WO2014033881A1 - Procédé permettant de produire un matériau de noyau de support destiné à des développateurs électrophotographiques, matériau de noyau de support destiné à des développateurs électrophotographiques, support destiné à des développateurs électrophotographiques, et développateurs électrophotographiques - Google Patents

Procédé permettant de produire un matériau de noyau de support destiné à des développateurs électrophotographiques, matériau de noyau de support destiné à des développateurs électrophotographiques, support destiné à des développateurs électrophotographiques, et développateurs électrophotographiques Download PDF

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Publication number
WO2014033881A1
WO2014033881A1 PCT/JP2012/072070 JP2012072070W WO2014033881A1 WO 2014033881 A1 WO2014033881 A1 WO 2014033881A1 JP 2012072070 W JP2012072070 W JP 2012072070W WO 2014033881 A1 WO2014033881 A1 WO 2014033881A1
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WIPO (PCT)
Prior art keywords
core material
carrier core
electrophotographic developer
carrier
electrophotographic
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PCT/JP2012/072070
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English (en)
Japanese (ja)
Inventor
晴日 関
智英 飯田
Original Assignee
Ｄｏｗａエレクトロニクス株式会社
Ｄｏｗａ Ｉｐクリエイション株式会社
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Priority to PCT/JP2012/072070 priority Critical patent/WO2014033881A1/fr
Publication of WO2014033881A1 publication Critical patent/WO2014033881A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/107—Developers with toner particles characterised by carrier particles having magnetic components
    • G03G9/108—Ferrite carrier, e.g. magnetite
    • G03G9/1085—Ferrite carrier, e.g. magnetite with non-ferrous metal oxide, e.g. MgO-Fe2O3
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/107—Developers with toner particles characterised by carrier particles having magnetic components
    • G03G9/1075—Structural characteristics of the carrier particles, e.g. shape or crystallographic structure

Definitions

  • the present invention relates to a method for producing a carrier core material for an electrophotographic developer (hereinafter sometimes simply referred to as “carrier core material”), a carrier core material for an electrophotographic developer, and a carrier for an electrophotographic developer (hereinafter simply referred to as “a carrier core material”).
  • Carrier and electrophotographic developer (hereinafter also simply referred to as “developer”), and particularly for electrophotographic developers used in copiers and MFPs (Multifunctional Printers).
  • developer electrophotographic developer
  • the present invention relates to an electrophotographic developer carrier core material, a method for producing the same, an electrophotographic developer carrier provided in the electrophotographic developer, and an electrophotographic developer.
  • a one-component developer using only toner as a component of developer and a two-component developer using toner and carrier as components of developer are provided. is there.
  • toner charged to a predetermined charge amount is supplied to the photoreceptor.
  • the electrostatic latent image formed on the photosensitive member is visualized with toner and transferred to a sheet.
  • the visible image with toner is fixed on the paper to obtain a desired image.
  • the developing device includes a rotatable magnet roller in which a plurality of S poles and N poles are alternately provided in the circumferential direction, and a stirring roller that stirs and mixes the toner and the carrier in the developing device.
  • a carrier made of magnetic powder is carried by a magnet roller.
  • a linear magnetic brush made of carrier particles is formed by the magnetic force of the magnet roller.
  • a plurality of toner particles adhere to the surface of the carrier particles by frictional charging by stirring. Toner is supplied to the surface of the photoconductor by rotating the magnet roller so that the magnetic brush is applied to the photoconductor. In a two-component developer, development is performed in this way.
  • the toner in the developing device is sequentially consumed by fixing to the paper, so new toner corresponding to the consumed amount is supplied from time to time to the developing device from the toner hopper attached to the developing device.
  • the carrier is not consumed by development and is used as it is until the end of its life.
  • the carrier which is a constituent material of the two-component developer includes a toner charging function and an insulating property for efficiently charging the toner by frictional charging by stirring, a toner transporting ability to appropriately transport and supply the toner to the photoreceptor, etc. Various functions are required.
