JP6001575B2 - Two-component developer and method for producing two-component developer - Google Patents

Two-component developer and method for producing two-component developer Download PDF

Info

Publication number
JP6001575B2
JP6001575B2 JP2014003284A JP2014003284A JP6001575B2 JP 6001575 B2 JP6001575 B2 JP 6001575B2 JP 2014003284 A JP2014003284 A JP 2014003284A JP 2014003284 A JP2014003284 A JP 2014003284A JP 6001575 B2 JP6001575 B2 JP 6001575B2
Authority
JP
Japan
Prior art keywords
layer
carrier
component developer
particles
fine particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
JP2014003284A
Other languages
Japanese (ja)
Other versions
JP2015132681A (en
Inventor
雄介 倉野
雄介 倉野
Original Assignee
京セラドキュメントソリューションズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 京セラドキュメントソリューションズ株式会社 filed Critical 京セラドキュメントソリューションズ株式会社
Priority to JP2014003284A priority Critical patent/JP6001575B2/en
Publication of JP2015132681A publication Critical patent/JP2015132681A/en
Application granted granted Critical
Publication of JP6001575B2 publication Critical patent/JP6001575B2/en
Application status is Active legal-status Critical
Anticipated expiration legal-status Critical

Links

Images

Description

  The present invention relates to a two-component developer containing toner particles and a carrier, and a method for producing the two-component developer.

  In image formation employing the electrophotographic method, a two-component developer containing toner particles and a carrier may be used. As a carrier, a carrier in which the surface of a carrier core is coated with a mixed resin is known (Patent Document 1). In Patent Document 1, this mixed resin is a mixture of one or more resins selected from silicone resins, polyethylene resins and fluororesins and one or more resins selected from acrylic resins, epoxy resins and melamine resins. It is described that it is a resin. Furthermore, it is described that conductive fine powder is dispersed in this mixed resin.

  As a carrier, a carrier in which a coating film having a two-layer structure including a lower layer and a surface layer is formed on the surface of a carrier core material is known (Patent Document 2). In Patent Document 2, the lower layer is at least one selected from a tetrafluoroethylene-based resin containing a polyamideimide resin, a tetrafluoroethylene-based resin containing an epoxy resin, and a fluorine-based resin containing vinylidene fluoride. It is described that it is composed of a fluorine-based resin and that the surface layer is composed of a silicone resin.

JP 2009-098348 A JP-A-4-3333861

  However, in the carrier described in Patent Document 1, since it is difficult to form a uniform coating film, it is considered that the durability of the obtained coating film is insufficient. Furthermore, the two-component developer containing this carrier is considered to be inferior in charging property.

  In the two-component developer described in Patent Document 2, it is considered that the charge imparting property is excessively increased due to the silicone resin constituting the surface layer formed on the carrier. Therefore, when an image is formed using this two-component developer, it is considered that the chargeability of the toner becomes unstable and it is difficult to obtain a high-quality image when the printing rate changes.

  The present invention has been made in view of the above problems, and can stably obtain a high-quality image even when the printing conditions (for example, the printing rate) change, and is excellent in durability. An object is to provide a two-component developer.

  The two-component developer of the present invention includes toner particles and a carrier. The toner particles include toner base particles containing a binder resin and external additives externally added to the surface of the toner base particles. The external additive includes silica fine particles coated with a melamine resin layer. The carrier includes a carrier core material, a first layer covering the surface of the carrier core material, and a second layer covering the surface of the first layer. The first layer is made of a fluorine resin, and the second layer is made of a melamine resin.

  Furthermore, the method for producing a two-component developer of the present invention is a method for producing a two-component developer containing toner particles and a carrier. This manufacturing method includes a step of preparing toner particles, a step of preparing a carrier, and a step of mixing the carrier and toner particles. The step of preparing toner particles includes a step of preparing toner base particles, a step of preparing external additives, and a step of externally adding external additives to toner base particles. The external additive contains fine silica particles coated with a melamine resin layer. The step of preparing the carrier includes a step of preparing a carrier core material, a step of supplying a first layer forming liquid containing a fluororesin to the surface of the carrier core material, and the first layer forming liquid supplied Supplying a liquid for forming a second layer containing a melamine resin on the surface of the carrier core, and heat-treating the carrier core supplied with the liquid for forming the first layer and the liquid for forming the second layer; including.

  According to the two-component developer of the present invention, it is possible to stably obtain a good image and achieve excellent durability even when the printing conditions (for example, the printing rate) change. Can do.

FIG. 3 is a diagram illustrating toner particles contained in a two-component developer according to the present embodiment. It is a figure explaining how to read the softening point Tm of binder resin. It is a figure which shows the carrier contained in the two-component developer of this embodiment. It is a figure which shows another aspect of the carrier contained in the two-component developer of this embodiment. It is a figure which shows the two-component developer of this embodiment.

  Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. In addition, although description may be abbreviate | omitted suitably about the location where description overlaps, the summary of invention is not limited.

  The two-component developer of this embodiment includes toner particles and a carrier. Hereinafter, the toner particles, the carrier, and the two-component developer will be described in this order.

(Toner particles)
In this embodiment, toner particles are mixed with a carrier and contained in a two-component developer.

  The toner particles will be described with reference to FIG. FIG. 1 shows toner particles 100. The toner particles 100 include toner base particles 110 containing a binder resin and an external additive 160 externally added to the surface of the toner base particles 110. External additive 160 includes coated silica fine particles 140. The coated silica fine particles 140 are silica fine particles 120 coated with the melamine resin layer 130. Further, external additive fine particles 150 other than the coated silica fine particles 140 may be included. In the present specification, “toner base particles” mean toner particles before being externally added using the external additive 160.

  The components constituting the toner base particles 110 will be described below. The toner base particles 110 contain a binder resin as an essential component. Specific examples of the binder resin include thermoplastic resins (styrene resin, acrylic resin, styrene acrylic resin, polyethylene resin, polypropylene resin, vinyl chloride resin, polyester resin, polyamide resin, polyurethane resin, Polyvinyl alcohol resin, vinyl ether resin, N-vinyl resin, or styrene-butadiene resin). As the binder resin, a styrene acrylic resin or a polyester resin is preferable in order to make the dispersibility of the colorant in the toner base particles 110, the charging property, or the fixing property to the recording medium suitable.

