JP2018097052A - Toner for electrostatic latent image development and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress a release agent from separating from a toner particle while securing sufficient heat resistant storage properties of toner.SOLUTION: Toner for electrostatic latent image development includes a plurality of toner particles each comprising a toner core 11 containing binding resin and a release agent and a multi-layered structure shell layer 12 partially covering a surface of the toner core 11. The multi-layered shell layer 12 comprises, in order from the side of the toner core 11, a first shell layer 12a containing a first polymer including a repeating unit having an oxazoline group, a second shell layer 12b containing a second polymer including a repeating unit having a carboxyl group, and a third shell layer 12c containing a third polymer including a repeating unit having an oxazoline group. The second shell layer 12b is in contact with a region, which is not covered with the first shell layer 12a, of a surface region of the toner core 11.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a toner for developing an electrostatic latent image and a manufacturing method thereof, and more particularly to a core-shell type toner and a manufacturing method thereof.

  For example, Patent Document 1 discloses a technique for improving the storage stability of a toner by using a reactive polymer having an oxazoline group as a crosslinking agent.

JP 2013-19971 A

  However, Patent Document 1 focuses only on the crosslinkability (reactivity) of the oxazoline group, and does not sufficiently study the suppression of the release of the release agent from the toner particles.

  The present invention has been made in view of the above problems, and an object thereof is to suppress release of a release agent from toner particles while ensuring sufficient heat-resistant storage stability of the toner.

  The electrostatic latent image developing toner according to the present invention includes a plurality of toner particles each including a core containing a binder resin and a release agent, and a multilayered shell layer that partially covers the surface of the core. The multilayer shell layer includes a first shell layer containing a first polymer containing a repeating unit having an oxazoline group, a second shell layer containing a second polymer containing a repeating unit having a carboxyl group, and an oxazoline group. And a third shell layer containing a third polymer including the repeating unit. The first shell layer, the second shell layer, and the third shell layer have a stacked structure in the order of the first shell layer, the second shell layer, and the third shell layer from the core side. The second shell layer is in contact with a region of the core surface region that is not covered with the first shell layer.

  The method for producing a toner for developing an electrostatic latent image according to the present invention includes a first shell layer forming step, a second shell layer forming step, and a third shell layer forming step. In the first shell layer forming step, an aqueous medium containing a core containing a binder resin and a release agent and an oxazoline group-containing polymer is heated to partially cover the surface of the toner core, and the oxazoline group Forming a first shell layer containing a first polymer comprising repeating units having In the second shell layer forming step, after the first shell layer forming step, a carboxyl group-containing polymer is put into the aqueous medium, and the carboxyl group-containing polymer is added to the first shell in the aqueous medium. By heating the aqueous medium and polymerizing the carboxyl group-containing polymer in a state where it is in contact with the surface of the layer and a region of the surface region of the core that is not covered with the first shell layer, A second shell layer containing a second polymer containing a repeating unit having a carboxyl group is formed on the first shell layer. In the third shell layer forming step, after the second shell layer forming step, an oxazoline group-containing polymer is placed in the aqueous medium, and the aqueous medium is heated, whereby the oxazoline is formed on the second shell layer. A third shell layer containing a third polymer including a repeating unit having a group is formed.

  According to the present invention, it is possible to suppress release of the release agent from the toner particles while ensuring sufficient heat-resistant storage stability of the toner.

It is a figure which shows an example of the cross-section of the toner particle contained in the electrostatic latent image developing toner according to the embodiment of the present invention. FIG. 2 is an enlarged view showing a part of the surface of toner base particles contained in the electrostatic latent image developing toner according to the embodiment of the present invention. FIG. 3A is a plan view showing, in an enlarged manner, a part of the surface of the toner core in a state before the multilayer shell layer is formed with respect to the toner base particles shown in FIG. FIG. 3B is a cross-sectional view of the toner core shown in FIG. FIG. 4A is a plan view showing particles (first layer-coated particles) in which a first shell layer is formed on the surface of the toner core shown in FIG. FIG. 4B is a cross-sectional view of the first layer-coated particles shown in FIG. It is sectional drawing which expands and shows a part of FIG. FIG. 6 is a diagram showing the positions of the edges of the carboxyl group-containing shell layer in the multilayer shell layer with respect to the toner mother particles shown in FIG. 5.

  Embodiments of the present invention will be described in detail. Note that the evaluation results (values indicating the shape or physical properties) of the powder (more specifically, the toner core, toner base particles, external additive, toner, etc.) are averaged from the powder unless otherwise specified. This is the number average of the values measured for each of the average particles by selecting a significant number of such particles.

The number average particle diameter of the powder is the number average value of the equivalent circle diameter of primary particles (diameter of a circle having the same area as the projected area of the particles) measured using a microscope unless otherwise specified. . Moreover, the measured value of the volume median diameter (D ₅₀ ) of the powder is measured using a laser diffraction / scattering particle size distribution measuring device (“LA-750” manufactured by Horiba, Ltd.) unless otherwise specified. It is the value.

  The glass transition point (Tg) is a value measured according to “JIS (Japanese Industrial Standard) K7121-2012” using a differential scanning calorimeter (“DSC-6220” manufactured by Seiko Instruments Inc.) unless otherwise specified. It is. In the endothermic curve (vertical axis: heat flow (DSC signal), horizontal axis: temperature) at the second temperature rise measured by the differential scanning calorimeter, the change point of the specific heat (outside the extrapolated line of the baseline and the falling line) The temperature (onset temperature) at the intersection with the insertion line corresponds to Tg (glass transition point). Moreover, the softening point (Tm) is a value measured using a Koka type flow tester (“CFT-500D” manufactured by Shimadzu Corporation) unless otherwise specified. In the S curve (horizontal axis: temperature, vertical axis: stroke) measured with the Koka type flow tester, the temperature that becomes "(baseline stroke value + maximum stroke value) / 2" is Tm (softening point). Equivalent to. Moreover, the measured value of a number average molecular weight (Mn) is the value measured using the gel permeation chromatography, if not prescribed | regulated at all.

  The “main component” of a material means a component most contained in the material on a mass basis unless otherwise specified. The chargeability means chargeability in frictional charging unless otherwise specified. The strength of positive chargeability (or strength of negative chargeability) in frictional charging can be confirmed by a known charge train or the like.

  Hereinafter, a compound and its derivatives may be generically named by adding “system” after the compound name. When the name of a polymer is expressed by adding “system” after the compound name, it means that the repeating unit of the polymer is derived from the compound or a derivative thereof. Acrylic and methacrylic are sometimes collectively referred to as “(meth) acrylic”. Further, acrylonitrile and methacrylonitrile may be collectively referred to as “(meth) acrylonitrile”.

  The toner according to the exemplary embodiment can be suitably used for developing an electrostatic latent image, for example, as a positively chargeable toner. The toner of the present exemplary embodiment is a powder that includes a plurality of toner particles (each having a configuration described later). The toner may be used as a one-component developer. Alternatively, a two-component developer may be prepared by mixing toner and carrier using a mixing device (for example, a ball mill). In order to form a high-quality image, it is preferable to use a ferrite carrier (ferrite particle powder) as a carrier. In order to form a high-quality image over a long period of time, it is preferable to use magnetic carrier particles including a carrier core and a resin layer covering the carrier core. In order to impart magnetism to the carrier particles, the carrier core may be formed of a magnetic material (for example, a ferromagnetic substance such as ferrite), or the carrier core may be formed of a resin in which magnetic particles are dispersed. Good. Further, magnetic particles may be dispersed in the resin layer covering the carrier core. Examples of the resin constituting the resin layer are 1 selected from the group consisting of a fluororesin (more specifically, PFA or FEP), a polyamideimide resin, a silicone resin, a urethane resin, an epoxy resin, and a phenol resin. More than one type of resin may be mentioned. In order to form a high-quality image, the amount of toner in the two-component developer is preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the carrier. The particle diameter of the carrier particles is preferably 20 μm or more and 120 μm or less. The positively chargeable toner contained in the two-component developer is positively charged by friction with the carrier.

  The toner particles contained in the toner according to the exemplary embodiment include a core (hereinafter referred to as a toner core) containing a binder resin and a release agent, and a shell layer (capsule layer) that covers the surface of the toner core. The toner core may contain an internal additive other than the release agent (for example, at least one of a colorant, a charge control agent, and a magnetic powder). The shell layer has a multilayer structure. For example, by covering a toner core that melts at a low temperature with a multilayer structure shell layer having excellent heat resistance, it is possible to achieve both heat-resistant storage stability and low-temperature fixability of the toner. An external additive may be attached to the surface of the multilayer structure shell layer (or the surface area of the toner core not covered with the multilayer structure shell layer). If not necessary, the external additive may be omitted. Hereinafter, the toner particles before the external additive adheres are referred to as toner mother particles. A material for forming the shell layer is referred to as a shell material.

  The toner core can be produced, for example, by a pulverization method or an aggregation method. These methods tend to favorably disperse the internal additive in the binder resin of the toner core. It is well known in the technical field to which the present invention pertains that the toner core is roughly divided into a pulverized core (also referred to as a pulverized toner) and a polymerized core (also referred to as a chemical toner). The toner core obtained by the pulverization method belongs to the pulverization core, and the toner core obtained by the aggregation method belongs to the polymerization core.

  The toner according to the exemplary embodiment can be used for image formation in, for example, an electrophotographic apparatus (image forming apparatus). Hereinafter, an example of an image forming method using an electrophotographic apparatus will be described.

  First, an image forming unit (charging device and exposure device) of an electrophotographic apparatus forms an electrostatic latent image on a photoconductor based on image data. Subsequently, a developing device of the electrophotographic apparatus (specifically, a developing device in which a developer containing toner is set) supplies the toner to the photoconductor to develop the electrostatic latent image formed on the photoconductor. The toner is charged by friction with the carrier, the developing sleeve, or the blade in the developing device before being supplied to the photoreceptor. For example, a positively chargeable toner is positively charged. In the developing process, toner (specifically, charged toner) on a developing sleeve (for example, a surface layer portion of a developing roller in the developing device) disposed in the vicinity of the photosensitive member is supplied to the photosensitive member, and the supplied toner is By attaching to the electrostatic latent image on the photoconductor, a toner image is formed on the photoconductor. The consumed toner is replenished to the developing device from a toner container containing replenishment toner.

  In the subsequent transfer process, after the transfer device of the electrophotographic apparatus transfers the toner image on the photosensitive member to an intermediate transfer member (for example, a transfer belt), the toner image on the intermediate transfer member is further transferred to a recording medium (for example, paper). Transcript to. Thereafter, a fixing device (fixing method: nip fixing with a heating roller and a pressure roller) of the electrophotographic apparatus heats and pressurizes the toner to fix the toner on the recording medium. As a result, an image is formed on the recording medium. For example, a full color image can be formed by superposing four color toner images of black, yellow, magenta, and cyan. After the transfer step, the toner remaining on the photoreceptor is removed by a cleaning member (for example, a cleaning blade). The transfer method may be a direct transfer method in which the toner image on the photosensitive member is directly transferred to the recording medium without using the intermediate transfer member. The fixing method may be a belt fixing method.

  The toner according to the exemplary embodiment is an electrostatic latent image developing toner having the following configuration (hereinafter referred to as a basic configuration).

