 15: 3 After 15 parts by weight are finely dispersed by a ball mill,
Polar resin saturated polyester resin (Tg 55 ° C., Mw 2.3 × 10 ⁴ , Mn 3.5 ×
10 ³ ) 10 parts by mass / release agent Ester wax (maximum endothermic peak 70 ° C., Mw 900, Mn 700)
50 parts by mass was added, and the mixture was uniformly dissolved and dispersed at 2000 s ⁻¹ using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) heated to 60 ° C. In this, 10 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

Then, the polymerizable monomer composition is put into the aqueous medium, and stirred at 1600 s ⁻¹ for 10 minutes with a TK homomixer at 60 ° C. in an N ₂ atmosphere. Granulated. Then, while stirring with a paddle stirring blade, the temperature was raised to 80 ° C. and reacted for 10 hours. After completion of the polymerization reaction, residual monomers were removed under reduced pressure, and after cooling, hydrochloric acid was added to dissolve calcium phosphate, followed by filtration, washing with water, and drying to obtain toner particles.

Then, to 100 parts by mass of the obtained toner particles, 1.0 part by mass of titanium oxide (T-1) having a primary average particle diameter of 55 nm surface-treated with isobutyltrimethoxysilane, and the number average particle diameter and aspect shown in Table 1 were used. 1.0 part by mass of hydrophobic silica (Z-6) having a ratio is mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) for 10 minutes at a rotational speed of 30 s ⁻¹ . Toner (B-6) was obtained. The obtained toner (B-6) had a weight average particle diameter of 8.3 μm, an average circularity of 0.975, and a UV transmittance of 12% when stirred and mixed in a 45% methanol solution.

<Toner Production Example 7>
-Preparation of resin particle dispersion 1 Styrene 370 gn-butyl acrylate 30 g Acrylic acid 6 g Dodecanethiol 24 g Carbon tetrabromide 4 g
6 g of nonionic surfactant (trade name: Novonyl, manufactured by Sanyo Kasei Co., Ltd.) and 10 g of anionic surfactant (trade name: Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were ionized. Dispersed in 550 g of exchange water, dispersed in a flask, emulsified, and slowly mixed for 10 minutes, charged with 50 g of ion exchange water in which 4 g of ammonium persulfate was dissolved, and after nitrogen replacement, While stirring in the flask, the contents were heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. Thus, a resin particle dispersion 1 was prepared by dispersing resin particles having an average particle size of 150 nm, a glass transition point of 62 ° C., and a weight average molecular weight (Mw) of 12,000.

-Preparation of resin particle dispersion 2 Styrene 280 gn-butyl acrylate 120 g
Acrylic acid 8g
While mixing and dissolving the above, 6 g of nonionic surfactant and 12 g of anionic surfactant dissolved in 550 g of ion-exchanged water are dispersed in a flask, emulsified, and slowly mixed for 10 minutes. Into this, 50 g of ion-exchanged water in which 3 g of ammonium persulfate was dissolved was added, and after nitrogen substitution, the contents in the flask were heated with an oil bath until the temperature reached 70 ° C. while stirring, and the emulsion polymerization was continued for 5 hours. The resin particle dispersion 2 was prepared by dispersing resin particles having an average particle size of 110 nm, a glass transition point of 55 ° C., and a weight average molecular weight (Mw) of 550,000.

Preparation of release agent particle dispersion 1 Polypropylene wax (maximum endothermic peak 85 ° C., Mw 800, Mn 600) 50 g anionic surfactant 5 g ion-exchanged water 200 g
The above was heated to 95 ° C. and dispersed using a homogenizer or the like, then dispersed with a pressure discharge type homogenizer, and a release agent particle dispersion 1 in which a release agent having an average particle size of 570 nm was dispersed was obtained. Prepared.

-Preparation of colorant particle dispersion 1 I. Pigment Blue 15: 3 20 g Anionic surfactant 2 g Ion-exchanged water 78 g
The above was mixed and dispersed for 10 minutes at an oscillation frequency of 26 kHz using an ultrasonic cleaner to prepare a colorant particle dispersion (anionic) 1.

-Preparation of mixed liquid Resin particle dispersion 1 180 g Resin particle dispersion 2 80 g Colorant dispersion 1 30 g Release agent dispersion 1 50 g
The above was mixed in a round stainless steel flask using a homogenizer and dispersed to prepare a mixed solution.