  The glass transition point Tg of the binder resin is preferably 20 ° C. or higher and 55 ° C. or lower in order to ensure fixability. The glass transition point Tg of the binder resin can be obtained from the change point of the specific heat of the binder resin using a differential scanning calorimeter (DSC). For example, using a differential scanning calorimeter (for example, “DSC-6200” manufactured by Seiko Instruments Inc.) as a measuring device, the endothermic curve of the binder resin is measured to obtain the glass transition point Tg. More specifically, 10 mg of a measurement sample is put in an aluminum pan, and an empty aluminum pan is used as a reference. An example is a method in which an endothermic curve is obtained and the glass transition point Tg of the binder resin is obtained based on the endothermic curve.

  The softening point Tm of the binder resin is preferably 100 ° C. or less, and more preferably 95 ° C. or less, in order to ensure fixability. In order to adjust the softening point Tm of the binder resin, for example, a plurality of binder resins having different softening points Tm may be combined.

For measurement of the softening point Tm of the binder resin, an elevated flow tester (for example, “CFT-500D” manufactured by Shimadzu Corporation) can be used. Specifically, a measurement sample is set in an elevated flow tester, and a 1 cm 3 sample is melted under predetermined conditions (die pore diameter 1 mm, plunger load 20 kg / cm 2 , heating rate 6 ° C./min). An S-shaped curve (that is, an S-shaped curve related to temperature (° C.) / Stroke (mm)) is obtained by flowing out, and the softening point Tm of the binder resin is read from the S-shaped curve.

  With reference to FIG. 2, how to read the softening point Tm of the binder resin will be described. In FIG. 2, the maximum stroke value is S1, and the baseline stroke value lower than the temperature of S1 is S2. The temperature at which the stroke value in the S-shaped curve is (S1 + S2) / 2 is defined as the softening point Tm of the measurement sample.

  Returning to FIG. 1, the description of the toner particles 100 will be continued. The toner base particles 110 may contain a colorant. As the colorant, a known pigment or dye can be used according to the color of the toner particles 100. Examples of the black colorant include carbon black. In addition, a colorant that is toned to black using a colorant such as a yellow colorant, a magenta colorant, or a cyan colorant described below can also be used as the black colorant.

  When the toner particles 100 are color toner particles, the toner base particles 110 can contain a yellow colorant, a magenta colorant, or a cyan colorant. As these colorants, known pigments and dyes can be used.

  The amount of the colorant used in the toner base particles 110 is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

  The toner base particles 110 may contain a release agent in order to improve the fixability and offset resistance of the toner particles 100. Examples of the release agent include various waxes.

  The amount of the release agent used in the toner base particles 110 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 in order to improve the fixability and offset resistance of the toner particles 100. More preferred is 20 parts by mass or more.

  The toner base particles 110 may contain a charge control agent in order to obtain toner particles that improve the charge level and charge rising property and are excellent in durability and stability. The charge rising property is an index of whether or not the toner can be charged to a predetermined charge level in a short time.

  The toner base particles 110 may have a configuration in which a shell layer is formed so as to cover the surface of the toner core (so-called core-shell structure). For example, the toner core may have the same composition or configuration as the toner base particles 110 described above. The resin constituting the shell layer may be composed of a resin including, for example, a thermosetting resin (for example, melamine resin, guanamine resin, sulfoamide resin, urea resin, glyoxal resin, aniline resin, or polyimide resin).

  The volume average particle diameter of the toner base particles 110 is preferably 4.0 μm or more and 10 μm or less in order to obtain a high-quality image. For the same reason, the number average particle size of the toner base particles 110 is preferably 3.0 μm or more and 9.0 μm or less.

  In the toner particles 100, an external additive 160 is externally added to the surface of the toner base particles 110 in order to improve fluidity and handling properties. The external additive 160 includes silica fine particles 120 (coated silica fine particles 140) coated with the melamine resin layer 130, and may further include external additive fine particles 150 other than the coated silica fine particles 140.

  The melamine resin layer 130 is a layer made of melamine resin. Melamine resin is a polycondensate of melamine and formaldehyde, and the monomer used to form melamine resin is melamine.

  By externally adding the external additive 160, the durability of the toner particles 100 is improved. Furthermore, since the carrier to be described later includes the second layer made of melamine resin in the outermost layer, it is possible to prevent the coated silica fine particles 140 dropped from the toner particles 100 from adhering to the carrier. As a result, it is possible to obtain a two-component developer that can stably form a high-quality image over a long period of time (that is, has excellent durability) even when the printing conditions change.

  The external additive fine particles 150 other than the coated silica fine particles 140 are not particularly limited as long as they are fine particles (for example, titanium oxide fine particles or uncoated silica fine particles) that can be used as normal external additives.

  The amount (covering amount) of the melamine resin layer 130 in the silica fine particles 120 is 50 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the silica fine particles 120 in order to improve the durability of the toner particles 100. preferable.

  In addition, it can confirm that the melamine resin layer 130 is formed in the surface of the covering silica fine particle 140 by quantifying the nitrogen atom contained in a melamine resin using a fluorescent X ray.

  The particle diameter of the coated silica fine particles 140 is preferably 0.01 μm or more and 1.0 μm or less in order to improve the fluidity and handleability of the toner particles 100.

  The amount of the coated silica fine particles 140 is 1 part by mass with respect to 100 parts by mass of the toner base particles 110 in order to improve fluidity, handleability, and durability of the toner particles 100 and the two-component developer described below. It is preferably 10 parts by mass or less, more preferably 1 part by mass or more and 5 parts by mass or less.

The specific surface area of the silica fine particles 120 is preferably 100 to 300 m 2 / g so that the uniform melamine resin layer 130 can be easily formed.

(Career)
The carrier will be described below with reference to FIG. FIG. 3 shows a carrier 200 included in the two-component developer of this embodiment. As shown in FIG. 3, the carrier 200 includes a carrier core material 210, a first layer 220 that covers the surface of the carrier core material 210, and a second layer 230 that covers the first layer 220. The first layer 220 is made of a fluorine resin, and the second layer 230 is made of a melamine resin.

  Since the fluororesin constituting the first layer 220 is excellent in charge imparting property, the carrier 200 can maintain appropriate charge imparting property. The charge imparting property means the ability to charge the toner particles 100. In addition, since the melamine resin constituting the second layer 230 is excellent in strength and hardness, the durability of the carrier 200 can be improved and the spent (adhesion of the toner particle 100 component on the carrier surface) can be suppressed. The durability of the developer can also be improved.