(Basic toner configuration)
The electrostatic latent image developing toner includes a plurality of toner particles including a toner core containing a binder resin and a release agent and a multilayered shell layer partially covering the surface of the toner core. The multilayer shell layer has a first shell layer containing a first polymer containing a repeating unit having an oxazoline group, a second shell layer containing a second polymer containing a repeating unit having a carboxyl group, and an oxazoline group And a third shell layer containing a third polymer including repeating units. The first shell layer, the second shell layer, and the third shell layer have a laminated structure in the order of the first shell layer, the second shell layer, and the third shell layer from the toner core side. The second shell layer is in contact with an area of the surface area of the toner core that is not covered with the first shell layer. Hereinafter, a shell layer containing a polymer containing a repeating unit having an oxazoline group is referred to as an “oxazoline group-containing shell layer”, and a shell layer containing a polymer containing a repeating unit having a carboxyl group is referred to as a “carboxyl group-containing shell layer”. Each may be listed.

  The inventor of the present application has made studies on core-shell type toner particles having an oxazoline group-containing shell layer, and solved the following problems by the above basic configuration.

  The oxazoline group-containing shell layer is easily bonded strongly to the binder resin of the toner core, but is not easily bonded to the release agent of the toner core. For this reason, the area where the release agent is present in the surface area of the toner core is not easily covered with the first shell layer. Since the release agent is exposed in an area not covered with the first shell layer in the surface area of the toner core, the toner releasability is improved. However, the release agent is easily detached from the toner particles. In addition, the release of the release agent from the toner particles can be suppressed by forming a very thick oxazoline group-containing shell layer on the surface of the toner core and completely covering the entire surface of the toner core with the oxazoline group-containing shell layer. Is also possible. However, with such a method, it becomes difficult to ensure sufficient heat-resistant storage stability of the toner.

  In the toner having the above basic configuration, the toner particles have a multilayer structure shell layer. The multilayer structure shell layer includes a first shell layer, a second shell layer, and a third shell layer. The carboxyl group in the second shell layer is easily chemically bonded to the oxazoline group. For this reason, the second shell layer is interposed between the first shell layer and the third shell layer and functions to tie the first shell layer and the third shell layer together. In the toner having the above basic configuration, a multilayered shell layer (specifically, three or more shell layers) facilitates ensuring sufficient heat-resistant storage stability of the toner. Further, the second shell layer functions to suppress detachment of the release agent from the toner particles by contacting an area of the surface area of the toner core that is not covered with the first shell layer.

  In order to suppress release of the release agent from the toner particles while ensuring sufficient release property of the toner, the release agent in the surface region of the toner core is exposed without being covered by the multilayer shell layer. The ratio of the region (hereinafter sometimes referred to as the releasing agent exposure ratio) is preferably 1% or more and less than 10% in terms of the peripheral length ratio measured from the cross section of the toner particles.

  In order to obtain a toner having excellent charging properties, it is preferable that the outermost layer of the multilayer structure shell layer contains a polymer containing a repeating unit having an oxazoline group. Oxazoline groups tend to exhibit strong positive chargeability in an unopened state. Even when the toner core contains a resin having a relatively strong negative chargeability (more specifically, a polyester resin or a styrene-acrylic acid resin), the oxazoline group-containing shell located in the outermost layer of the multilayer shell layer The layer easily suppresses the charge attenuation of the toner. In addition, in order to suppress excessive charging of the toner, it is possible to moderately weaken the positive chargeability of the shell layer by opening a suitable amount of oxazoline groups in the shell layer. In the toner having the above basic configuration, the innermost layer of the multilayer structure shell layer is the first shell layer.

  In order to obtain a toner having excellent chargeability, the outermost layer of the multilayer structure shell layer is an oxazoline group-containing shell layer, and the amount of oxazoline groups contained in 1 g of toner is 0.50 μmol or more and 1.50 μmol or less. It is particularly preferred. The “amount of oxazoline group” corresponds to the total amount of both the oxazoline group that remains unopened and the ring-opened oxazoline group. In addition, the measuring method of the quantity of an oxazoline group is the method shown in the Example mentioned later, or its alternative method.

  The multilayer shell layer preferably has a multilayer structure in which an oxazoline group-containing shell layer and a carboxyl group-containing shell layer are alternately laminated from the toner core side, and the innermost layer and the outermost layer are each an oxazoline group-containing shell layer. The number of layers of the multilayer structure shell layer (the total of the number of oxazoline group-containing shell layers and the number of carboxyl group-containing shell layers) is preferably an odd number, 3 layers, 5 layers, 7 layers, 9 layers, 11 layers , 13 or 15 layers are particularly preferred. From the viewpoint of toner productivity and fixability, the thickness of the multilayer shell layer is preferably 50 nm or more and 300 nm or less.

  In order to strengthen the bond between the binder resin of the toner core and the first shell layer, in the above basic configuration, the toner core preferably contains a polyester resin as the binder resin. The oxazoline group in the first shell layer is easily chemically bonded to the carboxyl group of the polyester resin. Even when a pulverized core is used as the toner core, the toner core contains a polyester resin, so that a uniform first shell layer can be easily formed on the surface of the toner core. By strengthening the bond between the binder resin of the toner core and the first shell layer, the detachment of the shell layer from the toner particles can be suppressed.

  In the toner having the above basic configuration, a set of an oxazoline group-containing shell layer (lower layer) and a carboxyl group-containing shell layer (upper layer) (laminated shell layer) may be further added on the third shell layer. For example, the multilayer shell layer further includes a fourth shell layer containing a fourth polymer containing a repeating unit having a carboxyl group, and a fifth shell layer containing a fifth polymer containing a repeating unit having an oxazoline group. , The first shell layer, the second shell layer, the third shell layer, the fourth shell layer, and the fifth shell layer from the toner core side, the first shell layer, the second shell layer, the third shell layer, and the fourth shell You may have the laminated structure of the order of a layer and a 5th shell layer. From the viewpoint of toner productivity, the first shell layer, the third shell layer, and the fifth shell layer are made of the same material, and the second shell layer and the fourth shell layer are the same material. It is preferable that it is comprised. The outermost layer of the multilayer structure shell layer preferably contains a polymer containing a repeating unit having an oxazoline group.

  In order to produce the toner having the above basic configuration, the following production method is particularly preferred.

(Preferable toner production method)
The method for producing a toner for developing an electrostatic latent image includes a first shell layer forming step, a second shell layer forming step, and a third shell layer forming step.
In the first shell layer forming step, an aqueous medium containing a toner core containing a binder resin and a release agent and an oxazoline group-containing polymer is heated to partially cover the surface of the toner core and to form an oxazoline group. Forming a first shell layer containing a first polymer comprising repeating units having;
In the second shell layer forming step, after the first shell layer forming step, the carboxyl group-containing polymer is put in an aqueous medium, and the carboxyl group-containing polymer is placed in the aqueous medium, the surface of the first shell layer, and the toner core. The carboxyl group-containing polymer is polymerized on the first shell layer by heating the aqueous medium and polymerizing the carboxyl group-containing polymer in a state where the surface region is in contact with the region not covered with the first shell layer. A second shell layer containing a second polymer containing repeating units having is formed.
In the third shell layer forming step, after the second shell layer forming step, an oxazoline group-containing polymer is placed in the aqueous medium, and the aqueous medium is heated, whereby the repeating unit having an oxazoline group on the second shell layer. Forming a third shell layer containing a third polymer comprising

  Hereinafter, the materials for forming the first shell layer, the second shell layer, and the third shell layer may be referred to as a first shell material, a second shell material, and a third shell material, respectively.

  In order to suppress dissolution or elution of the toner core components (particularly the binder resin and the release agent) during the formation of the shell layer, it is preferable to form the shell layer in an aqueous medium. The aqueous medium is a medium containing water as a main component (more specifically, pure water or a mixed liquid of water and a polar medium). The aqueous medium may function as a solvent. A solute may be dissolved in the aqueous medium. The aqueous medium may function as a dispersion medium. The dispersoid may be dispersed in the aqueous medium. As a polar medium in the aqueous medium, for example, alcohol (more specifically, methanol or ethanol) can be used. The boiling point of the aqueous medium is about 100 ° C.

  The second shell material (carboxyl group-containing polymer) is preferably attached to the surface of the first shell layer in a gel state. When the second shell material having a relatively high viscosity adheres to the surface of the first shell layer, the second shell layer moves from the upper surface of the first shell layer toward the toner core along the side surface of the first shell layer, It becomes easy to contact the area | region which is not covered with the 1st shell layer among surface area of this.

  Hereinafter, an example of toner particles contained in the toner having the above-described basic configuration will be described with reference to FIGS.

  The toner particles 10 shown in FIG. 1 include toner base particles 10a and external additives (a plurality of external additive particles 13). The toner base particle 10 a includes a toner core 11 and a multilayered shell layer 12 that partially covers the surface of the toner core 11. The toner core 11 contains a binder resin and a release agent. In FIG. 1, the surface F <b> 1 indicates the surface of the toner core 11, and the surface F <b> 2 indicates the surface of the multilayer structure shell layer 12. Each of the plurality of external additive particles 13 (for example, silica particles) is attached to the surface (surface F1 or F2) of the toner base particle 10a.

  FIG. 2 is an enlarged cross-sectional view showing a part of the surface of the toner base particle 10a shown in FIG. 1 (particularly, the multilayer structure shell layer 12). For convenience of explanation, FIG. 2 shows only the toner base particles 10a without the external additive in the toner particles 10.

  In the example shown in FIG. 2, the multilayer shell layer 12 includes a first shell layer 12a, a second shell layer 12b, a third shell layer 12c, a fourth shell layer 12d, and a fifth shell layer 12e. . The first shell layer 12a, the third shell layer 12c, and the fifth shell layer 12e are each an oxazoline group-containing shell layer, and the second shell layer 12b and the fourth shell layer 12d are each a carboxyl group-containing shell layer. The first shell layer 12a, the second shell layer 12b, the third shell layer 12c, the fourth shell layer 12d, and the fifth shell layer 12e are the first shell layer 12a, the second shell layer 12b, the second shell layer 12e from the toner core 11 side. It has a laminated structure in the order of a three shell layer 12c, a fourth shell layer 12d, and a fifth shell layer 12e. The multilayer structure shell layer 12 is a shell layer having a five-layer structure. The innermost layer of the multilayer structure shell layer 12 is a first shell layer 12a, and the outermost layer of the multilayer structure shell layer 12 is a fifth shell layer 12e. Hereinafter, among the multilayered shell layers, the shell layer located on the lower layer side than the specific shell layer may be referred to as the lower shell layer of the specific shell layer. For example, in the multilayer shell layer 12, the lower shell layer of the fourth shell layer 12d means the first shell layer 12a, the second shell layer 12b, and the third shell layer 12c.

  A plurality of release agent domains 11 a are dispersed in the toner core 11. On the surface of the toner core 11, there is a region where the release agent domain 11 a is exposed without being covered by the first shell layer 12 a (hereinafter, sometimes referred to as a first release agent exposure region). The second shell layer 12b extends to the toner core 11 along the first shell layer 12a, and the first release agent exposed region (the release agent is exposed to the first shell layer 12a) in the surface region of the toner core 11. The area). Since the second shell layer 12b presses the edge portion of the release agent domain 11a, detachment of the release agent domain 11a from the toner particles 10 is suppressed.