  • the above-described carrier is composed of a core material, that is, a carrier core material constituting a core portion, and a coating resin provided so as to cover the surface of the carrier core material.
  • Patent Document 1 the technique regarding the magnetic body particle
  • Patent Document 1 it is described that there is a metal compound such as CaO (calcium oxide) or CaCO 3 (calcium carbonate) as a component for controlling the electric resistance and charge amount of the magnetic particles of the carrier or as a sintering accelerator. Yes.
  • the electrical characteristics are good, specifically, for example, the charge amount of the carrier core material itself is high.
  • the carrier core material is used by coating the surface with a coating resin from the viewpoint of improving the electrical characteristics thereof.
  • a part of the coating resin may be peeled off due to stress caused by stirring in the developing device, and the surface of the carrier core material may be exposed.
  • it is preferable that other characteristics such as magnetic characteristics are also favorable.
  • the carrier core material is coated with the coating resin as described above, but it is desired to reduce the amount of the coating resin to be coated. That is, when manufacturing a carrier having equivalent performance, if the coating resin for coating the carrier core material is small, it is possible to reduce the manufacturing cost. Furthermore, in addition to reducing the overall amount of coating resin, the physical effects due to the coating conditions, that is, the labor required to examine the coating conditions of the coating resin on the carrier core material, and errors in the coating conditions, etc. Can also be reduced.
  • An object of the present invention is to provide a method for producing a carrier core material for an electrophotographic developer that has good characteristics and can be produced at low cost.
  • Another object of the present invention is to provide a carrier core material for an electrophotographic developer that has good characteristics and can be manufactured at low cost.
  • Still another object of the present invention is to provide a carrier for an electrophotographic developer that has good characteristics and can be manufactured at low cost.
  • Still another object of the present invention is to provide an electrophotographic developer that has high image quality and can be manufactured at low cost.
  • the inventors of the present application have improved the frictional charging ability of the carrier core material.
  • calcium (Ca) which is a metal element, was added as a core component of the carrier core material.
  • this inventor considered that it was necessary to consider the influence on the surface property of the carrier core material manufactured about calcium contained as a constituent material of a carrier core material.
  • the inventors of the present invention have the general formula: Z x Ca y Fe 3-xy O 4 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, where Z is Mg, Mn, Ti, Cu, Zn , At least one metal selected from the group consisting of Sr and Ni), the carrier core material having a core composition as a main component, good surface properties, specifically, the degree of unevenness on the surface of the carrier core material It was considered that the amount of the coating resin can be reduced if is low.
  • the carrier core material obtained through the granulation step and the firing step it was considered to realize a surface property with less unevenness during the production, specifically, good grain growth of the crystal at the time of firing. .
  • the method for producing a carrier core material for an electrophotographic developer according to the present invention has a general formula: Z x Ca y Fe 3-xy O 4 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, provided that Z Is a method for producing a carrier core material for an electrophotographic developer having as a main component a core composition represented by at least one metal selected from the group consisting of Mg, Mn, Ti, Cu, Zn, Sr, and Ni).
  • the raw material containing calcium mixed in the mixing step is a raw material containing a water-soluble calcium salt.
  • the carrier core material manufactured by such a manufacturing method of the carrier core material for electrophotographic developer since calcium is added as a core composition, charging performance which is one of the characteristics required for the carrier core material Can be high.
  • a raw material containing calcium it is a raw material containing a water-soluble calcium salt, not CaO or CaCO 3 insoluble in water, which is generally used as an inexpensive material disclosed in Patent Document 1.
  • the degree of unevenness on the surface of the carrier core material can be reduced, and a relatively smooth surface can be obtained.
  • the resin necessary for filling the recessed portion is not required in the subsequent coating with the coating resin, and the amount of the coating resin can be greatly reduced. Also, a high level can be maintained in the magnetic characteristics and the like. Therefore, according to such a method for producing a carrier core material for an electrophotographic developer, a carrier core material for an electrophotographic developer having good characteristics can be produced at low cost.