  When the carrier core material 210 is covered only with a layer composed of a mixed resin of a fluorine-based resin and a melamine resin without adopting the two-layer configuration of the first layer 220 and the second layer 230, A part of the fluororesin having low hardness is exposed on the surface. Therefore, only a carrier and a two-component developer having poor durability can be obtained.

  Examples of the material of the carrier core material 210 include known materials that can be used for carriers of two-component developers. For example, metals such as ferrite, magnetite, iron, nickel, or cobalt; the above metals and copper, zinc, antimony, aluminum, lead, tin, bismuth, beryllium, manganese, magnesium, selenium, tungsten, zirconium, or vanadium Alloys or mixtures with metals such as: Metal oxides such as ferrite, iron oxide, titanium oxide or magnesium oxide; Mixtures of the above metals or metal oxides with nitrides such as chromium nitride or vanadium nitride A mixture of the above metals or metal oxides and carbides such as silicon carbide or tungsten carbide; ferromagnetic ferrites. As the material of the carrier core material, ferrite or magnetite is preferable because it is easy to obtain necessary magnetic characteristics.

  The average particle diameter of the carrier core material 210 is preferably 30 μm or more and 100 μm or less. When the average particle diameter of the carrier core material 210 is 30 μm or more and 100 μm or less, the two-component developer of this embodiment including the carrier 200 can achieve good developability. Said average particle diameter can be measured using a scanning electron microscope (SEM), for example.

  The first layer 220 will be described below. In the present embodiment, as described above, since the first layer 220 is made of a fluororesin, the charge imparting property of the carrier 200 can be made favorable.

  Examples of the fluororesin include tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polytetrafluoroethylene (PTFE), and polyvinylidene fluoride (PVDF). ) Or polyvinyl fluoride (PVF). The fluororesin is selected from tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and polytetrafluoroethylene in order to make the charge imparting property sufficiently suitable. One or more are preferable.

  The amount of the fluororesin used for forming the first layer 220 in the carrier 200 is preferably 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the carrier core material 210. When the amount of the fluororesin used is 1 part by mass or more, the charge imparting property of the carrier 200 does not deteriorate, and thus fog (a phenomenon in which toner particles adhere even in non-exposed areas) can be suppressed. Furthermore, it is possible to suppress only toner particles from flying excessively during development. In addition, when the amount of the fluororesin used is 15 parts by mass or less, the charge imparting property is appropriately lowered and does not become too high, so that the image density of the formed image due to the decrease in developability is desired. It can suppress falling below the value.

  The thickness of the first layer 220 is preferably 100 nm or more and 2000 nm or less in order to make the charge imparting property suitable.

  The second layer 230 will be described below. Melamine resin has high hardness and is excellent in friction resistance and heat resistance. By being covered with the second layer 230 made of melamine resin, the carrier 200 has excellent durability.

  The amount of the melamine resin used for forming the second layer 230 is preferably 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the carrier core material 210. When the usage-amount of a melamine resin is 1 mass part or more, the intensity | strength and durability of the carrier 200 can fully be improved. On the other hand, when the amount of the melamine resin used is 15 parts by mass or less, the cationic property is not too strong and the toner particles and the carrier 100 are uniformly mixed in the two-component developer. When the amount is 15 parts by mass or less, sufficient charging performance for the toner particles of fluorine in the first layer is sufficiently obtained, so that the toner can be suitably charged. If the second layer becomes too thick due to the use of too much melamine resin, the function of charging the toner of the fluororesin of the first layer is impaired.

  The thickness of the second layer 230 is preferably 100 nm or more and 2000 nm or less in order to achieve good durability.

  With reference to FIG. 4, the carrier contained in the two-component developer of this embodiment will be further described. FIG. 4 shows another aspect of the carrier contained in the two-component developer of this embodiment. As shown in FIG. 4, the carrier 300 includes a carrier core material 210, a first layer 220, a second layer 230, and an inorganic fine particle layer 310. The inorganic fine particle layer 310 includes inorganic fine particles and is formed between the first layer 220 and the second layer 230.

  The inorganic fine particle layer 310 functions as a developing electrode due to the conductivity of the inorganic fine particles. Therefore, the carrier 300 can form a high-quality image in which the edge effect (the effect that the density is high in the peripheral part of the image and the density is low in the central part of the image) is suppressed. Further, when the inorganic fine particle layer 310 is formed, the toner particles can be prevented from being excessively charged due to the conductivity of the inorganic fine particles. In general, when printing is continuously performed on a recording medium at a low printing rate, the image density of the formed image tends to decrease. However, by forming the inorganic fine particle layer 310, it is possible to obtain a carrier that can suppress a decrease in image density that occurs during continuous printing at a low printing rate. In general, since the fluorine-based resin is insufficient in compatibility (compatibility) with other resins, the uniform second layer 230 may not be formed on the surface of the first layer 220 in some cases. However, when the inorganic fine particle layer 310 is formed between the first layer 220 and the second layer 230, the inorganic fine particles serve as a base point, and the melamine resin diffuses well on the surface of the first layer 220. As a result, the second layer 230 can be uniformly formed.

  Examples of the inorganic fine particles contained in the inorganic fine particle layer 310 include magnetite fine particles, titanium oxide fine particles, silica fine particles, and alumina fine particles. As the inorganic fine particles, magnetite fine particles are preferable because they have high conductivity.

  The average particle size of the inorganic fine particles contained in the inorganic fine particle layer 310 is a primary particle size of preferably 1000 nm or less, more preferably 10 nm or more and 500 nm or less, and particularly preferably 50 nm or more and 300 nm or less. When the average particle diameter of the inorganic fine particles is 1000 nm or less, the drop of the inorganic fine particles from the inorganic fine particle layer 310 can be suppressed. Further, when the average particle size of the inorganic fine particles is 50 nm or more, the charge imparting property of the carrier 300 can be improved.

  The amount of the inorganic fine particles used for forming the inorganic fine particle layer 310 is preferably 0.1% by mass or more and 10% by mass or less with respect to the carrier core material. When the amount of the inorganic fine particles used is 0.1% by mass or more, it is possible to suppress the occurrence of image defects due to the edge effect in the formed image. In addition, since an excessive increase in the charge amount of the toner particles 100 can be suppressed, it is possible to prevent the image density of the formed image from falling below a desired value. As a result, a high-quality image can be formed. On the other hand, when the amount of the inorganic fine particles used is 10% by mass or less, the inorganic fine particle layer 310 is a uniform layer in which the removal of the inorganic fine particles is suppressed.