  In addition, the release agent domain 11a is exposed on the surface of the toner core 11 without being covered by the lower shell layers (first shell layer 12a, second shell layer 12b, and third shell layer 12c) of the fourth shell layer 12d. Area (hereinafter, may be referred to as a second release agent exposure area). The second release agent exposure area is narrower than the first release agent exposure area. The fourth shell layer 12d extends to the toner core 11 along the lower shell layer (the first shell layer 12a, the second shell layer 12b, and the third shell layer 12c) of the fourth shell layer 12d. Among them, the second release agent exposed region (region where the release agent is exposed to the first shell layer 12a, the second shell layer 12b, and the third shell layer 12c) is in contact. Together with the second shell layer 12b, the fourth shell layer 12d presses the edge portion of the release agent domain 11a, so that the release agent domain 11a is prevented from being detached from the toner particles 10.

  In FIG. 2, the release agent exposure region R <b> 2 is a region in the surface region of the toner core 11 where the release agent is exposed without being covered by the multilayer structure shell layer 12 (hereinafter referred to as a third release agent exposure region). In some cases). Each of the second shell layer 12 b and the fourth shell layer 12 d is in contact with a region where the release agent is present in the surface region of the toner core 11. For this reason, the second shell layer 12b and the fourth shell layer 12d act so as to reduce the release agent exposure rate (the ratio of the third release agent exposure region to the surface region of the toner core 11).

  FIG. 3A is an enlarged plan view showing a part of the surface (surface F1) of the toner core 11 in a state before the multilayer structure shell layer 12 is formed. FIG. 3B is a cross-sectional view of the toner core 11 shown in FIG.

  As shown in FIGS. 3A and 3B, the plurality of release agent domains 11 a are exposed on the surface of the toner core 11, so that the release agent domain 11 a is formed on the surface (surface F <b> 1) of the toner core 11. There are a plurality of regions (release agent exposure regions R0) where the is exposed. For example, the pulverized core can be obtained by melt-kneading a material containing a binder resin and a release agent and pulverizing the obtained melt-kneaded product. The release agent is exposed on the surface of the obtained pulverized core. Note that the shape (planar shape) of the release agent exposure region R0 is not necessarily circular as shown in FIG. The shape (planar shape) of the release agent exposure region R0 may be an ellipse or a shape close to a polygon.

  FIG. 4A is a plan view showing particles in which the first shell layer 12a is formed on the surface of the toner core 11 shown in FIG. 3A (hereinafter sometimes referred to as first layer coated particles). . FIG. 4B is a cross-sectional view of the first layer-coated particles shown in FIG.

  For example, an aqueous medium containing a toner core 11 containing a binder resin and a release agent and a first shell material (specifically, an oxazoline group-containing polymer) is heated with stirring, so that the surface of the toner core 11 is partially covered. The first shell layer 12a that covers the surface can be formed. The first shell layer 12a is an oxazoline group-containing shell layer. The oxazoline group-containing shell layer easily binds strongly to the binder resin of the toner core 11, but does not easily bond to the release agent of the toner core 11. For this reason, on the surface of the first layer-coated particles, as shown in FIGS. 4A and 4B, the region where the release agent domain 11a is present in the surface region of the toner core 11 is the first shell. It is easy to selectively expose the layer 12a. In each of FIG. 4A and FIG. 4B, the release agent exposure region R1 includes a first release agent exposure region (the release agent domain 11a covers the first shell layer 12a on the surface of the toner core 11). It corresponds to an unexposed area).

  When the first shell layer 12a is not formed in the area where the release agent is present in the surface area of the toner core 11, and the first shell layer 12a is reliably formed in the other area, the release is performed. The mold agent exposure region R1 coincides with the release agent exposure region R0 (FIGS. 3A and 3B). However, in actual manufacturing, the region where the release agent domain 11a exists in the surface region of the toner core 11 is selectively exposed to the first shell layer 12a, so that the release agent exposure region R1 is the release agent. Although it has a form close to the exposure region R0, the release agent exposure region R1 and the release agent exposure region R0 do not always coincide with each other.

  For example, a second shell material (specifically, a carboxyl group-containing polymer) is placed in an aqueous medium containing the first layer-coated particles (see FIGS. 4A and 4B), The second shell material is heated by heating the aqueous medium with the second shell material in contact with the surface of the first shell layer 12a and the region of the surface area of the toner core 11 that is not covered with the first shell layer 12a. By polymerizing, the second shell layer 12b can be formed on the first shell layer 12a. The second shell layer 12b is a carboxyl group-containing shell layer and has high adhesion to the toner core 11 and the first shell layer 12a. The second shell layer 12b faces the toner core 11 along the upper surface and side surface of the first shell layer 12a, and the first release agent exposed region (releasing agent with respect to the first shell layer 12a) of the surface region of the toner core 11 is formed. Is considered to contact the exposed area). Hereinafter, the particles in which the second shell layer is formed on the surface of the first layer coated particles may be referred to as second layer coated particles.

  After forming the second shell layer 12b, a third shell layer 12c, a fourth shell layer 12d, and a fifth shell layer 12e are further formed on the surface of the second layer-coated particles, as shown in FIG. A multilayer shell layer 12 can be formed on the surface of the toner core 11. The third shell layer 12c and the fifth shell layer 12e can be formed in the same manner as the first shell layer 12a. The fourth shell layer 12d can be formed in the same manner as the second shell layer 12b.

  FIG. 5 is an enlarged cross-sectional view showing a part of FIG. FIG. 6 is a view showing the positions of the edges of the carboxyl group-containing shell layer in the multilayer structure shell layer 12. In each of FIGS. 5 and 6, the edge E1 indicates the edge (contour) of the first release agent exposure region, the edge E2 indicates the edge (contour) of the second release agent exposure region, and the edge E3 is The edge (contour) of the 3rd mold release agent exposure area | region is shown.

  In the example shown in FIGS. 5 and 6, the first release agent exposure region (release agent exposure region R1 shown in FIG. 4 (a)) matches the release agent exposure region R0 shown in FIG. 3 (a). . The edge E1 coincides with the edge of the first shell layer 12a (the oxazoline group-containing shell layer). The edge E2 coincides with the edge of the second shell layer 12b (carboxyl group-containing shell layer). The edge E3 coincides with the edge of the fourth shell layer 12d (carboxyl group-containing shell layer). A region surrounded by the edge E1 corresponds to a first release agent exposure region (release agent exposure region R1). A region surrounded by the edge E2 corresponds to a second release agent exposure region. A region surrounded by the edge E3 corresponds to a third release agent exposure region (release agent exposure region R2).

In order to form a good quality multilayer structure shell layer on the surface of the toner core, in the multilayer structure shell layer defined by the basic structure described above, the first polymer contained in the first shell layer and the third shell layer contain It is preferable that the third polymer is a copolymer of two or more kinds of vinyl compounds each independently containing at least a compound represented by the following formula (1). The vinyl compound can be polymerized by addition polymerization (“C═C” → “—C—C—”) by a carbon double bond “C═C” to become a polymer (resin). The vinyl compound is a compound having a vinyl group (CH ₂ ═CH—) or a group in which hydrogen in the vinyl group is substituted. Examples of the vinyl compound include ethylene, propylene, butadiene, vinyl chloride, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, or styrene.

In Formula (1), R ¹ represents a hydrogen atom or an alkyl group (which may be linear, branched or cyclic) which may have a substituent. Examples of the substituent in the case where R ¹ represents an alkyl group having a substituent include phenyl group. R ¹ is particularly preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group. For example, in 2-vinyl-2-oxazoline, R ¹ in formula (1) represents a hydrogen atom.

  As a material for forming the oxazoline group-containing shell layer, for example, an oxazoline group-containing polymer aqueous solution (“Epocross (registered trademark) WS series” manufactured by Nippon Shokubai Co., Ltd.) can be used. “Epocross WS-300” and “Epocross WS-700” each include a polymer of a monomer (resin raw material) containing 2-vinyl-2-oxazoline and one or more (meth) acrylic acid alkyl esters. .

  The compound represented by the above formula (1) (hereinafter referred to as the compound (1)) becomes a repeating unit represented by the following formula (1-1) by addition polymerization to constitute a copolymer.

The repeating unit represented by formula (1-1) (hereinafter referred to as repeating unit (1-1)) has an unopened oxazoline group. The unopened oxazoline group has a cyclic structure and exhibits strong positive chargeability. An unopened oxazoline group easily reacts with a functional group of the resin (more specifically, a carboxyl group, an aromatic sulfanyl group, an aromatic hydroxyl group, or the like). For example, when the repeating unit (1-1) reacts with a carboxyl group present on the surface of the resin R ⁰ , the oxazoline group is opened as shown in the following formula (1-2), and an amide ester bond is formed. Hereinafter, the repeating unit represented by Formula (1-2) is referred to as a repeating unit (1-2).

The oxazoline group-containing shell layer in the multilayer shell layer contains a copolymer of two or more kinds of vinyl compounds (hereinafter referred to as a specific copolymer) containing at least the compound represented by the formula (1). In such a case, the repeating unit (1-1) is present in the specific copolymer. The oxazoline group of the repeating unit (1-1) can open a ring by reacting with a functional group present on the surface of the binder resin constituting the toner core to form a chemical bond, for example. For example, when the binder resin of the toner core is a polyester resin, the oxazoline group of the repeating unit (1-1) reacts with the carboxyl group of the polyester resin (resin R ⁰ shown in Formula (1-2)). Thus, it is considered that the repeating unit (1-2) is generated.

  In order to obtain a toner suitable for image formation, the glass transition point (Tg) of the toner core is preferably 30 ° C. or higher and 55 ° C. or lower. In order to obtain a toner suitable for image formation, the softening point (Tm) of the toner core is preferably 70 ° C. or higher and 105 ° C. or lower.

In order to obtain a toner suitable for image formation, the volume median diameter (D ₅₀ ) of the toner core is preferably 4 μm or more and 9 μm or less.

  Next, the toner core (binder resin and internal additive), shell layer, and external additive will be described in order. Depending on the use of the toner, unnecessary components may be omitted.

[Toner core]
(Binder resin)
In the toner core, the binder resin generally occupies most of the components (for example, 85% by mass or more). For this reason, it is considered that the properties of the binder resin greatly affect the properties of the entire toner core. By using a combination of a plurality of types of resins as the binder resin, the properties of the binder resin (more specifically, the hydroxyl value, acid value, Tg, Tm, etc.) can be adjusted. When the binder resin has an ester group, a hydroxyl group, an ether group, an acid group, or a methyl group, the toner core tends to be anionic, and when the binder resin has an amino group, the toner core The tendency to become cationic becomes stronger.

  The binder resin for the toner core is preferably a thermoplastic resin (more specifically, a styrene-acrylic acid resin or a polyester resin), and particularly preferably a polyester resin.

  For example, the styrene-acrylic acid resin is a copolymer of one or more styrene monomers and one or more acrylic monomers. The polyester resin can be obtained by polycondensation of one or more polyhydric alcohols and one or more polyhydric carboxylic acids.