  • Z x Ca y Fe 3- x-y O 4 (0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1, however, Z is, Mg, Mn, Ti, Cu , Zn, Sr, of Ni
  • Z is, Mg, Mn, Ti, Cu , Zn, Sr, of Ni
  • x 0, iron and calcium except for so-called inevitable impurities Is included as a core composition.
  • the salt of the water-soluble calcium salt is composed of a reducing substance.
  • the carrier core material whose surface unevenness degree is lower can be manufactured.
  • the water-soluble calcium salt contains Ca (CH 3 COO) 2 (calcium acetate).
  • Ca (CH 3 COO) 2 calcium acetate
  • the carrier core material for an electrophotographic developer has a general formula: Z x Ca y Fe 3-xy O 4 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, where Z is , Mg, Mn, Ti, Cu, Zn, Sr, Ni, and a carrier core material for an electrophotographic developer having a core composition as a main component represented by a core composition represented by: And a raw material containing calcium and a calcium containing raw material are mixed to granulate the mixture, and the granulated particles are fired at a predetermined temperature to form a magnetic phase.
  • the raw material containing calcium is a raw material containing a water-soluble calcium salt.
  • Such a carrier core material for an electrophotographic developer has good characteristics and can be manufactured at low cost.
  • the electrophotographic developer carrier core material according to the invention have the general formula: Z x Ca y Fe 3- x-y O 4 (0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1, however, Z is, Mg , At least one metal selected from the group consisting of Mn, Ti, Cu, Zn, Sr, and Ni), and a carrier core material for an electrophotographic developer having a core composition as a main component.
  • the length in the X direction in the cross-sectional curved surface is L
  • the length in the Y direction in the cross-sectional curved surface is M
  • the core charge amount of the carrier core material for an electrophotographic developer is 10 ⁇ C / g or more.
  • an electrophotographic developer carrier is an electrophotographic developer carrier used for an electrophotographic developer, and the carrier core material for an electrophotographic developer described above, And a resin that covers the surface of the carrier core material for the electrophotographic developer.
  • Such a carrier for an electrophotographic developer has good characteristics and can be manufactured at low cost.
  • the electrophotographic developer is an electrophotographic developer used for electrophotographic development, and the triboelectric charging between the above-described electrophotographic developer carrier and the electrophotographic developer carrier. And a toner capable of being charged in electrophotography.
  • electrophotographic developer includes the electrophotographic developer carrier having the above-described configuration, it has high image quality and can be manufactured at low cost.
  • a carrier core material for an electrophotographic developer having good characteristics can be produced at low cost.
  • Such a carrier core material for an electrophotographic developer has good characteristics and can be manufactured at low cost.
  • Such a carrier for an electrophotographic developer has good characteristics and can be manufactured at low cost.
  • Such an electrophotographic developer has high image quality and can be manufactured at low cost.
  • FIG. 3 is a schematic view showing a crystal grain boundary portion with lines in the appearance of the surface of the carrier core material according to Reference Example 1 shown in FIG. 2. It is the schematic which showed the part of the crystal grain boundary with the line
  • FIG. 3 is a schematic view showing a crystal grain boundary portion with lines in the appearance of the surface of the carrier core material according to Reference Example 1 shown in FIG. 2. It is the schematic which showed the part of the crystal grain boundary with the line
  • FIG. 5 is a schematic view showing a crystal grain boundary portion with lines in the appearance of the surface of the carrier core material according to Example 3 shown in FIG. 4.
  • the carrier core material which concerns on the comparative example 3 it is the schematic of the granular powder in the formation process of a magnetic phase.
  • the carrier core material which concerns on Example 3 it is the schematic of the granular powder in the formation process of a magnetic phase.
  • 6 is an electron micrograph showing an appearance of a carrier surface after resin coating according to Comparative Example 3.
  • FIG. 4 is an electron micrograph showing the appearance of a carrier surface after resin coating according to Example 3.
  • FIG. 12 is a schematic view showing a rough boundary portion of a coating resin application region with a line in the appearance of the surface of the carrier core material according to Example 3 shown in FIG. 11.
  • the external shape is a substantially spherical shape.