  As shown in FIG. 4, the inorganic fine particle layer 310 is preferably formed so that the inorganic fine particles have a gap. This is because, in such a case, the first layer and the second layer are not completely separated by the inorganic fine particle layer 310, so that the adhesion between the first layer and the second layer is not impaired, and the first layer has the first layer. This is because the two layers adhere well and do not fall off.

(Two-component developer)
With reference to FIG. 5, the two-component developer of this embodiment will be described. FIG. 5 shows a two-component developer 400 of this embodiment. As shown in FIG. 5, the two-component developer 400 of this embodiment includes toner particles 100 and a carrier 200.

  In the two-component developer 400, the content of the toner particles 100 is preferably 1 part by mass or more and 20 parts by mass or less, and preferably 3 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the carrier 200. More preferred. By setting the content of the toner particles 100 to 1 part by mass or more and 20 parts by mass or less, the two-component developer 400 can achieve both good prevention of toner scattering and chargeability.

(Method for producing two-component developer)
The manufacturing method of the two-component developer 400 includes a step of preparing the toner particles 100 (toner particle preparation step), a step of preparing the carrier 200 (carrier preparation step), and a step of mixing the toner particles 100 and the carrier 200 ( Mixing step).

  The toner particle preparation process will be described with reference to FIG. The step of preparing toner particles 100 includes a step of preparing toner base particles 110 (toner base particle preparation step), a step of preparing external additive 160 (external additive preparation step), and external additive 160 as a toner base. A step of externally adding the particles 110 (external addition step). The external additive 160 includes silica fine particles 120 (coated silica fine particles 140) coated with the melamine resin layer 130.

  In order to execute the toner base particle preparation step, commercially available toner base particles may be used as they are. Alternatively, a method of preparing toner base particles by appropriately dispersing components other than the binder resin (for example, a colorant, a charge control agent, or a release agent) in the binder resin as necessary. Good. Specific examples of such a method include a melt-kneading method.

  The toner base particle preparation step using the melt-kneading method will be described below. The toner base particle preparation step using the melt kneading method is executed by performing a melt kneading step, a pulverizing step, and a classification step. In the melt-kneading step, the binder resin and components other than the binder resin are mixed as necessary, and the resulting mixture is melt-kneaded to obtain a melt-kneaded product. In the pulverization step, the obtained melt-kneaded product is appropriately cooled and solidified, and then pulverized by a known method to obtain a pulverized product. In the classification step, the obtained pulverized product is classified by a known method to obtain toner base particles 110 having a desired particle size.

  The external additive preparation process will be described. The surface of the silica fine particles 120 is coated with a melamine resin layer 130 to prepare coated silica fine particles 140. Specifically, the melamine resin precursor and silica fine particles are added to an appropriate solvent (for example, water). Then, the melamine resin precursor is reacted at an appropriate reaction temperature and reaction time. The coated silica fine particles 140 can be prepared by filtering and drying the precipitate precipitated in the solution after the reaction using a known method.

  The coated silica fine particles 140 may be used as the external additive 160 as they are, or the coated silica fine particles 140 and, if necessary, the external additive fine particles 150 other than the coated silica fine particles 140 may be mixed using a known method. The external additive 160 can be used.

  In the external addition process, the external additive 160 is externally added to the surface of the toner base particles 110. As a suitable external addition method, the external additive conditions are adjusted so that the external additive 160 is not completely buried in the surface of the toner base particles 110, and a toner (for example, a Henschel mixer or a Nauter mixer) is used. A method of mixing the base particles 110 and the external additive 160 is exemplified.

  The carrier preparation process will be described with reference to FIG. In the carrier preparation step, the carrier 200 is prepared. The carrier preparation step includes a step of preparing the carrier core material 210 (carrier core material preparation step), a step of supplying a first layer forming solution (first layer forming solution supplying step), and a second layer forming solution. Including a step (second layer forming liquid supply step) and a heat treatment step.

  In the carrier core material preparation step, the carrier core material 210 is prepared. Specifically, the carrier core material 210 can be prepared by pulverizing a metal such as ferrite or magnetite using a pulverizer such as a ball mill and then firing the metal. For the firing, for example, a burner firing furnace, a rotary firing furnace, or an electric furnace can be used. The firing temperature in the carrier core material preparation step can be, for example, 900 ° C. or higher and 1200 ° C. or lower. Similarly, the firing time can be, for example, 1 hour or more and 24 hours or less. In the carrier core material preparation step, a commercially available carrier core material may be prepared.

  In the first layer forming liquid supply step, a first layer forming liquid is prepared, and this first layer forming liquid is supplied to the surface of the carrier core material 210. The first layer forming liquid contains a fluororesin and is prepared by dispersing the fluororesin in a suitable solvent. The first layer 220 can be formed by performing a heat treatment step to be described later on the first layer forming liquid containing the fluorine resin and curing the fluorine resin on the surface of the carrier core material 210. Examples of the solvent include methyl ethyl ketone or tetrahydrofuran. These solvents may be used as a mixture.

  In order to supply the first layer forming liquid to the surface of the carrier core material 210, for example, a method of immersing the carrier core material 210 in the first layer forming liquid, or a state in which the carrier core material 210 is fluidized in advance A method of spraying the first layer forming liquid can be employed.

  In the second layer forming liquid supply step, a second layer forming liquid is prepared, and this second layer forming liquid is supplied to the surface of the carrier core material 210 supplied with the first layer forming liquid. The liquid for forming the second layer contains a melamine resin and is prepared by dispersing the melamine resin in an appropriate solvent. Then, the second layer forming liquid containing the melamine resin is subjected to a heat treatment step to be described later, and the second melamine resin is cured on the surface of the carrier core material 210 supplied with the first layer forming liquid. Layer 230 can be formed. Examples of the solvent include methyl ethyl ketone or tetrahydrofuran. These solvents may be used as a mixture.

  In order to supply the liquid for forming the second layer to the carrier core material 210 supplied with the first layer forming solution, for example, the carrier core material 210 supplied with the liquid for forming the first layer is formed as the second layer. A method of immersing in a liquid for use, or a method of spraying a liquid for forming a second layer onto the carrier core 210 in a state in which the carrier core 210 supplied with the liquid for forming a first layer is fluidized in advance. Can be adopted.