  As the alcohol for synthesizing the polyester resin, for example, a dihydric alcohol (more specifically, an aliphatic diol or bisphenol) or a trihydric or higher alcohol as shown below can be preferably used. As the carboxylic acid for synthesizing the polyester resin, for example, divalent carboxylic acids or trivalent or higher carboxylic acids as shown below can be suitably used. The polyester resin may contain a repeating unit derived from another monomer (a monomer that is neither a polyhydric alcohol nor a polyvalent carboxylic acid).

  Suitable examples of the aliphatic diol include diethylene glycol, triethylene glycol, neopentyl glycol, 1,2-propanediol, α, ω-alkanediol (more specifically, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, etc. ), 2-butene-1,4-diol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, or polytetramethylene glycol.

  Preferable examples of bisphenol include bisphenol A, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, or bisphenol A propylene oxide adduct.

  Preferable examples of trihydric or higher alcohols include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butane. Triol, 1,2,5-pentanetriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, or 1,3,5- Trihydroxymethylbenzene is mentioned.

  Preferable examples of the divalent carboxylic acid include aromatic dicarboxylic acid (more specifically, phthalic acid, terephthalic acid, or isophthalic acid), α, ω-alkanedicarboxylic acid (more specifically, malonic acid). Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, or 1,10-decanedicarboxylic acid), unsaturated dicarboxylic acid (more specifically, maleic acid, fumaric acid, citraconic acid, itaconic acid, Or glutaconic acid or the like), or cycloalkane dicarboxylic acid (more specifically, cyclohexane dicarboxylic acid or the like).

  Preferred examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) Examples include methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, or empole trimer acid.

  As the binder resin, an amorphous polyester resin is particularly preferable. The toner core may contain a crystalline polyester resin. By containing a crystalline polyester resin in the toner core, sharp melt properties can be imparted to the toner core. In order to achieve both heat-resistant storage stability and low-temperature fixability of the toner, the amount of the crystalline polyester resin contained in the toner core is the total amount of the polyester resin in the toner core (the sum of the crystalline polyester resin and the amorphous polyester resin). It is preferable that they are 5 mass% or more and 20 mass% or less with respect to quantity.

  As a first preferred example of the non-crystalline polyester resin, bisphenol (for example, bisphenol A ethylene oxide adduct and / or bisphenol A propylene oxide adduct) is used as the alcohol component, and aromatic dicarboxylic acid is used as the acid component. Non-crystalline polyester resin containing (for example, terephthalic acid) is mentioned.

  As a second preferred example of the non-crystalline polyester resin, bisphenol (for example, bisphenol A ethylene oxide adduct and / or bisphenol A propylene oxide adduct) is used as the alcohol component, and unsaturated dicarboxylic acid is used as the acid component. Non-crystalline polyester resin containing (for example, fumaric acid) is mentioned.

  Preferred examples of the crystalline polyester resin include one or more α, ω-alkanediols having 2 to 6 carbon atoms (for example, two types of α, ω-alkanediols: 1,4-butane having 4 carbon atoms). Diols and 1,6-hexanediol having 6 carbon atoms) and α, ω-alkanedicarboxylic acids having 4 to 10 carbon atoms (including carbons of two carboxyl groups) (for example, having 4 carbon atoms) A polymer of a monomer (resin raw material) containing succinic acid), one or more styrene monomers (for example, styrene), and one or more acrylic monomers (for example, acrylic acid).

  In order for the toner core to have an appropriate sharp melt property, it is preferable to contain a crystalline polyester resin having a crystallinity index of 0.90 or more and 1.20 or less in the toner core. The crystallinity index of the resin corresponds to the ratio (= Tm / Mp) of the softening point (Tm) of the resin to the melting point (Mp) of the resin. For amorphous resins, it is often impossible to measure a clear Mp. The crystallinity index of the crystalline polyester resin can be adjusted by changing the type or amount (blending ratio) of the material for synthesizing the crystalline polyester resin. The toner core may contain only one type of crystalline polyester resin, or may contain two or more types of crystalline polyester resins.

  When the binder resin contained most in the toner core on a mass basis is an amorphous polyester resin, in order to ensure sufficient toner strength and fixability, the number average molecular weight of the amorphous polyester resin ( Mn) is preferably 1000 or more and 2000 or less.

(Coloring agent)
The toner core may contain a colorant. As the colorant, a known pigment or dye can be used according to the color of the toner. In order to obtain a toner suitable for image formation, the amount of the colorant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

  The toner core may contain a black colorant. An example of a black colorant is carbon black. The black colorant may be a colorant that is toned to black using a yellow colorant, a magenta colorant, and a cyan colorant.

  The toner core may contain a color colorant such as a yellow colorant, a magenta colorant, or a cyan colorant.

  As the yellow colorant, for example, one or more compounds selected from the group consisting of condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and arylamide compounds can be used. Examples of the yellow colorant include C.I. I. Pigment Yellow (3, 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155 168, 174, 175, 176, 180, 181, 191, or 194), naphthol yellow S, Hansa yellow G, or C.I. I. Vat yellow can be preferably used.

  The magenta colorant is, for example, selected from the group consisting of condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. One or more compounds can be used. Examples of the magenta colorant include C.I. I. Pigment Red (2, 3, 5, 6, 7, 19, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 150, 166, 169, 177 184, 185, 202, 206, 220, 221 or 254) can be preferably used.

  As the cyan colorant, for example, one or more compounds selected from the group consisting of a copper phthalocyanine compound, an anthraquinone compound, and a basic dye lake compound can be used. Examples of cyan colorants include C.I. I. Pigment blue (1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, or 66), phthalocyanine blue, C.I. I. Bat Blue, or C.I. I. Acid blue can be preferably used.

(Release agent)
The toner core contains a release agent. The release agent is used, for example, for the purpose of improving the fixing property or offset resistance of the toner. In order to improve the fixing property or offset resistance of the toner, the amount of the release agent is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

  As the release agent, wax is preferable. Examples of the wax include ester wax, polyethylene wax, polypropylene wax, fluororesin wax (for example, Teflon (registered trademark) -containing wax), Fischer-Tropsch wax, paraffin wax, or montan wax. One type of release agent may be used alone, or two or more types of release agents may be used in combination.

  When the binder resin of the toner core is a polyester resin, in order to improve the compatibility between the binder resin and the release agent in the toner core, the release agent is an ester wax (for example, carnauba wax), or Polyethylene wax is preferred. When the binder resin of the toner core is a styrene resin or a copolymer thereof, in order to improve the compatibility between the binder resin and the release agent in the toner core, the release agent is a paraffin wax or a fisher. Tropsch wax is preferred. In order to improve the compatibility between the binder resin and the release agent, a compatibilizer may be added to the toner core.

  In order to improve the fixing property and offset resistance of the toner, ester wax is preferable. Examples of the ester wax include natural ester wax (for example, carnauba wax or rice wax), or synthetic ester wax. In order to ensure sufficient heat-resistant storage stability and low-temperature fixability of the toner while suppressing charge attenuation of the toner, it is preferable that the toner core contains two or more release agents. Synthetic ester wax and natural ester wax It is particularly preferred to contain both (eg carnauba wax). By using a synthetic ester wax as a mold release agent, the melting point of the mold release agent can be easily adjusted to a desired range. A synthetic ester wax can be synthesized, for example, by reacting an alcohol and a carboxylic acid (or carboxylic acid halide) in the presence of an acid catalyst. The raw material of the synthetic ester wax may be, for example, a substance derived from a natural product such as a long-chain fatty acid prepared from natural fats and oils or a commercially available synthetic product.

(Charge control agent)
The toner core may contain a charge control agent. The charge control agent is used, for example, for the purpose of improving the charging stability or charging rising property of the toner. The toner charge rising characteristic is an indicator of whether or not the toner can be charged to a predetermined charge level in a short time.

  By adding a negatively chargeable charge control agent (more specifically, an organometallic complex or a chelate compound) to the toner core, the anionicity of the toner core can be enhanced. Further, by adding a positively chargeable charge control agent (more specifically, pyridine, nigrosine, quaternary ammonium salt, or the like) to the toner core, the toner core can be made more cationic. However, if sufficient chargeability is ensured in the toner, it is not necessary to include a charge control agent in the toner core.

(Magnetic powder)
The toner core may contain magnetic powder. Examples of magnetic powder materials include ferromagnetic metals (more specifically, iron, cobalt, nickel, or alloys containing one or more of these metals), ferromagnetic metal oxides (more specifically, Ferrite, magnetite, chromium dioxide, or the like) or a material subjected to ferromagnetization treatment (more specifically, a carbon material or the like imparted with ferromagnetism by heat treatment) can be suitably used. One type of magnetic powder may be used alone, or a plurality of types of magnetic powder may be used in combination. In order to suppress elution of metal ions (for example, iron ions) from the magnetic powder, it is preferable to surface-treat the magnetic powder.

[Multilayer shell layer]
The oxazoline group-containing shell layer (more specifically, the first shell layer or the third shell layer) in the multilayer structure shell layer is composed of one or more vinyl compounds represented by the above formula (1), 1 It is preferable to contain a copolymer with other vinyl compounds of a kind or more (a vinyl compound other than the compound represented by the above formula (1)).

  The other vinyl compound is preferably at least one vinyl compound selected from the group consisting of styrene monomers and acrylic monomers. Suitable examples of the styrenic monomer include styrene, alkyl styrene (more specifically, α-methyl styrene, p-ethyl styrene, 4-tert-butyl styrene, etc.), hydroxy styrene (more specifically, p-hydroxystyrene, m-hydroxystyrene, or the like), or halogenated styrene (specifically, α-chlorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, or the like). Moreover, as a suitable example of an acrylic acid monomer, (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid aryl ester, (meth) acrylonitrile, or (Meth) acrylamide is mentioned.

  For example, when the other vinyl compound is an alkyl acrylate ester that may have a substituent on the alkyl group, the alkyl acrylate ester is, for example, a repeating unit represented by the following formula (2) by addition polymerization. To constitute a copolymer.

In formula (2), R ² represents an alkyl group (which may be linear, branched or cyclic) which may have a substituent. As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferable. When R ² represents an alkyl group having a substituent, the substituent of the alkyl group is preferably a hydroxyl group. R ² is preferably a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, 2-ethylhexyl group, hydroxyethyl group, hydroxypropyl group, or hydroxybutyl group. .

  For example, when the other vinyl compound is a methacrylic acid alkyl ester which may have a substituent, the methacrylic acid alkyl ester which may have a substituent is represented by, for example, the following formula (3) by addition polymerization. To form a copolymer.

In formula (3), R ³ represents an alkyl group (which may be linear, branched or cyclic) which may have a substituent. As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferable. When R ³ represents an alkyl group having a substituent, a hydroxyl group is preferable as the substituent of the alkyl group. R ³ is preferably a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a 2-ethylhexyl group, a hydroxyethyl group, a hydroxypropyl group, or a hydroxybutyl group. .

  For example, when the other vinyl compound is a styrene monomer, the styrene monomer becomes a repeating unit represented by, for example, the following formula (4) by addition polymerization to constitute a copolymer.