  • the particle diameter of the carrier core material according to one embodiment of the present invention is about 38 ⁇ m and has an appropriate particle size distribution. That is, the above-mentioned particle size means a volume average particle size.
  • the particle size and particle size distribution are arbitrarily set depending on required developer characteristics, yield in the manufacturing process, and the like.
  • minute irregularities formed mainly in the baking step described later are formed. This unevenness degree will be described later.
  • the outer shape of the carrier is substantially spherical, similar to the carrier core material.
  • the carrier is obtained by thinly coating the surface of the carrier core material with a resin, that is, the particle diameter of the carrier is almost the same as that of the carrier core material.
  • the developer according to one embodiment of the present invention is composed of the above carrier and toner.
  • the outer shape of the toner is also substantially spherical.
  • the toner is mainly composed of a styrene acrylic resin or a polyester resin, and contains a predetermined amount of pigment, wax or the like.
  • Such a toner is manufactured by, for example, a pulverization method or a polymerization method.
  • a toner having a particle diameter of about 5 ⁇ m, which is about 1/7 of the particle diameter of the carrier is used.
  • the mixing ratio of the toner and the carrier is also arbitrarily set according to the required developer characteristics and the like.
  • Such a developer is produced by mixing a predetermined amount of carrier and toner with an appropriate mixer.
  • FIG. 1 is a flowchart showing typical steps in a manufacturing method for manufacturing a carrier core material according to an embodiment of the present invention. A method for manufacturing a carrier core material according to an embodiment of the present invention will be described below with reference to FIG.
  • a raw material containing iron and a raw material containing calcium are prepared. And the prepared raw material is mix
  • an appropriate blending ratio is a blending ratio that the finally obtained carrier core material contains.
  • the raw material containing water-soluble calcium salt is used about the raw material containing calcium.
  • corrugations can be obtained on the surface.
  • the salt of the water-soluble calcium salt a salt composed of a reducing substance is preferably used.
  • corrugations can be obtained on the surface.
  • a raw material containing Ca (CH 3 COO) 2 (calcium acetate) is used.
  • the raw materials (iron raw material, calcium raw material) may be used as raw materials by calcining and pulverizing raw materials obtained by mixing the respective raw materials (iron raw material and calcium raw material) so as to have a desired composition.
  • the carrier core material the general formula: Z x Ca y Fe 3- x-y O 4 (0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1, however, Z is, Mg, Mn, Ti, Cu, You may comprise so that the core composition represented by the at least 1 type of metal selected from the group which consists of Zn, Sr, and Ni) may be made into a main component.
  • the mixed raw material is slurried (FIG. 1 (B)). That is, these raw materials are weighed according to the target composition of the carrier core material and mixed to obtain a slurry raw material.
  • a reducing agent may be further added to the slurry raw material described above in order to advance the reduction reaction in a part of the baking process described later.
  • the reducing agent carbon powder, polycarboxylic acid organic substances, polyacrylic acid organic substances, maleic acid, acetic acid, polyvinyl alcohol (PVA (polyvinyl alcohol)) organic substances, and mixtures thereof are preferably used.
  • the water is added to the slurry raw material described above and mixed and stirred, so that the solid content concentration is 40% by weight or more, preferably 50% by weight or more. If the solid content concentration of the slurry raw material is 50% by weight or more, it is preferable because the strength of the granulated pellet can be maintained.
  • the slurryed raw material is granulated (FIG. 1 (C)).
  • Granulation of the slurry obtained by mixing and stirring is performed using a spray dryer.
  • the atmospheric temperature during spray drying may be about 100 to 300 ° C. Thereby, a granulated powder having a particle diameter of 10 to 200 ⁇ m can be obtained.
  • the obtained granulated powder is preferably adjusted for particle size at this point in consideration of the final particle size of the product by removing coarse particles and fine powder using a vibration sieve or the like.
  • the granulated product is fired (FIG. 1D). Specifically, the obtained granulated powder is put into a furnace heated to about 900 to 1500 ° C., held for 1 to 24 hours and fired to produce a desired fired product.