  In the heat treatment step, the heat treatment is performed on the carrier core material 210 after the second layer forming liquid is supplied. Thereby, the resin (that is, fluorine-based resin or melamine resin) contained in the first layer forming liquid or the second layer forming liquid is cured to form the first layer 220 or the second layer 230. Specifically, the heat treatment step can be performed by heat-treating the carrier core material 210 to which the first-layer forming liquid and the second-layer forming liquid are supplied in this order while being fluidized by a known method. it can. The heat treatment temperature can be, for example, 200 ° C. or higher and 300 ° C. or lower. The heat treatment time can be, for example, 30 minutes or more and 90 minutes or less.

  When the inorganic fine particle layer 310 is formed between the first layer 220 and the second layer 230 as shown in FIG. 4, the first layer forming liquid supply step and the second layer forming liquid supply step In the meantime, the step of forming the inorganic fine particle layer 310 (inorganic fine particle layer forming step) may be executed. Specifically, in the inorganic fine particle layer forming step, the carrier fine particles 210 and the inorganic fine particles after the first layer forming liquid is supplied are agitated using a known mixing stirrer, whereby the inorganic fine particles are The inorganic fine particle layer 310 can be formed by adhering to the surface of the single layer forming liquid. Examples of the mixing stirrer include a ball mill, a V-type mixer, and a Henschel mixer.

  In the mixing step in the manufacturing method of the present embodiment, the toner particles 100 and the carrier 200 are mixed under appropriate conditions to obtain the two-component developer of the present embodiment as described above. In the mixing step, a mixer such as a ball mill, a Nauter mixer, or a rocking mixer (registered trademark) can be used.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the range of this Example at all.

Example 1
Preparation of Coated Silica Fine Particles 50 g of water-soluble famed silica (manufactured by Nippon Aerosil Co., Ltd., “AEROSIL 200”, specific surface area 200 m 2 / g) was added and dispersed in 500 ml of ion-exchanged water. Subsequently, after adjusting pH to 3-4 using 0.5N hydrochloric acid (the Wako Pure Chemical Industries Ltd. make, "Wako first grade 087-01076"), methylol melamine (methylol melamine precursor) (Nippon Carbide Industries, Ltd.) 50 g of “Nikaresin S-260” (manufactured by Co., Ltd.) was dissolved to obtain a solution. This solution was placed in a 1 L separable flask and reacted at 70 ° C. for 30 minutes in a thermostatic chamber (Yamato Scientific Co., Ltd., “Constant water bath BK400”). After the reaction, the precipitate precipitated in the separable flask was filtered and dried using a dryer (Yamato Kagaku Co., Ltd., “Square vacuum constant temperature dryer DP43 / 63”). Next, the silica fine particles agglomerated after drying are pulverized using a pulverizer (Nippon Pneumatic Kogyo Co., Ltd., “supersonic jet pulverizer PJM-80SP”), and the silica fine particles coated with the melamine resin layer are obtained. Obtained.

(Preparation of toner particles a)
Cyan toner (cyan toner for “TAKalpha5550” manufactured by Kyocera Document Solutions Co., Ltd.) was used as toner base particles. To the total amount of toner mother particles, 1.0% by mass of titanium oxide fine particles (manufactured by Titanium Industry Co., Ltd., “EC-100”) and 0.7% by mass of the coated silica fine particles were added as external additives. . Thereafter, using a Henschel mixer (“FM-10B” manufactured by Nippon Coke Kogyo Co., Ltd.), the mixture was mixed for 5 minutes at a rotational speed of 3500 rpm, and an external addition process was performed to obtain toner particles a.

(Preparation of carrier A)
First, a carrier core preparation process was executed. 40 parts by mass of manganese (II) oxide, 9 parts by mass of magnesium oxide, 50 parts by mass of iron (III) oxide, and 1 part by mass of strontium oxide were mixed and pulverized with a ball mill for 2 hours. Then, it baked at 1000 degreeC for 5 hours, and obtained the manganese type ferrite carrier core material. The obtained manganese-based ferrite carrier core had a particle size of 40 μm and a saturation magnetization of 65 Am 2 / kg when a magnetic field of 3000 × 10 3 / 4π · A / m was applied.

  Subsequently, the liquid supply process for 1st layer formation was performed. A liquid for forming a first layer was prepared by dispersing 10 parts by mass of tetrafluoroethylene / hexafluoropropylene copolymer (FEP) as a fluororesin in 100 parts by mass of methyl ethyl ketone. The first layer forming solution having a solid content of 5 parts by mass was spray-coated on 100 parts by mass of the manganese-based ferrite carrier core material using a fluid coating apparatus.

  Subsequently, the liquid supply process for 2nd layer formation was performed. Melamine resin solution (Methylolated urea resin solution (manufactured by Showa Denko KK, “Milben Resin SUM-100”) and ion-exchanged water adjusted to pH 4 with hydrochloric acid (solid content concentration: 80% by mass)) Was used as the second layer forming solution. While fluidizing 100 parts by mass of the manganese-based ferrite carrier core material, the second layer forming liquid having a solid content of 5 parts by mass was spray-coated.

  Then, the heat processing process for 1 hour was performed at 280 degreeC with the fluid tank, the fluororesin and the melamine resin were hardened, and the carrier A was obtained.

(Manufacture of two-component developer)
The toner particles a and the carrier A are mixed so that the ratio of the toner particles a is 10% by mass (that is, the added amount of the toner particles a is 10% by mass with respect to 100 parts by mass of the total amount of the toner particles a and the carrier A). The two-component developer of Example 1 was obtained by mixing and mixing with a rocking mixer (registered trademark) for 1 hour.

(Example 2)
As a fluororesin blended in the first layer forming liquid, the same operation as in Example 1 was performed except that tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) was used instead of FEP, A two-component developer of Example 2 was obtained.

(Example 3)
The two-component development of Example 3 was carried out in the same manner as in Example 1 except that polytetrafluoroethylene (PTFE) was used in place of FEP as the fluororesin blended in the first layer forming solution. An agent was obtained.

Example 4
As fluororesin blended in the liquid for forming the first layer, tetrafluoroethylene / hexafluoropropylene copolymer [FEP (4.6 fluoride)] and polytetrafluoroethylene (PTFE) are 1 instead of FEP. A two-component developer of Example 4 was obtained in the same manner as in Example 1 except that a mixed resin mixed at a ratio of 1 (mass ratio) was used.

(Example 5)
A two-component developer was obtained by performing the same operation as in Example 1 except that the inorganic fine particle layer forming step was performed after the first layer forming liquid supplying step. That is, 100 mass parts of the carrier core material after passing through the first layer forming liquid supply step was fluidized in a fluidized tank, and magnetite fine particles (“RB-BL-P”, volume produced by Titanium Industry Co., Ltd.) were added thereto. 3.0 parts by mass of an average particle size of 0.1 μm) is added, the magnetite fine particles are adhered to the surface of the first layer forming liquid to form an inorganic fine particle layer, and then the second layer forming liquid supplying step is executed. A two-component developer of Example 5 was obtained by performing the same operation as in Example 1 except that.