-Formation of Aggregated Particles 1.5 g of a cationic surfactant as an aggregating agent was added to the above mixed solution, and the mixture was heated to 50 ° C. while stirring the inside of the flask in a heating oil bath. After maintaining at 50 ° C. for 1 hour, observation with an optical microscope confirmed that aggregated particles having a weight average particle diameter of about 6.1 μm were formed.

Fusion After that, 3 g of an anionic surfactant was added thereto, and then the stainless steel flask was sealed, heated to 105 ° C. while continuing stirring using a magnetic seal, and held for 3 hours. Then, after cooling, the reaction product was filtered, thoroughly washed with ion exchange water, and then dried to obtain toner particles.

Then, to 100 parts by mass of the obtained toner particles, 1.0 part by mass of titanium oxide (T-1) having a primary average particle diameter of 55 nm surface-treated with isobutyltrimethoxysilane, and the number average particle diameter and aspect shown in Table 1 were used. was added hydrophobic silica (Z-7) 1.0 parts by weight with a ratio, a Henschel mixer (FM-75 type, Mitsui Miike Machinery Co., Ltd.) rpm 30s ^-1, with mixing for 10 minutes, Toner (B-7) was obtained. The toner (B-7) obtained had a weight average particle diameter of 6.2 μm, an average circularity of 0.965, and a UV transmittance of 21% when stirred and mixed in a 45% methanol solution.

<Toner Production Example 8>
In toner production example 1, the hybrid resin is changed to the above polyester resin, and the titanium oxide (T-1) mixed with the obtained toner particles is surface-treated with isobutyltrimethoxysilane without performing the surface modification treatment. Toner (b) was prepared in the same manner as in Toner Production Example 1 except that titanium oxide (T-2) and silica (Z-1) having an average particle diameter of 75 nm were changed to silica (Z-8) shown in Table 1. -1) was obtained. The toner (b-1) obtained had a weight average particle diameter of 4.3 μm, an average circularity of 0.901, and a UV transmittance of 82% when stirred and mixed in a 45% methanol solution.

<Toner Production Example 9>
In Toner Production Example 6, the granulating time of the polymerizable monomer composition was changed, and titanium oxide (T-1) mixed with the obtained toner particles was changed to (T-2), and silica (Z-1). Was changed to silica (Z-9) shown in Table 1, and toner (b-2) was obtained in the same manner as in Toner Production Example 6. The obtained toner (b-2) had a weight average particle diameter of 8.8 μm, an average circularity of 0.976, and a UV transmittance of 7% when stirred and mixed in a 45% methanol solution.
<Toner Production Example 10>
In the toner production example 1, the hybrid resin is changed to the above polyester resin, and the silica (Z-1) mixed with the obtained toner particles without performing the surface modification treatment is shown in Table 1 as silica (Z-8). The toner (b-3) was obtained in the same manner as in Toner Production Example 1 except that the toner (b-3) was changed. The toner (b-3) obtained had a weight average particle diameter of 4.4 μm, an average circularity of 0.902, and a UV transmittance of 81% when stirred and mixed in a 45% methanol solution.

<Example 1 of production of magnetic fine particle-dispersed resin carrier core>
A magnetic fine particle-dispersed resin carrier core (R-1) was produced using the materials shown below.
Phenol 10 parts by mass Formaldehyde solution (37% by weight aqueous solution) 6 parts by mass Magnetite particles (particle size 0.31 μm, σ ₁₀₀₀ = 60.2 Am ² / kg) 76 parts by mass Hematite particles (non-magnetic, particle size 0 .45 μm) 8 parts by mass The above material, 5 parts by mass of 28% by mass ammonia water, and 10 parts by mass of water are placed in a flask, heated and maintained at 85 ° C. for 30 minutes while stirring and mixing, and allowed to undergo polymerization reaction for 3 hours. And cured. Then, after cooling to 30 ° C. and further adding water, the supernatant was removed, and the precipitate was washed with water and then air-dried. Next, this was dried under reduced pressure (5 hPa or less) at a temperature of 60 ° C. to obtain a magnetic fine particle dispersed resin carrier core (R-1) in which magnetic fine particles were dispersed.