In formula (4), R ^{41 to} R ⁴⁷ each independently represent a hydrogen atom or an arbitrary substituent. R ^{41 to} R ⁴⁵ are each independently preferably a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent, a halogen atom, a methyl group, An ethyl group or a hydroxyl group is particularly preferred. R ⁴⁶ and R ⁴⁷ are each independently preferably a hydrogen atom or a methyl group.

[External additive]
An external additive (specifically, a powder containing a plurality of external additive particles) may be adhered to the surface of the toner base particles. Unlike the internal additive, the external additive does not exist inside the toner base particles, but selectively exists only on the surface of the toner base particles (surface layer portion of the toner particles). For example, toner base particles (specifically, a powder containing a plurality of toner base particles) and an external additive (specifically, a powder containing a plurality of external additive particles) are stirred together to form toner base particles. External additive particles can be adhered to the surface of the substrate. The toner base particles and the external additive particles do not chemically react with each other and are physically bonded instead of chemically. The strength of the bond between the toner base particles and the external additive particles depends on the stirring conditions (more specifically, the stirring time, the rotation speed of the stirring, etc.), the particle diameter of the external additive particles, and the shape of the external additive particles. And the surface condition of the external additive particles. In order to suppress the detachment of the external additive particles from the toner particles, it is preferable that the external additive particles are strongly bonded to the surface of the toner base particles. The external additive particles may be fixed on the surface of the toner base particles by mechanical bonding by embedding. For example, for external additive particles having a large particle size, the toner base particles and the external additive are vigorously stirred to embed a part (bottom part) of the external additive particles in the surface layer of the toner base particles. External additive particles can be fixed on the surface of the mother particles. However, if the particle diameter of the external additive particles is too large, it is difficult to fix the external additive particles on the surface of the toner base particles. It is preferable that the external additive particles for improving the fluidity of the toner adhere to the surface of the toner base particles mainly by van der Waals force or electrostatic force.

  As inorganic particles (external additive particles), particles of silica particles or metal oxides (more specifically, alumina, titanium oxide, magnesium oxide, zinc oxide, strontium titanate, barium titanate, etc.) are suitable. Can be used for One type of external additive may be used alone, or a plurality of types of external additives may be used in combination.

  The external additive particles may be surface-treated. For example, when silica particles are used as the external additive particles, hydrophobicity and / or positive chargeability may be imparted to the surface of the silica particles by the surface treatment agent. Examples of the surface treatment agent include a coupling agent (more specifically, a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent), a silazane compound (for example, a chain silazane compound or a cyclic silazane compound). ) Or silicone oil (more specifically, dimethyl silicone oil or the like) can be preferably used. As the surface treatment agent, a silane coupling agent or a silazane compound is particularly preferable. Preferable examples of the silane coupling agent include silane compounds (more specifically, methyltrimethoxysilane or aminosilane). A preferred example of the silazane compound is HMDS (hexamethyldisilazane). When the surface of the silica substrate (untreated silica particles) is treated with the surface treatment agent, a large number of hydroxyl groups (—OH) present on the surface of the silica substrate are partially or entirely derived from the surface treatment agent. Substituted with a functional group. As a result, silica particles having a functional group derived from the surface treating agent (specifically, a functional group that is more hydrophobic and / or positively charged than the hydroxyl group) on the surface can be obtained.

[Toner Production Method]
Hereinafter, preferable conditions of the above-mentioned “preferable toner manufacturing method” will be described.

(Preparation of toner core)
In order to easily obtain a high-quality toner core, it is preferable to produce the toner core by an aggregation method or a pulverization method.

  Hereinafter, an example of the pulverization method will be described. First, a binder resin, a release agent, and an optional internal additive (for example, at least one of a colorant, a charge control agent, and magnetic powder) are mixed. Subsequently, the obtained mixture is melt-kneaded. Subsequently, the obtained melt-kneaded product is pulverized, and the obtained pulverized product is classified. As a result, a toner core having a desired particle size can be obtained.

  Hereinafter, an example of the aggregation method will be described. First, the fine particles of the binder resin, the release agent, and the colorant are aggregated in an aqueous medium to obtain aggregated particles containing the binder resin, the release agent, and the colorant. Subsequently, the obtained aggregated particles are heated to unite the components contained in the aggregated particles. As a result, a toner core dispersion is obtained. Thereafter, an unnecessary substance (such as a surfactant) is removed from the dispersion liquid of the toner core to obtain the toner core.

(Formation of multilayer structure shell layer: Formation of shell layer containing oxazoline group)
The oxazoline group-containing shell layer is formed on predetermined target particles (more specifically, a toner core or second layer-coated particles). After adjusting the pH of the aqueous medium (for example, ion-exchanged water), target particles (for example, a toner core containing a binder resin and a release agent) and a shell material (for example, an oxazoline group-containing water-soluble polymer) in the aqueous medium And put. Subsequently, while stirring the aqueous medium containing the target particles and the shell material, the temperature of the aqueous medium is set at a predetermined holding temperature at a predetermined speed (for example, a speed selected from 0.1 ° C./min to 3 ° C./min). (Eg, a temperature selected from 45 ° C. to 80 ° C.). Furthermore, the temperature of the aqueous medium is maintained at the above holding temperature for a predetermined time (for example, a time selected from 30 minutes to 4 hours) while stirring the aqueous medium. It is considered that the reaction (immobilization of the shell layer) proceeds between the target particles and the shell material while the temperature of the aqueous medium is maintained at a high temperature (or during the temperature increase). For example, it is considered that the oxazoline group of the shell material is opened by reacting with a functional group present on the surface of the binder resin constituting the target particle, and the target particle and the oxazoline group-containing shell layer are chemically bonded. . The oxazoline group-containing shell layer is easily bonded strongly to the resin, but is difficult to bond to the release agent. Therefore, when the target particle is a toner core, an oxazoline group-containing shell layer that partially covers the surface of the toner core is easily formed. Of the surface area of the toner core, the area where the release agent is present is likely to be selectively exposed to the first shell layer.

  In order to form a homogeneous oxazoline group-containing shell layer, it is preferable to dissolve or disperse the shell material in the liquid by, for example, stirring the liquid containing the shell material. In order to adjust the chargeability of the toner, in a liquid containing a basic substance (more specifically, ammonia, sodium hydroxide, etc.) and / or a ring-opening agent (more specifically, acetic acid, etc.). It is preferable to form an oxazoline group-containing shell layer on the surface of the target particle. By changing the amount of each of the basic substance and the ring-opening agent, the amount of unopened oxazoline groups contained in the toner can be adjusted. As the amount of the basic substance in the liquid increases, the amount of unopened oxazoline groups tends to increase. It is considered that the basic substance neutralizes (traps) the carboxylic acid, thereby suppressing the ring-opening reaction (nucleophilic addition reaction to the carbonyl group) of the oxazoline group. On the other hand, since the ring-opening agent promotes the ring-opening reaction of the oxazoline group, the amount of the unopened oxazoline group tends to decrease as the amount of the ring-opening agent in the liquid increases.

  After the formation of the oxazoline group-containing shell layer, the aqueous medium is cooled. Subsequently, target particles on which an oxazoline group-containing shell layer is formed are obtained by solid-liquid separation (for example, filtration). Thereafter, the target particles may be washed and the washed target particles may be dried.

(Formation of multilayer structure shell layer: formation of carboxyl group-containing shell layer)
The carboxyl group-containing shell layer is formed on predetermined target particles (more specifically, first layer-coated particles and the like). After adjusting the pH of the aqueous medium containing the target particles, a shell material (for example, a carboxyl group-containing water-soluble polymer) is added to the aqueous medium. Subsequently, the aqueous medium containing the target particles and the shell material is stirred for a predetermined time (for example, a time selected from 30 minutes to 2 hours) to bring the shell material into contact with the surfaces of the target particles. Subsequently, the temperature of the aqueous medium is set at a predetermined rate (for example, a temperature selected from 0.1 ° C./min to 3 ° C./min) at a predetermined holding temperature (for example, a temperature selected from 45 ° C. to 80 ° C.). Raise to. Furthermore, the temperature of the aqueous medium is maintained at the above holding temperature for a predetermined time (for example, a time selected from 30 minutes to 4 hours) while stirring the aqueous medium. While the temperature of the aqueous medium is kept high (or during the temperature rise), the polymerization reaction of the carboxyl group-containing polymer attached to the surface of the target particle proceeds, and the carboxyl group-containing shell layer is formed on the surface of the target particle. It is formed. The target particles and the carboxyl group-containing shell layer are considered to be chemically bonded.

  After the formation of the carboxyl group-containing shell layer, the aqueous medium is cooled. Subsequently, target particles in which a carboxyl group-containing shell layer is formed are obtained by solid-liquid separation (for example, filtration). Thereafter, the target particles may be washed and the washed target particles may be dried.

  By alternately forming an oxazoline group-containing shell layer and a carboxyl group-containing shell layer on the surface of the toner core, toner mother particles having a multilayer structure shell layer partially covering the surface of the toner core are obtained. The number of multilayer shell layers (the total of the number of oxazoline group-containing shell layers and the number of carboxyl group-containing shell layers) is preferably an odd number. An external additive may be adhered to the surface of the toner base particles by the following external addition process.

(External addition process)
The toner base particles and the external additive (for example, silica particle powder) are mixed using a mixer (for example, FM mixer manufactured by Nippon Coke Kogyo Co., Ltd.), and the external additive is applied to the surface of the toner base particles. Adhere. When a spray dryer is used in the drying step, the drying step and the external addition step can be performed simultaneously by spraying a dispersion of an external additive (for example, silica particle powder) onto the toner base particles. it can.

  The contents and order of the toner manufacturing method can be arbitrarily changed according to the required configuration or characteristics of the toner. For example, when reacting a material (for example, a shell material) in a liquid, the material may be reacted in the liquid for a predetermined time after the material is added to the liquid, or the material is added to the liquid over a long period of time. Then, the material may be reacted in the liquid while adding the material to the liquid. In addition, the material (for example, shell material) may be added to the liquid at a time, or may be added to the liquid in a plurality of times. After obtaining the powder, classification and / or sieving may be performed. For example, the toner may be sieved after the external addition step. Further, unnecessary steps may be omitted. For example, when a commercially available product can be used as a material as it is, the step of preparing the material can be omitted by using a commercially available product. Moreover, even if it does not adjust pH of a liquid, when reaction for forming a shell layer advances favorably, you may omit a pH adjustment process. If an external additive is unnecessary, the external addition process may be omitted. When the external additive is not attached to the surface of the toner base particles (the step of external addition is omitted), the toner base particles correspond to the toner particles. As a material for synthesizing the resin, a prepolymer may be used instead of the monomer, if necessary. In order to obtain a predetermined compound, a salt, ester, hydrate, or anhydride of the compound may be used as a raw material. In order to produce the toner efficiently, it is preferable to form a large number of toner particles simultaneously. The toner particles produced at the same time are considered to have substantially the same configuration.

  Examples of the present invention will be described. Table 1 shows toners TA-1 to TA-4 and TB (electrostatic latent image developing toners) according to Examples or Comparative Examples.

  Hereinafter, a manufacturing method, an evaluation method, and an evaluation result of toners TA-1 to TA-4 and TB will be described in order. In the evaluation in which an error occurs, a considerable number of measurement values with sufficiently small errors are obtained, and the arithmetic average of the obtained measurement values is used as the evaluation value.