(Example 6)
As a fluororesin blended in the first layer forming liquid, the same operation as in Example 5 was performed except that tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) was used instead of FEP, A two-component developer of Example 6 was obtained.

(Example 7)
The two-component development of Example 7 was carried out in the same manner as in Example 5 except that polytetrafluoroethylene (PTFE) was used instead of FEP as the fluororesin blended in the first layer forming solution. An agent was obtained.

(Example 8)
As fluororesin blended in the liquid for forming the first layer, tetrafluoroethylene / hexafluoropropylene copolymer [FEP (4.6 fluoride)] and polytetrafluoroethylene (PTFE) are 1 instead of FEP. A two-component developer of Example 8 was obtained in the same manner as in Example 5 except that a mixed resin mixed at a ratio of 1 (mass ratio) was used.

Example 9
The same operation as in Example 8 was performed except that the magnetite fine particles used in the inorganic fine particle layer forming step were changed to magnetite fine particles “TN-15” (volume average particle diameter 0.17 μm) manufactured by Mitsui Mining & Smelting Co., Ltd. Thus, a two-component developer of Example 9 was obtained.

(Example 10)
The same operation as in Example 8 was performed except that the magnetite fine particles used in the inorganic fine particle layer forming step were changed to titanium oxide fine particles (manufactured by Teika Co., Ltd., “JA-C”, volume average particle size 0.18 μm). Thus, a two-component developer of Example 10 was obtained.

(Example 11)
A two-component developer of Example 11 was obtained in the same manner as in Example 5 except that the amount of methylolmelamine used was 10 g in the production of silica fine particles.

(Example 12)
A two-component developer of Example 12 was obtained in the same manner as in Example 5 except that the amount of methylolmelamine used was changed to 100 g in the production of silica fine particles.

(Example 13)
A two-component developer of Example 13 was obtained by performing the same operation as in Example 5 except that the amount of methylolmelamine used was 500 g in the production of silica fine particles.

(Comparative Example 1)
A comparative example was carried out in the same manner as in Example 5 except that an untreated product of water-soluble famed silica (manufactured by Nippon Aerosil Co., Ltd., “AEROSIL200”, specific surface area 200 m 2 / g) was used as the silica fine particles. 1 two-component developer was obtained.

(Comparative Example 2)
In the production of the coated silica fine particles, a water-soluble famed silica (“AEROSIL200” manufactured by Nippon Aerosil Co., Ltd., specific surface area 200 m 2 / g) treated with amino-modified silicone oil instead of the melamine resin solution was used. The two-component developer of Comparative Example 2 was obtained in the same manner as in Example 5.

(Comparative Example 3)
The same operation as in Example 1 was performed except that only the second layer (layer composed of FEP) was formed on the surface of the carrier core to obtain carrier A, and the first layer was not formed. The two-component developer of Example 3 was obtained.

(Comparative Example 4)
Only the second layer (layer composed of melamine resin) was formed on the surface of the carrier core material to obtain carrier A, and the same operation as in Example 1 was performed except that the first layer was not formed. The two-component developer of Example 4 was obtained.

(Comparative Example 5)
A resin solution in which a tetrafluoroethylene / hexafluoropropylene copolymer (FEP) and a melamine resin were mixed and dispersed was applied to the surface of the carrier core material to form only a layer composed of a fluororesin and a melamine resin. Except for the above, in other words, the carrier A does not adopt the two-layer configuration in which the first layer and the second layer are laminated, and implements a coating layer composed of a mixed resin of a fluororesin and a melamine resin. The same operation as in Example 1 was performed to obtain a two-component developer of Comparative Example 5. The resin solution used in Comparative Example 5 was prepared in a resin solution in which 5 parts by mass of FEP was mixed with 100 parts by mass of ion-exchanged water and the second layer forming liquid supply step of Example 1. It was obtained by mixing 5 parts by mass of the prepared melamine resin solution.

(Comparative Example 6)
Except for supplying the liquid for forming the second layer in Example 1 to the carrier core material and supplying the liquid for forming the first layer in Example 1 onto the inorganic fine particle layer, that is, compared with Example 1, A two-component developer of Comparative Example 6 was obtained in the same manner as in Example 1 except that the stacking order of the layer and the second layer was changed.

(Comparative Example 7)
In the second layer forming solution, the same operation as in Example 5 was performed except that a urea resin (“Milben Resin 3HSP-H” manufactured by Showa Denko KK) was used instead of the methylolated urea resin in the melamine resin solution. Thus, a two-component developer of Comparative Example 7 was obtained.

(Comparative Example 8)
In the second layer forming solution, the same operation as in Example 5 was performed except that a silicone resin (“SR2410” manufactured by Toray Dow Corning Co., Ltd.) was used instead of the methylolated urea resin in the melamine resin solution. A two-component developer of Comparative Example 8 was obtained.

The evaluation methods of the two-component developers obtained in the examples and comparative examples are as follows.
(1) Image density (ID)
Using the two-component developer obtained in the examples and comparative examples and the toner particles for replenishment, in a normal environment (temperature 20 ° C., relative humidity 50%), a multifunction machine (manufactured by Kyocera Document Solutions Inc., “ The image sample A for initial evaluation was output using “Taksalfa 500ci”). Thereafter, 10,000 sheets were continuously printed at a printing rate of 1.0%. Then, an image sample (image sample B) after continuous printing of 10,000 sheets was output. Thereafter, 100,000 sheets were continuously printed at a printing rate of 5.0%. And the image sample (image sample C) after 100,000 sheets continuous printing was output. The image sample includes a solid image area (5 cm × 5 cm) and a non-printing area. The image density (ID) of the solid images of the image sample A, the image sample B, and the image sample C was measured using a Macbeth reflection densitometer (“RD914” manufactured by Sakata Inx Engineering Co., Ltd.). The average of the measurement values at five locations was used as the image density of the image to be measured. The image density was evaluated according to the following criteria.
A (very good): ID is 1.3 (-) or more. In this case, the image density is particularly high and the image quality is very good.
○ (good): ID is 1.0 (−) or more and less than 1.3 (−). In this case, the image density is high and the image quality is good.
X (defect): ID is less than 1.0 (-). In this case, the image density is very thin and the image quality is poor.