<Production Example 2 of Magnetic Fine Particle Dispersed Resin Carrier Core>
A magnetic fine particle-dispersed resin carrier core (R-2) was produced using the materials shown below.
-Phenol 20 parts by mass-Formaldehyde solution (37% by weight aqueous solution) 12 parts by mass-Magnetite particles (particle size 0.32 μm, σ ₁₀₀₀ = 59.8 Am ² / kg) 61 parts by mass-Hematite particles (non-magnetic, particle size 0 .44 μm) 7 parts by mass The above materials, 10 parts by mass of 28% by mass ammonia water, and 10 parts by mass of water were placed in a flask, heated and maintained at 85 ° C. over 30 minutes with stirring and mixing, and allowed to undergo a polymerization reaction for 3 hours. And cured. Then, after cooling to 30 ° C. and further adding water, the supernatant was removed, and the precipitate was washed with water and then air-dried. Next, this was dried under reduced pressure (5 hPa or less) at a temperature of 60 ° C. to obtain a magnetic fine particle dispersed resin carrier core (R-2) in which magnetic fine particles were dispersed.

<Production Example 3 of Magnetic Fine Particle-Dispersed Resin Carrier Core>
A magnetic fine particle-dispersed resin carrier core (R-3) was prepared using the materials shown below.
・ Phenol 10 parts by mass ・ Formaldehyde solution (37% by mass aqueous solution) 6 parts by mass ・ Magnetite particles (particle size 0.31 μm, magnetic properties σ ₁₀₀₀ = 62.2 Am ² / kg)
59 parts by mass-hematite particles (non-magnetic, particle size 0.45 μm) 25 parts by mass The above materials, 5 parts by mass of 28% by mass ammonia water, and 10 parts by mass of water are placed in a flask and stirred for 85 minutes over 30 minutes. The temperature was raised to and maintained at 0 ° C., and a polymerization reaction was performed for 3 hours to cure. Then, after cooling to 30 ° C. and further adding water, the supernatant was removed, and the precipitate was washed with water and then air-dried. Subsequently, this was dried under reduced pressure (5 hPa or less) at a temperature of 60 ° C. to obtain a magnetic fine particle dispersed resin carrier core (R-3) in which magnetic fine particles were dispersed.

<Production Example 4 of Magnetic Fine Particle Dispersed Resin Core>
A magnetic fine particle-dispersed resin carrier core (R-4) was produced using the materials shown below.
・ Phenol 30 parts by mass ・ Formaldehyde solution (37 mass% aqueous solution) 18 parts by mass ・ Magnetite particles (particle size 0.33 μm, magnetic properties σ ₁₀₀₀ = 55.6 Am ² / kg)
47 parts by mass, hematite particles (non-magnetic, particle size 0.46 μm)
5 parts by mass The above material, 15 parts by mass of 28% by mass ammonia water, and 10 parts by mass of water are placed in a flask, heated to 85 ° C. in 30 minutes with stirring and mixing, and allowed to cure by polymerization for 3 hours. It was. Then, after cooling to 30 ° C. and further adding water, the supernatant was removed, and the precipitate was washed with water and then air-dried. Subsequently, this was dried under reduced pressure (5 hPa or less) at a temperature of 60 ° C. to obtain a magnetic fine particle dispersed resin carrier core (R-4) in which magnetic fine particles were dispersed.

<Manufacture example 1 of coating material for coating layers>
3 parts by mass of a methyl methacrylate macromonomer having an ethylenically unsaturated group at one end and a weight average molecular weight of 5,000, 46 parts by mass of a monomer having the following compound (g) as a unit, and 51 parts by mass of methyl methacrylate were added to a reflux condenser. , A thermometer, a nitrogen suction tube, and a four-necked flask equipped with a mixing method stirrer, and further 100 parts by mass of toluene, 100 parts by mass of methyl ethyl ketone, 2.4 parts by mass of azobisisovaleronitrile, and under nitrogen flow The graft copolymer solution (solid content 35 mass%) was obtained by maintaining at 80 ° C. for 10 hours. The weight average molecular weight according to gel permeation chromatogram (GPC) of the graft copolymer was 20,000.