  • the oxygen concentration in the firing furnace may be any condition as long as the ferritization reaction proceeds. Specifically, at 1200 ° C., the oxygen concentration of the introduced gas is set to be 10 ⁇ 7 % or more and 3% or less. Adjust and fire under flow conditions.
  • the reducing atmosphere necessary for ferritization may be controlled by adjusting the reducing agent.
  • a temperature of 900 ° C. or higher is preferable.
  • the firing temperature is 1500 ° C. or lower, the particles are not excessively sintered, and a fired product can be obtained in the form of powder.
  • the fired product is coarsely pulverized with a hammer mill or the like. That is, pulverization is performed on the baked granular material (FIG. 1E). After that, classification is performed using a vibrating screen. That is, classification is performed on the pulverized granular material (FIG. 1 (F)).
  • grains of the carrier core material with a desired particle size can be obtained.
  • the carrier core material according to one embodiment of the present invention is manufactured. That is, the method for producing a carrier core material for an electrophotographic developer according to an embodiment of the present invention has a general formula: Z x Ca y Fe 3-xy O 4 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1
  • Z is at least one metal selected from the group consisting of Mg, Mn, Ti, Cu, Zn, Sr, and Ni).
  • a firing step of firing the material at a predetermined temperature to form a magnetic phase is a raw material containing a water-soluble calcium salt.
  • the carrier core material manufactured by such a manufacturing method of the carrier core material for electrophotographic developer since calcium is added as a core composition, charging performance which is one of the characteristics required for the carrier core material Can be high.
  • a raw material containing calcium it is a raw material containing a water-soluble calcium salt, not CaO or CaCO 3 insoluble in water, which is generally used as an inexpensive material disclosed in Patent Document 1.
  • the degree of unevenness on the surface of the carrier core material can be lowered to obtain a relatively smooth surface.
  • the resin necessary for filling the recessed portion is not required in the subsequent coating with the coating resin, and the amount of the coating resin can be greatly reduced. This will be described later.
  • a high level can be maintained in the magnetic characteristics and the like. Therefore, according to such a method for producing a carrier core material for an electrophotographic developer, a carrier core material for an electrophotographic developer having good characteristics can be produced at low cost.
  • the carrier core material for an electrophotographic developer has a general formula: Z x Ca y Fe 3-xy O 4 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, Z is a carrier core material for an electrophotographic developer whose main component is a core composition represented by (at least one metal selected from the group consisting of Mg, Mn, Ti, Cu, Zn, Sr, Ni).
  • a raw material containing iron and a raw material containing calcium are mixed to granulate the mixture, and the granulated granule is fired at a predetermined temperature to form a magnetic phase.
  • the raw material containing calcium is a raw material containing a water-soluble calcium salt.
  • Such a carrier core material for an electrophotographic developer has good characteristics and can be manufactured at low cost.
  • an electrophotographic developer carrier according to an embodiment of the present invention is obtained.
  • a coating method such as silicone resin or acrylic resin can be performed by a known method. That is, an electrophotographic developer carrier according to an embodiment of the present invention is an electrophotographic developer carrier used for an electrophotographic developer, and includes the above-described carrier core material for an electrophotographic developer, and electrophotography. And a resin that covers the surface of the carrier core material for developer. Such a carrier for an electrophotographic developer has good characteristics and can be produced at low cost.
  • the carrier for an electrophotographic developer according to one embodiment of the present invention obtained by the above-described manufacturing method is mixed with an appropriate known toner.
  • the electrophotographic developer according to one embodiment of the present invention can be obtained.
  • an arbitrary mixer such as a ball mill is used.
  • An electrophotographic developer according to an embodiment of the present invention is an electrophotographic developer used for electrophotographic development, and is obtained by frictional charging between the above-described electrophotographic developer carrier and the electrophotographic developer carrier. And a toner capable of being charged in electrophotography. Since such an electrophotographic developer includes the electrophotographic developer carrier having the above-described configuration, the electrophotographic developer has high image quality and can be manufactured at low cost.