[Preparation of materials]
(Synthesis of Amorphous Polyester Resin APES-1)
In a 10 L four-necked flask equipped with a thermometer (thermocouple), dehydration tube, nitrogen introduction tube, and stirrer, 370 g of bisphenol A propylene oxide adduct, 3059 g of bisphenol A ethylene oxide adduct, terephthalic acid 1194 g, 286 g of fumaric acid, 10 g of tin (II) 2-ethylhexanoate, and 2 g of gallic acid were added. Subsequently, the contents of the flask were reacted in a nitrogen atmosphere and at a temperature of 230 ° C. until the reaction rate reached 90% by mass or more. The reaction rate was calculated according to the formula “reaction rate = 100 × actual amount of reaction product water / theoretical product water amount”. Subsequently, the flask contents were reacted under a reduced pressure atmosphere (pressure 8.3 kPa) and a temperature of 230 ° C. until the Tm of the reaction product (resin) reached a predetermined temperature (89 ° C.). As a result, an amorphous polyester resin APES-1 having a Tm of 89 ° C. and a Tg of 50 ° C. was obtained.

(Synthesis of amorphous polyester resin APES-2)
The method for synthesizing the non-crystalline polyester resin APES-2 was to replace 370 g of bisphenol A propylene oxide adduct, 3059 g of bisphenol A ethylene oxide adduct, 1194 g of terephthalic acid and 286 g of fumaric acid, 1286 g of bisphenol A propylene oxide adduct, bisphenol. A It was the same as the synthesis method of the amorphous polyester resin APES-1 except that 2218 g of ethylene oxide adduct and 1603 g of terephthalic acid were used. Regarding the obtained amorphous polyester resin APES-2, Tm was 111 ° C. and Tg was 69 ° C.

(Synthesis of Amorphous Polyester Resin APES-3)
In a 10 L four-necked flask equipped with a thermometer (thermocouple), dehydration tube, nitrogen introduction tube, and stirring device, 4907 g of bisphenol A propylene oxide adduct, 1942 g of bisphenol A ethylene oxide adduct, and fumaric acid 757 g, 2078 g of dodecyl succinic anhydride, 30 g of tin (II) 2-ethylhexanoate, and 2 g of gallic acid were added. Subsequently, the contents of the flask were reacted in a nitrogen atmosphere and at a temperature of 230 ° C. until the reaction rate represented by the above formula reached 90% by mass or more. Subsequently, the contents of the flask were reacted for 1 hour in a reduced pressure atmosphere (pressure 8.3 kPa) and a temperature of 230 ° C. Subsequently, 548 g of trimellitic anhydride is added to the flask, and Tm of the reaction product (resin) reaches a predetermined temperature (127 ° C.) under a reduced pressure atmosphere (pressure 8.3 kPa) and a temperature of 220 ° C. The flask contents were reacted. As a result, an amorphous polyester resin APES-3 having Tm of 127 ° C. and Tg of 51 ° C. was obtained.

(Synthesis of crystalline polyester resin CPES)
In a 10-L four-necked flask equipped with a thermometer (thermocouple), dehydration tube, nitrogen introduction tube, and stirring device, 2643 g of 1,6-hexanediol, 864 g of 1,4-butanediol, and 2945 g of succinic acid Put. Subsequently, the flask contents were heated to a temperature of 160 ° C. to dissolve the added material. Subsequently, using a dropping funnel, a mixed liquid such as styrene (a mixed liquid of 1831 g of styrene, 161 g of acrylic acid and 110 g of dicumyl peroxide) was dropped into the flask over 1 hour. Subsequently, the contents of the flask were reacted at a temperature of 170 ° C. for 1 hour while stirring to polymerize styrene and acrylic acid in the flask. Thereafter, the inside of the flask was maintained in a reduced-pressure atmosphere (pressure 8.3 kPa) for 1 hour to remove unreacted styrene and acrylic acid in the flask. Subsequently, 40 g of tin (II) 2-ethylhexanoate and 3 g of gallic acid were added to the flask. Subsequently, the flask contents were heated and reacted at a temperature of 210 ° C. for 8 hours. Subsequently, the contents of the flask were reacted for 1 hour in a reduced pressure atmosphere (pressure 8.3 kPa) and a temperature of 210 ° C. As a result, a crystalline polyester resin CPES having Tm of 92 ° C., Mp of 96 ° C. and a crystallinity index of 0.95 was obtained.

[Toner Production Method]
(Production of toner core)
Using an FM mixer ("FM-20B" manufactured by Nippon Coke Kogyo Co., Ltd.), 100 g of the first binder resin (crystalline polyester resin CPES synthesized by the above procedure) and the second binder resin (by the above procedure). 300 g of the synthesized amorphous polyester resin APES-1), 100 g of the third binder resin (amorphous polyester resin APES-2 synthesized by the procedure described above), and the fourth binder resin (synthesized by the procedure described above). 600 g of amorphous polyester resin APES-3, 144 g of colorant (“Colortex (registered trademark) Blue B1021” manufactured by Sanyo Pigment Co., Ltd., component: phthalocyanine blue), and first release agent (manufactured by Hiroyuki Kato) “Carnauba wax No. 1”, 12 g of ingredient: carnauba wax, and second mold release agent (“Nissan Electol (registered trademark) W” manufactured by NOF Corporation) P-3 ", component: a synthetic ester wax) 48 g, were mixed at a rotational speed 2400 rpm.

Subsequently, the obtained mixture was subjected to conditions using a twin-screw extruder (“PCM-30” manufactured by Ikegai Co., Ltd.) at a material supply speed of 5 kg / hour, a shaft rotation speed of 160 rpm, and a set temperature (cylinder temperature) of 100 ° C. Was melt kneaded. Thereafter, the obtained kneaded material was cooled. Subsequently, the cooled kneaded material was coarsely pulverized using a pulverizer (“Rotoplex 16/8” manufactured by Toa Machinery Co., Ltd.). Subsequently, the obtained coarsely pulverized product was finely pulverized using a jet mill (“Ultrasonic Jet Mill Type I” manufactured by Nippon Pneumatic Industry Co., Ltd.). Subsequently, the obtained finely pulverized product was classified using a classifier (“Elbow Jet EJ-LABO type” manufactured by Nippon Steel Mining Co., Ltd.). As a result, a toner core having a Tm of 90 ° C., a Tg of 49 ° C., and a volume median diameter (D ₅₀ ) of 6.7 μm was obtained.

(First shell layer forming step)
A 1 L three-necked flask equipped with a thermometer and a stirring blade was set in a water bath, and 300 mL of ion-exchanged water was placed in the flask. Thereafter, the temperature in the flask was kept at 30 ° C. using a water bath. Subsequently, 30 g of an oxazoline group-containing polymer aqueous solution (“Epocross WS-300” manufactured by Nippon Shokubai Co., Ltd., solid content concentration: 10% by mass) was added to the flask, and then the contents of the flask were sufficiently stirred. The aqueous oxazoline group-containing polymer solution (Epocross WS-300) contained a copolymer of methyl methacrylate and 2-vinyl-2-oxazoline as the oxazoline group-containing polymer.

  Subsequently, 300 g of toner core was added to the flask, and the contents of the flask were stirred for 1 hour at a rotation speed of 200 rpm. Thereafter, 300 mL of ion exchange water was added to the flask.

  Subsequently, 6 mL of a 1% strength by weight aqueous ammonia solution was added into the flask. Subsequently, while stirring the contents of the flask at a rotational speed of 150 rpm, the temperature in the flask was raised to 60 ° C. at a rate of 0.5 ° C./min. Subsequently, the contents of the flask were kept at that temperature (60 ° C.) for 1 hour while stirring the contents of the flask at a rotation speed of 100 rpm. While the liquid temperature was kept high, the first shell layer was formed on the surface of the toner core. The first shell layer was an oxazoline group-containing shell layer containing a copolymer of two or more kinds of vinyl compounds (specifically, methyl methacrylate and 2-vinyl-2-oxazoline).

  Subsequently, a 1% by mass aqueous ammonia solution was added to the flask to adjust the pH of the flask contents to 7. Subsequently, the contents of the flask were cooled until the temperature reached room temperature (about 25 ° C.) to obtain a dispersion liquid containing the first layer-coated particles (particles in which the surface of the toner core was covered with the first shell layer). .

(Washing process)
The dispersion of the first layer coated particles obtained as described above was filtered (solid-liquid separation) using a Buchner funnel to obtain wet cake-like first layer coated particles. Thereafter, the obtained wet cake-like first layer-coated particles were redispersed in ion-exchanged water. Further, dispersion and filtration were repeated 5 times to wash the first layer coated particles.

  Next, the second to ninth shell layer forming steps will be described. In the production of the toner TB, the following second to ninth shell layer forming steps were not performed. Further, in the production of the toner TA-4, the following sixth to ninth shell layer forming steps were not performed. In the toner TB, the first layer covering particles correspond to toner base particles. In the toner TA-4, the fifth layer covering particles correspond to toner base particles.

(Second shell layer forming step)
A 1 L three-necked flask equipped with a thermometer and a stirring blade was set in a water bath, and 300 mL of ion-exchanged water was placed in the flask. Thereafter, the temperature in the flask was kept at 30 ° C. using a water bath. Then, after adding the carboxyl group-containing polymer (any one of the carboxyl group-containing polymers C-1 to C-3 defined for each toner) of the type and amount shown in Table 1 into the flask, the flask contents The thing was fully stirred. For example, in the production of each of toners TA-1 and TA-4, 3.0 g of carboxyl group-containing polymer C-1 was added. In the production of toner TA-2, 10 g of carboxyl group-containing polymer C-2 was added. In the production of the toner TA-3, 1.5 g of the carboxyl group-containing polymer C-3 was added.

The carboxyl group-containing polymer C-1 is a gel-state polyacrylic acid aqueous solution (“Aron (registered trademark) A-10SL” manufactured by Toagosei Co., Ltd., solid concentration: 40 mass%, viscosity at a temperature of 25 ° C .: 40˜ 150 mPa · s).
The carboxyl group-containing polymer C-2 is a carboxylic acid copolymer emulsion (“Aron (registered trademark) A-7075” manufactured by Toagosei Co., Ltd., solid concentration: 20 mass%, viscosity at a temperature of 25 ° C .: 5 to 5%. 45 mPa · s).
The carboxyl group-containing polymer C-3 is a polyacrylic acid powder (“Durimer (registered trademark) AC-10LHP” manufactured by Toagosei Co., Ltd., viscosity of a 10% by weight aqueous solution at a temperature of 25 ° C .: 500 to 1000 mPa · s). Met.

  Subsequently, 300 g of the first layer-coated particles were added to the flask, and the flask contents were stirred for 1 hour at a rotation speed of 200 rpm. Thereby, the gel-like 2nd shell material adhered to the surface of the 1st layer covering particle. Thereafter, 300 mL of ion exchange water was added to the flask.

  Subsequently, while stirring the contents of the flask at a rotational speed of 100 rpm, the temperature in the flask was raised to 60 ° C. at a rate of 1.0 ° C./min. Subsequently, the flask contents were stirred at a rotational speed of 100 rpm and kept at that temperature (60 ° C.) for 2 hours. While the liquid temperature was kept high, a second shell layer was formed on the surface of the first layer-coated particles. The second shell layer was a carboxyl group-containing shell layer containing an acrylic acid polymer.