  0.7 parts by mass of melamine resin (number average particle diameter 0.25 μm), carbon black (number average particle diameter 35 nm, DBP oil absorption 50 ml / 100 g) with respect to 30 parts by mass of the obtained graft copolymer solution 2 parts by mass and 100 parts by mass of toluene were stirred with a homogenizer to obtain a coating material (L-1).

<Manufacture example 2 of coating material for coating layers>
20 parts by mass of toluene, 20 parts by mass of butanol, 10 parts by mass of water, and 40 parts by mass of ice were placed in a four-necked flask, and a mixture 4 having a molar ratio of CH ₃ SiCl ₃ and SiCl ₂ of 4: 2 with stirring.
After 0 parts by mass and a catalyst were added and further stirred for 30 minutes, a condensation reaction was performed at 60 ° C. for 1 hour. Thereafter, the siloxane was thoroughly washed with water and dissolved in a toluene-methyl ethyl ketone-butanol mixed solvent to prepare a silicone varnish having a solid content of 10%.

  In this silicone varnish, with respect to 100 parts by mass of siloxane solids, 2.0 parts by mass of ion-exchanged water and 2.0 parts by mass of the following curing agent

と、２．０質量部の下記アミノシランカップリング剤
（ＣＨ₃）₂Ｎ−Ｃ₃Ｈ₆−Ｓｉ−（ＯＣＨ₃）₃
を同時添加し、コート材（Ｌ−２）を得た。

And 2.0 parts by mass of the following aminosilane coupling agent (CH ₃ ) ₂ N—C ₃ H ₆ —Si— (OCH ₃ ) ₃
Were simultaneously added to obtain a coating material (L-2).

<Magnetic carrier production example 1>
While stirring 100 mass parts of the magnetic fine particle dispersed resin carrier core (R-1) while continuously applying shear stress, the coating material (L-1) is gradually added and the solvent is volatilized at 70 ° C. Resin coating was applied to the surface. The resin-coated magnetic carrier particles were heat-treated with stirring at 100 ° C. for 2 hours, pulverized, and then classified with a sieve having an aperture of 76 μm, and a number average particle size of 35 μm and a specific resistance of 5.9 × 10 ⁹ Ω. A magnetic carrier (C-1) having cm, true specific gravity of 3.6 g / cm ³ , magnetization strength (σ1000) of 50.6 Am ² / kg, and residual magnetization of 4.8 Am ² / kg was obtained. Table 2 shows the physical properties of the obtained magnetic carrier.

<Magnetic carrier production example 2>
In Magnetic Carrier Production Example 1, except that Cu—Zn ferrite particles (particle size: 41 μm, σ ₁₀₀₀ = 69.0 Am ² / kg) were used instead of the magnetic fine particle dispersed resin carrier core (R-1), the magnetic carrier In the same manner as in Production Example 1, a magnetic carrier (C-2) was obtained. Table 2 shows the physical properties of the obtained magnetic carrier.

<Magnetic carrier production example 3>
In the magnetic carrier production example 1, the magnetic carrier (C-3) was prepared in the same manner as in the magnetic carrier production example 1 except that (R-2) was used instead of the magnetic fine particle dispersed resin carrier core (R-1). Obtained. Table 2 shows the physical properties of the obtained magnetic carrier.

<Magnetic carrier production example 4>
In the magnetic carrier production example 1, the magnetic carrier (C-4) was prepared in the same manner as in the magnetic carrier production example 1 except that (R-3) was used instead of the magnetic fine particle dispersed resin carrier core (R-1). Obtained. Table 2 shows the physical properties of the obtained magnetic carrier.

<Magnetic carrier production example 5>
In Magnetic Carrier Production Example 1, Magnetic Carrier (C-5) was obtained in the same manner as Magnetic Carrier Production Example 1 except that (L-2) was used instead of the coating material for coating (L-1). Table 2 shows the physical properties of the obtained magnetic carrier.

<Magnetic carrier production example 6>
Magnetic carrier production example 1 except that Mg-Mn ferrite particles (particle size 32 μm, σ ₁₀₀₀ = 63.1 Am ² / kg) were used instead of the magnetic fine particle dispersed resin carrier core (R-1). In the same manner as in Production Example 1, a magnetic carrier (C-6) was obtained. Table 2 shows the physical properties of the obtained magnetic carrier.