(2) Fog value (FD)
The fog values (FD) of the non-printed areas of the image sample A, the image sample B, and the image sample C obtained by the above image density evaluation were measured with a reflection densitometer (“R710” manufactured by Ihara Electronics Co., Ltd.). The FD was calculated by the following formula. In addition, the average of the measured values at five locations was defined as the fogging value.
FD = (reflection density of the blank portion of the printed paper) − (reflection density of the non-printed paper)
The fogging value was evaluated according to the following criteria.
A (very good): FD is 0.005 (−) or less. In this case, FD is particularly low and very good.
○ (good): FD exceeds 0.005 (−) and is 0.010 (−) or less. In this case, the FD is low and good.
X (defect): FD exceeds 0.010 (-). In this case, the FD is very high and the image quality is poor.

Table 1 summarizes the evaluation results of the two-component developers obtained in the examples and comparative examples.

  In Table 1, “-” indicates that the inorganic fine particle layer was not formed. “* 1” indicates that silica fine particles whose surface was not coated were used. “* 2” indicates that only the first layer was formed in the carrier A and the second layer was not formed. “* 3” indicates that only the second layer was formed in the carrier A, and the first layer was not formed. “* 4” indicates that the carrier A did not have a two-layer structure in which the first layer and the second layer were laminated, but formed a coating layer composed of a fluororesin and a melamine resin. The amount of the material for treating the surface of the silica fine particle is in “parts by mass”.

  As is apparent from Table 1, the two-component developers obtained in Examples 1 to 4 are toner particles externally added with an external additive containing silica fine particles on which a melamine resin layer is formed, and a carrier core material. And a carrier including a second layer covering the surface of the first layer. For this reason, even when the printing rate is changed and printing is performed continuously, the charge amount of the toner particles is stable, the image density of the formed image does not decrease below a desired value, and the fogging is suppressed.

  The two-component developers obtained in Examples 5 to 9 contained a carrier in which an inorganic fine particle layer containing magnetite fine particles was formed between the first layer and the second layer. Therefore, compared with Examples 1-4 in which the inorganic fine particle layer is not formed in the carrier, the uniformity of the second layer in the carrier is improved, and the fog after continuous printing at a printing rate of 5.0% is suppressed. It was. Furthermore, the image density of the image formed after continuous printing at a printing rate of 1.0% is lower than desired because the charge-up is suppressed because the magnetite fine particles have high conductivity. However, it was suppressed rather than Examples 1-4.

  The two-component developer obtained in Example 10 contained a carrier in which an inorganic fine particle layer containing titanium oxide fine particles was formed between the first layer and the second layer. Therefore, compared with the two-component developers of Examples 1 to 4 in which the inorganic fine particle layer is not formed on the carrier, the uniformity of the second layer on the carrier is good, and after continuous printing at a printing rate of 5.0% The fog was suppressed. However, since the conductivity of the titanium oxide fine particles is lower than the conductivity of the magnetite fine particles, the image density after continuous printing at a printing rate of 1.0% includes a carrier in which the inorganic fine particle layer is not formed. The image density was similar to that when the two-component developers of Examples 1 to 4 were used.

  In the two-component developer obtained in Example 11, the amount of melamine resin was reduced and the melamine resin layer was coated on the surface of the silica fine particles. In the two-component developer obtained in Example 12, the amount of melamine resin constituting the melamine resin layer was increased. Regarding these two-component developers, the same results as in Example 5 were obtained in both the image density and the fog.

  In the two-component developer obtained in Example 13, the silica fine particles were slightly agglomerated by increasing the amount of the melamine resin on the surface of the silica fine particles and covering the melamine resin layer. However, good results were obtained for both image density and fog.

  The two-component developer obtained in Comparative Example 1 contained toner particles externally added with silica fine particles that were not subjected to any surface treatment. The two-component developer obtained in Comparative Example 2 contained toner particles externally added with silica fine particles surface-treated with amino-modified silicone oil. For these two-component developers, fogging occurred after continuous printing at a printing rate of 5.0%. This is presumably because the silica fine particles adhere to the carrier and contaminate the carrier, whereby the charge imparting property of the carrier is lowered, and the charge amount of the toner is thereby lowered.

  The two-component developer obtained in Comparative Example 3 contained a carrier on which the second layer was not formed. Therefore, the image density has been low since the initial printing due to the fact that the charge imparting property of the carrier has become too high.

  The two-component developer obtained in Comparative Example 4 contained a carrier on which the first layer was not formed. For this reason, the charge imparting property was extremely lowered, the image density was low from the initial printing, and fogging occurred. Further, during continuous printing, the toner particles flew into the developing machine, and the evaluation could not be continued.

  The two-component developer obtained in Comparative Example 5 contained a carrier on which a layer composed of a mixed resin of a fluororesin and a melamine resin was formed. For this reason, the coating layer becomes non-uniform, the charge imparting property is not stable, and the image density is lowered after continuous printing at a printing rate of 1.0%. Further, fogging occurred after continuous printing at a printing rate of 5.0%. This is probably because the two-component developer of Comparative Example 5 has a low ability to charge the carrier toner.

  The two-component developer obtained in Comparative Example 6 contained a carrier in which the stacking order of the first layer and the second layer was reversed. Therefore, the charge imparting property becomes too high, and the image density is lowered from the initial printing.

  The two-component developer obtained in Comparative Example 7 used urea resin instead of melamine resin as the resin constituting the second layer. For this reason, carrier contamination occurs due to silica fine particles adhering to the carrier, and fogging occurs due to a decrease in charge imparting property of the carrier during printing at a printing rate of 5.0%.

  The two-component developer obtained in Comparative Example 8 used a silicone resin instead of a melamine resin as the resin constituting the second layer. For this reason, the image density decreased from the initial printing due to the fact that the charge imparting property of the carrier became too high.

  The two-component developer of this embodiment is excellent in chargeability and durability. Therefore, the two-component developer of this embodiment can be suitably used in image printing that employs electrophotography.