  Subsequently, the flask contents are cooled until the temperature reaches room temperature (about 25 ° C.), and the dispersion contains the second layer coated particles (particles in which the second shell layer is formed on the surface of the first layer coated particles). A liquid was obtained. Thereafter, the second layer-coated particles were washed in the same manner as in the “washing step” after the first shell layer was formed.

(Third shell layer forming step)
A third shell layer was formed on the surface of the second layer coated particles in the same manner as in the “first shell layer forming step” described above. As a result, a dispersion liquid containing the third layer-coated particles (particles in which the third shell layer was formed on the surface of the second layer-coated particles) was obtained. The third shell layer was an oxazoline group-containing shell layer containing a copolymer of two or more kinds of vinyl compounds (specifically, methyl methacrylate and 2-vinyl-2-oxazoline). Thereafter, the third layer-coated particles were washed in the same manner as in the “washing step” after the first shell layer was formed.

(Fourth shell layer forming step)
A fourth shell layer was formed on the surface of the third layer coated particles in the same manner as in the “second shell layer forming step” described above. As a result, a dispersion liquid containing the fourth layer-coated particles (particles in which the fourth shell layer was formed on the surface of the third layer-coated particles) was obtained. The fourth shell layer was a carboxyl group-containing shell layer containing an acrylic acid polymer. Thereafter, the fourth layer coated particles were washed in the same manner as in the “washing step” after the first shell layer was formed.

(Fifth shell layer forming step)
A fifth shell layer was formed on the surface of the fourth layer coated particles in the same manner as in the “first shell layer forming step” described above. As a result, a dispersion liquid containing the fifth layer-coated particles (particles in which the fifth shell layer was formed on the surface of the fourth layer-coated particles) was obtained. The fifth shell layer was an oxazoline group-containing shell layer containing a copolymer of two or more kinds of vinyl compounds (specifically, methyl methacrylate and 2-vinyl-2-oxazoline). Thereafter, the fifth layer-coated particles were washed in the same manner as in the “washing step” after the first shell layer was formed.

(Sixth shell layer forming step)
In the same manner as in the “second shell layer forming step” described above, a sixth shell layer was formed on the surface of the fifth layer-coated particles. As a result, a dispersion liquid containing sixth layer coated particles (particles in which the sixth shell layer was formed on the surface of the fifth layer coated particles) was obtained. The sixth shell layer was a carboxyl group-containing shell layer containing an acrylic acid polymer. Thereafter, the sixth layer-coated particles were washed in the same manner as in the “washing step” after the first shell layer was formed.

(Seventh shell layer forming step)
A seventh shell layer was formed on the surface of the sixth layer-coated particles in the same manner as in the “first shell layer forming step” described above. As a result, a dispersion liquid containing the seventh layer-coated particles (particles in which the seventh shell layer was formed on the surface of the sixth layer-coated particles) was obtained. The seventh shell layer was an oxazoline group-containing shell layer containing a copolymer of two or more types of vinyl compounds (specifically, methyl methacrylate and 2-vinyl-2-oxazoline). Thereafter, the seventh layer-coated particles were washed in the same manner as in the “washing step” after the first shell layer was formed.

(Eighth shell layer forming step)
An eighth shell layer was formed on the surface of the seventh layer-coated particles in the same manner as in the “second shell layer forming step” described above. As a result, a dispersion liquid containing the eighth layer-coated particles (particles in which the eighth shell layer was formed on the surface of the seventh layer-coated particles) was obtained. The eighth shell layer was a carboxyl group-containing shell layer containing an acrylic acid polymer. Thereafter, the eighth layer-coated particles were washed in the same manner as in the “washing step” after the first shell layer was formed.

(9th shell layer forming step)
A ninth shell layer was formed on the surface of the eighth layer-coated particles in the same manner as in the “first shell layer forming step” described above. As a result, a dispersion liquid containing toner base particles (particles in which the ninth shell layer was formed on the surface of the eighth layer covering particles) having a multilayered shell layer (specifically, a shell layer having a nine-layer structure) was obtained. The ninth shell layer was an oxazoline group-containing shell layer containing a copolymer of two or more vinyl compounds (specifically, methyl methacrylate and 2-vinyl-2-oxazoline). Thereafter, the toner base particles were washed in the same manner as in the “washing step” after the first shell layer was formed.

  In each of toners TA-1 to TA-3, the toner base particles have a nine-layer shell layer (from the toner core side, the first shell layer, the second shell layer, the third shell layer, the fourth shell layer, and the fifth shell layer). , 6th shell layer, 7th shell layer, 8th shell layer, and 9th shell layer). The first shell layer, the third shell layer, the fifth shell layer, the seventh shell layer, and the ninth shell layer are made of the same material (copolymer of methyl methacrylate and 2-vinyl-2-oxazoline). And had the same thickness as each other. Further, the second shell layer, the fourth shell layer, the sixth shell layer, and the eighth shell layer are the same as each other (the carboxyl group-containing polymers C-1 to C-3 shown in Table 1 defined for each toner). And have the same thickness (thickness corresponding to the addition amount of the carboxyl group-containing polymer shown in Table 1 defined for each toner).

  In toner TA-4, the toner base particles have a shell layer having a five-layer structure (from the toner core side, the first shell layer, the second shell layer, the third shell layer, the fourth shell layer, and the fifth shell layer). It was.

  In the toner TB, the toner base particles were provided with a single shell layer (only the first shell layer).

(Drying process)
Subsequently, the obtained toner base particles were dispersed in an aqueous ethanol solution having a concentration of 50% by mass. As a result, a slurry of toner base particles was obtained. Subsequently, the toner base particles in the slurry were removed under the conditions of a hot air temperature of 45 ° C. and a blower air volume of 2 m ³ / min using a continuous surface reformer (“Coat Mizer (registered trademark)” manufactured by Freund Sangyo Co., Ltd.). Dried. As a result, a powder of dried toner base particles was obtained.

(External addition process)
Subsequently, the obtained toner base particles were externally added. Specifically, 100 parts by mass of toner base particles, hydrophobic fumed silica particles (“AEROSIL® R972” manufactured by Nippon Aerosil Co., Ltd.), hydrophobizing agent: dimethyldichlorosilane (DDS), number average primary particle size: 1.50 parts by mass) and conductive titanium oxide particles (“EC-100” manufactured by Titanium Industry Co., Ltd., substrate: TiO ₂ particles, coating layer: Sb-doped SnO ₂ film, number average primary particle size: about 0.35 μm) 1.00 parts by mass and 1.25 parts by mass of cross-linked resin particles (resin: cross-linked styrene-acrylic acid resin, number average primary particle size: about 0.08 μm) 10 L capacity FM mixer (Nippon Coke Kogyo Co., Ltd.) is used for mixing for 10 minutes to attach external additives (silica particles, titanium oxide particles, and crosslinked resin particles) to the surface of the toner base particles. It was. Subsequently, the obtained powder was sieved using a sieve of 200 mesh (aperture 75 μm). As a result, toners (toners TA-1 to TA-4 and TB) containing a large number of toner particles were obtained.

  For each of toners TA-1 to TA-4 and TB obtained as described above, the release agent exposure rate in the cross section of the toner particles and the amount of oxazoline groups contained in the toner were measured. The measurement results were as shown in Table 1. The “amount of oxazoline group” shown in Table 1 corresponds to the total amount of both the oxazoline group present in an unopened ring and the ring-opened oxazoline group. For example, for toner TA-1, the release agent exposure rate in the cross section of the toner particles was 7%, and the amount of oxazoline groups was 0.97 μmol with respect to 1 g of toner.

[Measurement method of amount of oxazoline group]
Using a calibration curve (a calibration curve based on a standard substance), quantitative analysis was performed by the GC / MS method under the following conditions.

<GC / MS method>
As a measuring apparatus, a gas chromatograph mass spectrometer ("GCMS-QP2010 Ultra" manufactured by Shimadzu Corporation) and a multi-shot pyrolyzer ("Frontier LAB Multi-functional Pyrolyzer (registered trademark) PY-3030D manufactured by Frontier Laboratories, Inc." )). As a column, a GC column ("Agilent (registered trademark) J & W Ultra Inert Capillary GC Column DB-5ms" manufactured by Agilent Technologies, Inc.), phase: an arylene phase in which allylene is reinforced with a siloxane polymer to strengthen the main chain of the polymer, inner diameter: 0.25 mm, film thickness: 0.25 μm, length: 30 m).

(Gas chromatograph)
Carrier gas: Helium (He) gas Carrier flow rate: 1 mL / min Vaporization chamber temperature: 210 ° C
・ Pyrolysis temperature: Furnace “600 ° C”, interface part “320 ° C”
-Temperature rising condition: After holding at 40 ° C for 3 minutes, the temperature was raised from 40 ° C to 300 ° C at a rate of 10 ° C / min, and held at 300 ° C for 15 minutes.

(Mass spectrometry)
-Ionization method: EI (Electron Impact) method-Ion source temperature: 200 ° C
・ Interface temperature: 320 ℃
Detection mode: scan (measurement range: 45 m / z to 500 m / z)

[Measurement method of exposure rate of release agent in cross section of toner particles]
A sample (toner) was embedded with a visible light curable resin (“Aronix (registered trademark) D-800” manufactured by Toagosei Co., Ltd.) to obtain a cured product. Thereafter, a knife for preparing an ultrathin section (“Sumiknife (registered trademark)” manufactured by Sumitomo Electric Industries, Ltd .: a diamond knife having a blade width of 2 mm and a blade tip angle of 45 °) and an ultramicrotome (“EM UC6” manufactured by Leica Microsystems) By cutting the cured product with a cutting speed of 0.3 mm / sec, a thin piece of 150 nm was produced. The resulting flakes were exposed to a ruthenium tetroxide vapor for 10 minutes on a copper mesh and stained with Ru. Then, the cross section of the dyed thin piece sample was image | photographed using the transmission electron microscope (TEM) ("JSM-6700F" by JEOL Ltd.).

  The release agent exposure rate was measured by analyzing the TEM photographic image (cross-sectional photographic image of toner particles) obtained as described above using image analysis software (“WinROOF” manufactured by Mitani Corporation). In a TEM image (a cross-sectional image of a toner particle), the ratio of the surface area of the toner core (contour line indicating the outer edge) where the release agent is exposed without being covered by the shell layer (release agent exposure) Rate) was measured. Specifically, based on the formula “release agent exposure rate = 100 × (total length of regions where release agent is exposed on the surface of the toner core without being covered by the shell layer) / (perimeter of toner core)”. The release agent exposure rate in the cross section of the toner particles was determined. The “region where the release agent is exposed on the surface of the toner core without being covered with the shell layer” includes a region where the external additive is directly attached to the surface of the toner core. The release agent exposure rate was measured for each of the 10 toner particles contained in the sample (toner). Then, the arithmetic average of the 10 measured values obtained was used as the evaluation value (release agent exposure rate) of the sample (toner).

[Evaluation method]
The evaluation method of each sample (toners TA-1 to TA-4 and TB) is as follows.