<Magnetic carrier production example 7>
In the magnetic carrier production example 1, the magnetic carrier (c-1) was prepared in the same manner as in the magnetic carrier production example 1 except that (R-4) was used instead of the magnetic fine particle dispersed resin carrier core (R-1). Obtained. Table 2 shows the physical properties of the obtained magnetic carrier.

<Magnetic carrier production example 8>
Magnetic carrier production example 1 except that magnetite particles (particle size 17 μm, σ ₁₀₀₀ = 74.2 Am ² / kg) were used in place of the magnetic fine particle dispersed resin carrier core (R-1) in magnetic carrier production example 1. In the same manner as above, a magnetic carrier (c-2) was obtained. Table 2 shows the physical properties of the obtained magnetic carrier.

<Developer Production Example 1>
To 92 parts by mass of the magnetic carrier (C-1), 8 parts by mass of the toner (B-1) is added and mixed by a tumbler mixer. The degree of compression C is 26% and the consolidation load is 4.0 × 10 ⁻⁴ N / mm ² shear stress under got 1.6 × 10 ^-4 N / mm ² of a two-component developer (D-1). Table 3 shows the physical properties of the developer thus obtained.

<Developer Production Examples 2 to 13>
In Developer Production Example 1, two-component developers (D-2) to (D-10) and 2 are prepared in the same manner as in Developer Production Example 1 except that the magnetic carrier and the toner are mixed in the combinations shown in Table 3. Component developers (d-1) to (d-3) were obtained. Table 3 shows the physical properties of the developer thus obtained.

<Example 1>
Using a two-component developer (D-1), a Canon full color copier CLC5000 remodeled machine (modified so that the laser spot diameter can be output at 600 dpi. The developing unit development sleeve is as shown in FIG. The upstream developing sleeve (diameter 20 mm) and the downstream developing sleeve (diameter 16 mm) were changed to two, each facing the photosensitive drum, and the surface layer of the fixing roller of the fixing unit was changed to a PFA tube, and the oil application mechanism was changed. Removed) under normal temperature and normal humidity (N / N; 23 ° C., 50% RH), normal temperature and low humidity (N / L; 23 ° C., 5% RH), high temperature and high humidity (H / H; 30 The image was printed and evaluated while replenishing the toner (B-1) at a temperature of 80 [deg.] C. and 80% RH. The developing condition is that each developing sleeve and the photosensitive member are rotated in the forward direction in the developing region, the peripheral speed of the developing sleeve is 1.6 times that of the photosensitive member, and the developing bias is Vd = −650V, Vl = −150V. Vpp = 2.0 kV and frequency 1.8 kHz. Evaluation items and evaluation criteria are shown below, and the evaluation results are shown in Table 4.

[Evaluation item]
(Solid uniformity)
A 30H image was formed using the developer and the modified machine, and this image was visually observed. The reproducibility of the solid uniformity of the image was evaluated using the following indices. The 30H image is a value obtained by displaying 256 gradations in hexadecimal, and is a halftone image of the 49th gradation from a solid white image in 256 gradations.
A: An image having no stripes or unevenness and no graininess.
B: Although there are no streaks or unevenness, the image has a slight graininess.
C: Slight streaks / unevenness is observed, and the image is grainy.
D: The image has a lot of streaks and unevenness and a strong graininess.
E: A noticeable image of streaks / unevenness.

(Image density)
When the solid image was fixed at 180 ° C., the density of the fixed image was measured with a densitometer X-Rite500 type, and the average value of 6 points was taken as the image density.

(Q / M on the developing sleeve after 10,000)
Using the above-mentioned two-component developer, 10,000 sheets are imaged by the above-mentioned remodeling machine, the developer on each developing sleeve is sampled, and each developing sleeve is obtained by an E-Spart analyzer (manufactured by Hosokawa Micron) equipped with a two-component feeder. The charge amount Q / M (mC / kg) per unit mass of the upper toner was measured and defined as Q / M on the sleeve after 10,000.

(Developer splash)
The above two-component developer is put in the above-mentioned modified developer, and the developing sleeve is rotated at a peripheral speed of 600 mm / sec for 1 hour in each environment. At that time, the developer scattered from the sleeve surface is collected and visually observed. Observed and evaluated for developer scattering according to the following criteria.
A: No developer is scattered at all. B: Among the developers, the toner is slightly scattered.
C: The toner is scattered, but the carrier is not scattered.
D: The carrier is slightly scattered along with the toner scattering.
E: Scattering as a developer is remarkable.