100 toner particles 110 toner base particles 120 silica fine particles 130 melamine resin layer 140 coated silica fine particles 150 external additive fine particles 160 other than silica fine particles external additive 200 carrier 210 carrier core material 220 first layer 230 second layer 300 carrier 310 inorganic fine particles Layer 400 Two-component developer

Claims (5)

  1. A two-component developer comprising toner particles and a carrier,
    The toner particles include toner base particles containing a binder resin, and an external additive externally added to the surface of the toner base particles.
    The external additive includes silica fine particles coated with a melamine resin layer,
    The carrier includes a carrier core material, a first layer covering the surface of the carrier core material, and a second layer covering the surface of the first layer;
    A two-component developer in which the first layer is made of a fluorine-based resin and the second layer is made of a melamine resin.
  2. The said fluororesin is 1 or more types selected from the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, the tetrafluoroethylene-hexafluoropropylene copolymer, and the polytetrafluoroethylene of Claim 1. Two component developer.
  3. The two-component developer according to claim 1 or 2, further comprising an inorganic fine particle layer formed between the first layer and the second layer, wherein the inorganic fine particle layer contains inorganic fine particles.
  4. The two-component developer according to claim 3, wherein the inorganic fine particles are magnetite fine particles.
  5. A method for producing a two-component developer comprising toner particles and a carrier,
    Preparing the toner particles;
    Preparing the carrier;
    Mixing the carrier and the toner particles,
    Preparing the toner particles comprises:
    A step of preparing toner base particles;
    A step of preparing an external additive;
    Externally adding the external additive to the toner base particles,
    The external additive contains silica fine particles coated with a melamine resin layer,
    Preparing the carrier comprises:
    Preparing a carrier core material;
    Supplying a first layer forming liquid containing a fluororesin to the surface of the carrier core;
    Supplying a second layer forming liquid containing a melamine resin to the surface of the carrier core material supplied with the first layer forming liquid;
    Heat-treating the carrier core material supplied with the first layer forming liquid and the second layer forming liquid. A method for producing a two-component developer.
JP2014003284A 2014-01-10 2014-01-10 Two-component developer and method for producing two-component developer Active JP6001575B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014003284A JP6001575B2 (en) 2014-01-10 2014-01-10 Two-component developer and method for producing two-component developer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2014003284A JP6001575B2 (en) 2014-01-10 2014-01-10 Two-component developer and method for producing two-component developer

Publications (2)

Publication Number Publication Date
JP2015132681A JP2015132681A (en) 2015-07-23
JP6001575B2 true JP6001575B2 (en) 2016-10-05

Family

ID=53899931

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2014003284A Active JP6001575B2 (en) 2014-01-10 2014-01-10 Two-component developer and method for producing two-component developer

Country Status (1)

Country Link
JP (1) JP6001575B2 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6390634B2 (en) * 2016-01-26 2018-09-19 京セラドキュメントソリューションズ株式会社 Toner for electrostatic latent image development and external additive
JP6432544B2 (en) * 2016-02-23 2018-12-05 京セラドキュメントソリューションズ株式会社 Method for producing toner for developing electrostatic latent image and image forming method

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03263052A (en) * 1990-03-13 1991-11-22 Mita Ind Co Ltd Carrier for two-component developer for dry processing
JPH04208943A (en) * 1990-11-30 1992-07-30 Matsushita Electric Ind Co Ltd One-component nonmagnetic developer
JPH04328757A (en) * 1991-04-30 1992-11-17 Canon Inc Toner for developing electrostatic charge image
JP2998633B2 (en) * 1996-04-01 2000-01-11 富士ゼロックス株式会社 An electrostatic latent image developer carrier, a method of manufacturing the same, an electrostatic latent image developer, an image forming method and an image forming apparatus
JP2004333931A (en) * 2003-05-08 2004-11-25 Canon Inc Magnetic carrier and two-component developer
JP4631016B2 (en) * 2003-08-26 2011-02-23 日産化学工業株式会社 Surface-treated cured amino resin particles and method for producing the same
US7157200B2 (en) * 2004-05-06 2007-01-02 Xerox Corporation Emulsion aggregation black toner and developer with superior image quality
JP2006251400A (en) * 2005-03-10 2006-09-21 Fuji Xerox Co Ltd Image forming method and image forming apparatus
JP5455967B2 (en) * 2011-04-22 2014-03-26 京セラドキュメントソリューションズ株式会社 Two component developer
JP5766162B2 (en) * 2012-09-07 2015-08-19 関東電化工業株式会社 Carrier and two-component developer

Also Published As

Publication number Publication date
JP2015132681A (en) 2015-07-23

Similar Documents

Publication Publication Date Title
RU2437133C2 (en) Two-component developer, replenishing developer and image forming method
US8142972B2 (en) Developer for replenishment and image forming method
JP4625417B2 (en) Carrier and two-component developer
JP5153792B2 (en) Toner and two-component developer
EP2252917B1 (en) Magnetic carrier and two-components developer
US8927188B2 (en) Method of producing magnetic carrier and magnetic carrier that uses this production method
EP1755004B1 (en) Colour image forming apparatus for adjusting a constant toner layer thickness by using a transparent toner
CN101055438B (en) Electrostatic latent image carrier, electrostatic latent image developer and image forming apparatus
US8062822B2 (en) Carrier for electrostatic latent image development and electrostatic latent image developer
KR100432760B1 (en) Carrier for developer of electrostatic latent image, method of producing carrier, developer of electrostatic latent image, image forming method, and image forming apparatus
KR101396011B1 (en) Method for producing magnetic carrier
EP1477863A2 (en) Carrier, developer, image forming apparatus and process cartridge
JP5522452B2 (en) Carrier for two-component developer
JP3123153B2 (en) Toner and manufacturing method thereof for developing an electrostatic charge image
JP4739316B2 (en) Electrophotographic carrier production method and electrophotographic carrier produced using the production method
JP5869450B2 (en) Evaluation method of difficulty in peeling of shell layer from toner core particles in toner for developing electrostatic latent image
US9606467B2 (en) Magnetic carrier for electrophotographic developer and process for producing the same, and two-component system developer
US20090197190A1 (en) Two-component developer, replenishing developer, and image-forming method using the developers
US9500975B2 (en) Magnetic carrier and two-component developer
US20090239173A1 (en) Resin-filled carrier for electrophotographic developer, and electrophotographic developer using the resin-filled carrier
JPWO2005013012A1 (en) Toner, toner manufacturing method, two-component developer, and image forming apparatus
JP5454081B2 (en) Career
US20030113650A1 (en) Image forming method
US7459254B2 (en) Toner and two-component developer
JP2010169842A (en) Electrostatic image developing green toner, electrostatic image developer, electrostatic image developing toner set, electrostatic image developer set and image forming apparatus

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20151120

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20160713

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20160809

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20160901

R150 Certificate of patent or registration of utility model

Ref document number: 6001575

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150