  • Example 1 74 g of calcium acetate monohydrate (Ca (CH 3 COO) 2 .H 2 O) is dispersed in 3 kg of water to form an aqueous solution, 10 kg of Fe 2 O 3 is added, and an ammonium polycarboxylate dispersant is added as a dispersant. 200 g and 105 g of carbon black as a reducing agent were added to form a mixture. As a result of measuring the solid content concentration at this time, it was 75% by weight. This mixture was pulverized by a wet bead mill (media diameter 2 mm) to obtain a mixed slurry.
  • the slurry was sprayed into hot air at about 130 ° C. with a spray dryer to obtain dry granulated powder. At this time, granulated powder other than the target particle size distribution was removed by sieving. This granulated powder was put into an electric furnace and fired at 1130 ° C. for 3 hours. At this time, the electric furnace was flowed to an electric furnace whose atmosphere was adjusted so that the oxygen concentration was 0.1% or less. The obtained fired product was classified using a sieve after pulverization to an average particle size of 38 ⁇ m. Thus, the carrier core material according to Example 1 was obtained.
  • Table 1 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material.
  • y the addition amount shown in Table 1
  • the composition of the above-described carrier core material is represented by a general formula: Ca y Fe 3-y O 4
  • the following analysis method is shown for the obtained carrier core material It is the result obtained by measuring with.
  • the value of y is the same in the second and subsequent examples.
  • x 0, that is, the general formula does not include Mn or the like as Z.
  • the Ca content of the carrier core material was analyzed by the following method.
  • the carrier core material according to the present invention was dissolved in an acid solution, and quantitative analysis was performed by ICP.
  • the Ca content of the carrier core material described in the present invention is the amount of Ca obtained by this quantitative analysis by ICP.
  • the average particle size means the central particle size in the volume particle size distribution, and the measurement uses Microtrack Model 9320-X100 manufactured by Nikkiso Co., Ltd.
  • the core charge amount as an electrical characteristic in Table 1 is the charge amount of the core, that is, the carrier core material.
  • the measurement of the charge amount will be described.
  • 9.5 g of carrier core material and 0.5 g of commercially available full-color toner are put into a 100 ml stoppered glass bottle and left to stand for 12 hours in an environment of 25 ° C. and 50% relative humidity to adjust the humidity.
  • the conditioned carrier core material and toner are shaken for 30 minutes with a shaker and mixed.
  • a NEW-YS type manufactured by Yayoi Co., Ltd. was used, and the shaking was performed 200 times / minute at an angle of 60 °.
  • the core charge amount ( ⁇ C (Coulomb) / g) measured charge (nC) ⁇ 10 3 ⁇ coefficient (1.00083 ⁇ 10 ⁇ 3 ) ⁇ toner weight (weight before suction (g) -Weight after suction (g)).
  • Example 2 A carrier core material according to Example 2 was obtained in the same manner as in Example 1 except that the amount of calcium acetate monohydrate added was 149 g. Table 1 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material.
  • Example 3 A carrier core material according to Example 3 was obtained in the same manner as in Example 1 except that the amount of calcium acetate monohydrate added was 223 g. Table 1 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material.
  • Example 4 About the calcium raw material to be added, as a calcium nitrate aqueous solution (containing 9.2% by weight of Ca), the addition amount was 182 g, and the amount of carbon black to be added was 118 g. A carrier core material according to Example 4 was obtained. Table 1 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material.
  • Example 5 A carrier core material according to Example 5 was obtained in the same manner as in Example 4 except that the addition amount of the calcium nitrate aqueous solution was 363 g and the addition amount of carbon black was 130 g. Table 1 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material.
  • Example 6 A carrier core material according to Example 6 was obtained in the same manner as in Example 4 except that the addition amount of the aqueous calcium nitrate solution was 545 g and the addition amount of carbon black was 143 g. Table 1 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material.
  • Example 7 is the same as Example 1 except that the amount of calcium acetate monohydrate added is 223 g, Fe 2 O 3 is 6.8 kg, and Mn 3 O 4 3.2 kg is further added. A carrier core was obtained. Table 2 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material. In this embodiment, the value of x is approximately 1, and in the general formula, Z is Mn.