(Toner spent)
The two-component developer is put into the modified developer, and the developing sleeve is idled at a process speed of 600 mm / s for 1 hour in each environment. Thereafter, the developer is sampled from the sleeve surface, and the toner and carrier are removed. The carrier surface after separation and idling was observed with a scanning electron microscope (SEM), a halftone image was output, and toner spent was evaluated according to the following criteria.
A: The toner hardly adheres to the carrier surface. B: The toner slightly adheres to the carrier surface.
C: Toner spent has occurred, but no background staining has occurred.
D: Toner spent occurs and some background stains are observed.
E: Toner spent occurs and the background is noticeable.

<Examples 2 to 10>
In Example 1, except that the two-component developer (D-1) is changed to (D-2) to (D-10) and the toner corresponding to each two-component developer shown in Table 3 is replenished. In the same manner as in Example 1, images were produced and evaluated. The evaluation results are shown in Table 4.

<Comparative Examples 1-3>
In Example 1, except that the two-component developer (D-1) is changed to (d-1) to (d-3) and the toner corresponding to each two-component developer shown in Table 3 is replenished. In the same manner as in Example 1, images were produced and evaluated. The evaluation results are shown in Table 4.

<Supplier developer production example 1>
As a developer for replenishing the two-component developer (D-1), 90 parts by mass of the toner (B-1) is added to 10 parts by mass of the magnetic carrier (C-1), and the mixture is mixed by a tumbler mixer. A replenishment developer (D-1) ′ for the component developer (D-1) was obtained.

<Other replenishment developer production examples>
In addition to the toner and magnetic carrier used in the manufacture of the two-component developer (D-9), (D-10), (d-1), and (d-2) in the replenishment developer production example 1. Were supplied developer (D-9) ′, (D-10) ′, (d-1) ′, and (d-2) ′, respectively, in the same manner as Supply Developer Production Example 1.

<Example 11>
In the first embodiment, the developer is further modified as shown in FIGS. 2 and 3 (developer chamber for supplying developer to the upstream developing sleeve, and developer after passing through the developing area. The developer chamber and the agitating chamber are separated from the agitating chamber to be collected, and a screw for circulating the developer is provided in the developing chamber and the agitating chamber, and each developing sleeve includes a magnet roll having a magnetic pole configuration as shown in FIG. In addition, a developer layer thickness regulating member is brought close to the upstream developing sleeve as shown in FIG. 2, and a replenishment port (not shown) for supplying replenishment developer and a discharge port for discharging excess developer. The image was evaluated and evaluated in the same manner as in Example 1 except that the image was developed and evaluated while supplying the replenishment developer (D-1) ′. As shown in FIG.

<Examples 12 and 13, Comparative Examples 4 and 5>
In Example 11, the two-component developer (D-1) is changed to the two-component developer (D-9), (D-10), (d-1), (d-2), and the replenishment developer. Was changed to (D-9) ′, (D-10) ′, (d-1) ′, and (d-2) ′, and imaged and evaluated in the same manner as in Example 11. The evaluation results are shown in Table 5.

It is a schematic diagram which shows an example of the image development apparatus using the image development method of this invention. It is a schematic diagram which shows an example of the image development apparatus using the image development method of this invention. It is a schematic diagram which shows an example of the image development apparatus using the image development method of this invention. FIG. 3 is a schematic diagram illustrating an example of a toner surface modifying apparatus. It is a schematic diagram which shows an example of the dispersion | distribution rotor of the surface modification apparatus of FIG. It is a schematic diagram of the apparatus used in order to measure the specific resistance of the magnetic carrier used for this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Developing device 2 Developing container 8 First developing sleeve 10 Image carrier 11 Second developing sleeve T Developer

Claims (7)