(Heat resistant storage stability)
2 g of the sample (toner) was placed in a 20 mL polyethylene container, and the container was left in a thermostat set at 58 ° C. for 3 hours. Thereafter, the toner was taken out from the thermostat, and an evaluation toner was obtained in the container.

Subsequently, the obtained toner for evaluation was placed on a sieve having a known mass of 100 mesh (aperture 150 μm). Then, the mass of the sieve containing the evaluation toner was measured, and the mass of the toner before sieving was determined. Subsequently, the sieve was set in a powder tester (manufactured by Hosokawa Micron Corporation), and the sieve for evaluation was sieved by vibrating the sieve for 30 seconds under the conditions of the rheostat scale 5 according to the manual of the powder tester. Then, after sieving, the mass of the sieve containing toner was measured to determine the mass of the toner remaining on the sieve (toner that did not pass through the sieve). From the mass of the toner before sieving and the mass of the toner after sieving (the mass of the toner remaining on the sieving after sieving), the aggregation rate (unit: mass%) was determined based on the following formula.
Aggregation rate = 100 × mass of toner after sieving / mass of toner before sieving

  When the aggregation rate was less than 10% by mass, it was evaluated as “good”, and when the aggregation rate was 10% by mass or more, it was evaluated as “poor” (not good).

(Preparation of developer for evaluation)
100 parts by weight of a developer carrier (carrier for “TASKalfa 5550ci” manufactured by Kyocera Document Solutions Co., Ltd.) and 5 parts by weight of a sample (toner) were mixed with a mixer (Wheel & Bacofen (WAB) “Turbler (registered) (Trademark) mixer ”) and mixed for 30 minutes to obtain a developer for evaluation (two-component developer).

(Low temperature fixability)
As an evaluator, a printer having a Roller-Roller type heat and pressure type fixing device (nip width: 8 mm) (evaluator that modifies "FS-C5250DN" manufactured by Kyocera Document Solutions Co., Ltd., and can change the fixing temperature) Was used. The evaluation developer prepared by the above-described procedure was put into the developing device of the evaluation machine, and the sample (replenishment toner) was put into the toner container of the evaluation machine.

Using the above-mentioned evaluation machine, under a temperature of 25 ° C. and a humidity of 50% RH, on a paper having a basis weight of 90 g / m ² (A4 size plain paper), a linear speed of 200 mm / second and a toner loading of 1.0 mg / cm ^Under the condition ² , a solid image having a size of 25 mm × 25 mm (specifically, an unfixed toner image) was formed. Subsequently, the paper on which the image was formed was passed through the fixing device of the evaluation machine.

  The minimum fixing temperature was measured in the range of the fixing temperature from 100 ° C. to 200 ° C. Specifically, the fixing temperature of the fixing device was increased by 2 ° C. from 100 ° C., and the lowest temperature (minimum fixing temperature) at which the solid image (toner image) can be fixed on the paper was measured. Whether or not the toner could be fixed was confirmed by a rub test. Specifically, the evaluation paper passed through the fixing device was bent so that the surface on which the image was formed was on the inside, and the image on the fold was rubbed 5 times with a 1 kg weight coated with a cloth. Subsequently, the paper was spread and the bent portion of the paper (the portion where the solid image was formed) was observed. Then, the length (peeling length) of toner peeling at the bent portion was measured. The lowest temperature among the fixing temperatures at which the peeling length was 1 mm or less was defined as the lowest fixing temperature. When the minimum fixing temperature was 145 ° C. or lower, it was evaluated as “good”, and when it exceeded 145 ° C., it was evaluated as “poor” (not good).

(Photoconductor drum contamination)
As an evaluation machine, a multifunction machine (“TASKalfa 5550ci” manufactured by Kyocera Document Solutions Inc.) was used. The evaluation developer prepared by the above-described procedure was put into the developing device of the evaluation machine, and the sample (replenishment toner) was put into the toner container of the evaluation machine.

  Under the environment of temperature 32 ° C. and humidity 80% RH, continuous printing with a printing rate of 5% is performed on 3000 sheets of paper (A4 size printing paper) while replenishing toner from the toner container using the evaluation machine. went. During continuous printing, solid images were output every 200 sheets from the start of printing up to 1000 sheets, and every 1000 sheets thereafter, and the surface of the photoconductive drum of the evaluator was visually observed. Then, the photosensitive drum contamination was evaluated according to the following criteria.

○ (good): Through 3000 continuous printing, no coloration by the toner was observed on the surface of the photosensitive drum.
X (not good): Coloring by the toner was observed on the surface of the photosensitive drum at any timing during continuous printing of 3000 sheets.

[Evaluation results]
Table 2 shows the evaluation results for each of toners TA-1 to TA-4 and TB (heat-resistant storage stability: aggregation rate, low-temperature fixability: minimum fixing temperature, photoconductor drum contamination: presence or absence of contamination). “1000 sheets” in Table 2 relating to the evaluation result of “photosensitive drum contamination” indicates that coloring by toner was observed on the surface of the photosensitive drum when 1000 sheets were printed.

  Each of the toners TA-1 to TA-4 (the toners according to Examples 1 to 4) had the above-described basic configuration. Specifically, each of the toners TA-1 to TA-4 includes a plurality of toner particles each including a toner core containing a binder resin and a release agent and a multilayered shell layer partially covering the surface of the toner core. . The multilayer shell layer has a first shell layer containing a first polymer containing a repeating unit having an oxazoline group, a second shell layer containing a second polymer containing a repeating unit having a carboxyl group, and an oxazoline group And a third shell layer containing a third polymer containing repeating units. The first shell layer, the second shell layer, and the third shell layer had a laminated structure in the order of the first shell layer, the second shell layer, and the third shell layer from the toner core side. The second shell layer was in contact with an area not covered with the first shell layer in the surface area of the toner core.

  In toners TA-1 to TA-4, each of the multilayer shell layers contains a fourth shell layer containing a fourth polymer containing a repeating unit having a carboxyl group and a fifth polymer containing a repeating unit having an oxazoline group A first shell layer, a second shell layer, a third shell layer, a fourth shell layer, and a fifth shell layer from the toner core side. , A third shell layer, a fourth shell layer, and a fifth shell layer in this order. In each of the toners TA-1 to TA-3, the multilayer shell layer further includes a sixth shell layer, a seventh shell layer, an eighth shell layer, and a ninth shell layer. Of the surface area of the toner core, the area where the release agent is present was selectively exposed to the first shell layer. The second shell layer extended to the toner core along the first shell layer, and was in contact with the area where the release agent was exposed to the first shell layer in the surface area of the toner core. Further, the fourth shell layer, the sixth shell layer, and the eighth shell layer also extend to the toner core along the lower shell layer, and the release agent is exposed to the lower shell layer in the surface region of the toner core. Was in contact with. In the toner TA-4, the multi-layered shell layer has substantially the same structure as that shown in FIG.

  As shown in Table 2, in each of the toners TA-1 to TA-4, it was possible to suppress release of the release agent from the toner particles while ensuring sufficient heat-resistant storage stability of the toner.

  The toner for developing an electrostatic latent image according to the present invention can be used for forming an image in, for example, a copying machine, a printer, or a multifunction machine.

10: Toner particles 10a: Toner mother particles 11: Toner core 11a: Release agent domain 12: Multi-layered shell layer 12a: First shell layer 12b: Second shell layer 12c: Third shell layer 12d: Fourth shell layer 12e: Fifth shell layer 13: External additive particles F1, F2: Surface R0 to R2: Release agent exposed region

Claims (12)

An electrostatic latent image developing toner comprising a plurality of toner particles comprising a core containing a binder resin and a release agent and a multilayered shell layer partially covering the surface of the core,
The multilayer shell layer is
A first shell layer containing a first polymer comprising a repeating unit having an oxazoline group;
A second shell layer containing a second polymer comprising a repeating unit having a carboxyl group;
A third shell layer containing a third polymer comprising repeating units having an oxazoline group;
With
The first shell layer, the second shell layer, and the third shell layer have a laminated structure in the order of the first shell layer, the second shell layer, and the third shell layer from the core side. ,
The electrostatic latent image developing toner, wherein the second shell layer is in contact with an area of the surface area of the core that is not covered with the first shell layer. A region where the release agent is present in the surface region of the core is selectively exposed to the first shell layer,
The second shell layer extends to the core along the first shell layer, and is in contact with the region where the release agent is exposed to the first shell layer in a surface region of the core. The toner for developing an electrostatic latent image according to claim 1.   Of the surface area of the core, the ratio of the area where the release agent is exposed without being covered by the multilayered shell layer is 1% or more and less than 10% as a circumference ratio measured from the cross section of the toner particles. The toner for developing an electrostatic latent image according to claim 2. Each of the first polymer and the third polymer is a copolymer of two or more kinds of vinyl compounds including at least a compound represented by the following formula (1). The toner for developing an electrostatic latent image.

In formula (1), R ¹ represents a hydrogen atom or an alkyl group which may have a substituent.   The electrostatic latent image developing toner according to claim 4, wherein the second polymer is an acrylic acid polymer.   The electrostatic latent image developing toner according to claim 4, wherein the core contains a polyester resin as the binder resin.   The electrostatic latent image developing toner according to claim 6, wherein the core is a pulverized core.   The toner for developing an electrostatic latent image according to claim 1, wherein the outermost layer of the multilayer structure shell layer contains a polymer containing a repeating unit having an oxazoline group.   The toner for developing an electrostatic latent image according to claim 8, wherein the amount of the oxazoline group contained in 1 g of the toner is 0.50 μmol or more and 1.50 μmol or less. The multilayer shell layer is
A fourth shell layer containing a fourth polymer comprising a repeating unit having a carboxyl group;
A fifth shell layer containing a fifth polymer comprising a repeating unit having an oxazoline group;
Further comprising
The first shell layer, the second shell layer, the third shell layer, the fourth shell layer, and the fifth shell layer are arranged from the core side, the first shell layer, the second shell layer, 10. The electrostatic latent image developing toner according to claim 1, wherein the toner for developing an electrostatic latent image has a laminated structure of an order of a third shell layer, the fourth shell layer, and the fifth shell layer. The first shell layer, the third shell layer, and the fifth shell layer are made of the same material,
The electrostatic latent image developing toner according to claim 10, wherein the second shell layer and the fourth shell layer are made of the same material. A first polymer containing a repeating unit having an oxazoline group, wherein the aqueous medium containing a core containing a binder resin and a release agent and an oxazoline group-containing polymer is heated to partially cover the surface of the toner core A first shell layer forming step of forming a first shell layer containing
After the first shell layer forming step, a carboxyl group-containing polymer is put into the aqueous medium, and the carboxyl group-containing polymer is separated from the surface of the first shell layer and the surface of the core in the aqueous medium. By heating the aqueous medium and polymerizing the carboxyl group-containing polymer in a state where the region is in contact with the region not covered with the first shell layer, a carboxyl group is formed on the first shell layer. A second shell layer forming step of forming a second shell layer containing a second polymer containing a repeating unit having a group;
After the second shell layer forming step, a third polymer containing a repeating unit having an oxazoline group is formed on the second shell layer by adding an oxazoline group-containing polymer to the aqueous medium and heating the aqueous medium. A third shell layer forming step of forming a third shell layer containing a polymer;
A method for producing a toner for developing an electrostatic latent image, comprising:

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