A first developer carrier disposed opposite to the image carrier, a developer layer thickness regulating member for forming a developer layer on the first developer carrier, and a first developer; At least a second developer carrier disposed downstream of the image carrier in the rotation direction of the image carrier, the first developer carrier and the second developer carrier, The developer is carried and transported to the development area where the first developer carrier and the second developer carrier and the image carrier face each other, and the latent image formed on the image carrier is A developing method using a developing device for developing with a developer,
The developing device transfers the developer supplied to the development area formed by the first developer carrier and the image carrier from the first developer carrier to the second developer carrier. The developed developer is provided to a development region formed by the second developer carrier and the image carrier,
The developer is a two-component developer having a toner having toner particles containing at least a binder resin and a colorant, and a magnetic carrier.
The developer is represented by the following formula (1)
Compression degree C (%) = 100 × (PA) / P (1)
[In the formula, A is a loose apparent density (g / cm ³ ), and P is a firm apparent density (g / cm ³ ). ]
The compression degree C obtained from is 20 to 32%,
Further, the developer has a shear stress of 0.5 × 10 ^{−4 to} 2.5 × 10 ⁻⁴ N / mm under a consolidation load of 4.0 × 10 ⁻⁴ N / mm ² according to shear stress measurement. ^2. A developing method, wherein   2. The developing method according to claim 1, wherein the magnetic carrier is a carrier having a coating layer on the surface of a magnetic fine particle-dispersed resin core containing at least magnetic fine particles and a binder resin.   The toner is obtained by externally adding inorganic fine particles to toner particles, the aspect ratio (major axis / minor axis) of the inorganic fine particles on the toner particle surface is 1.0 to 1.5, and the toner particle surface The developing method according to claim 1, wherein the number average particle size at 0.06 to 0.30 μm.   The developing device is provided in a developing chamber for supplying the developer to the first developer carrying member and below the developing chamber, and collects the developer from the second developer carrying member. 4. The developer according to claim 1, further comprising: a stirring chamber, wherein the collected developer is pushed up from the stirring chamber to the developing chamber by the pressure of the developer at the end of the stirring chamber, and then delivered. The developing method according to any one of the above. The first developer carrying member includes a first magnetic field generating unit provided so as not to rotate, and a first developing sleeve including the first magnetic field generating unit and provided rotatably. And
The first magnetic field generating means is provided so as to be adjacent to the first magnetic pole downstream of the development region in the moving direction of the first developer carrier and adjacent to the downstream side of the first magnetic pole in the moving direction. Having at least a first magnetic pole and a second magnetic pole of the same polarity;
The developer layer thickness regulating member is disposed in a region substantially opposite to the second magnetic pole;
The second developer carrying member includes a second magnetic field generating unit provided so as not to rotate, and a second developing sleeve including the second magnetic field generating unit and provided rotatably. And
The second magnetic field generating means includes a third magnetic pole opposite in polarity to the first magnetic pole provided in a region substantially opposite to the first magnetic pole, and the second developer carrier rotating direction of the third magnetic pole. 5. The developing method according to claim 1, further comprising at least a fourth magnetic pole having the same polarity as the third magnetic pole provided adjacent to the upstream side.   The developing device has a developer discharging mechanism, and the developer discharging mechanism discharges excess developer, and the developing device contains at least the toner and the magnetic carrier. The developing method according to claim 1, wherein the toner is replenished. A first developer carrier disposed opposite to the image carrier, a developer layer thickness regulating member for forming a developer layer on the first developer carrier, and a first developer; At least a second developer carrier disposed downstream of the image carrier in the rotation direction of the image carrier, the first developer carrier and the second developer carrier, The developer is carried and transported to the development area where the first developer carrier and the second developer carrier and the image carrier face each other, and the latent image formed on the image carrier is A developing device for developing with a developer,
The developing device transfers the developer supplied to the development area formed by the first developer carrier and the image carrier from the first developer carrier to the second developer carrier. The developed developer is provided to a development region formed by the second developer carrier and the image carrier,
The developer is a two-component developer having a toner having toner particles containing at least a binder resin and a colorant, and a magnetic carrier.
The developer is represented by the following formula (1)
Compression degree C (%) = 100 × (PA) / P (1)
[In the formula, A is a loose apparent density (g / cm ³ ), and P is a firm apparent density (g / cm ³ ). ]
The compression degree C obtained from is 20 to 32%,
Further, the developer has a shear stress of 0.5 × 10 ^{−4 to} 2.5 × 10 ⁻⁴ N / mm under a consolidation load of 4.0 × 10 ⁻⁴ N / mm ² according to shear stress measurement. ^2. A developing device, wherein

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