  • Reference Example 1 A carrier core material according to Reference Example 1 was obtained in the same manner as in Example 1 except that the calcium raw material was not added. Table 1 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material.
  • Comparative Example 1 The carrier core material according to Comparative Example 1 was obtained in the same manner as in Example 1 except that the calcium raw material to be added was calcium carbonate and the amount added was 42 g. Table 1 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material.
  • Comparative Example 2 A carrier core material according to Comparative Example 2 was obtained in the same manner as Comparative Example 1, except that the amount of calcium carbonate added was 84 g. Table 1 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material.
  • Comparative Example 3 A carrier core material according to Comparative Example 3 was obtained in the same manner as in Comparative Example 1, except that the amount of calcium carbonate added was 125 g. Table 1 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material.
  • Reference Example 2 A carrier core material according to Reference Example 2 was obtained in the same manner as in Example 7 except that the calcium raw material was not added. Table 2 shows the magnetic characteristics and electrical characteristics of the obtained carrier core material. In this embodiment, the value of x is approximately 1, and in the general formula, Z is Mn.
  • the value of ⁇ 1000 is 59 to 70 Am 2 / kg in any of the examples, reference examples, and comparative examples, and ⁇ s indicating saturation magnetization It can be understood that the value of is 80 to 92 Am 2 / kg. Also, the value of ⁇ r indicating the remanent magnetization is 0.9 to 2.6 Am 2 / kg, which can be understood as a relatively low value. In particular, in Examples 1 to 3 and 7, it is 1.1 to 1.4 Am 2 / kg, and a considerably low value is maintained. If such a carrier core material having a low residual magnetization is used, the magnetic brush can be formed satisfactorily.
  • the core charge amounts were 11.7 ⁇ C / g, 16.0 ⁇ C / g, and 16.4 ⁇ C / g, respectively. 10.0 ⁇ C / g or more.
  • the core charge amounts were 11.7 ⁇ C / g, 17.0 ⁇ C / g, and 19.2 ⁇ C / g, respectively, and in each case, 10.0 ⁇ C / g or more.
  • the core charge amount is 24.8 ⁇ C / g, which is a considerably high value. That is, when a high charge amount is desired, the structure may include Mn as Z.
  • FIG. 2 is an electron micrograph showing the appearance of the surface of the carrier core material according to Reference Example 1.
  • FIG. 3 is an electron micrograph showing the appearance of the surface of the carrier core material according to Comparative Example 3.
  • FIG. 4 is an electron micrograph showing the appearance of the surface of the carrier core material according to Example 3.
  • FIG. 5 is a schematic view showing the crystal grain boundary portion with lines in the appearance of the surface of the carrier core material according to Reference Example 1 shown in FIG.
  • FIG. 6 is a schematic view showing the crystal grain boundary portion with lines in the appearance of the surface of the carrier core material according to Comparative Example 3 shown in FIG.
  • FIG. 1 is a schematic view showing the crystal grain boundary portion with lines in the appearance of the surface of the carrier core material according to Comparative Example 3 shown in FIG.
  • FIG. 7 is a schematic view showing the crystal grain boundary portion with lines in the appearance of the surface of the carrier core material according to the third embodiment shown in FIG. FIG. 2 to FIG. 4 show the case where the magnification is 5000 times. 5 to 7 are illustrated based on the electron micrographs shown in FIGS. 2 to 4 from the viewpoint of easy understanding.
  • Reference Example 1 is a system in which calcium is not added, but the surface of carrier core material 11 has a relatively high degree of unevenness, and boundary 12 seen as a crystal grain boundary is present. There are many grains 13, and grains 13 as particles grow moderately.
  • corrugation degree of the surface of the carrier core material 14 is still higher. And there are quite a large number of boundaries 15 that are seen as crystal grain boundaries, and the grains 16 hardly grow, and the size remains small.
  • Example 3 as compared with Reference Example 1, the degree of unevenness on the surface of the carrier core material 17 is low, and there are few boundaries 18 seen as crystal grain boundaries. And it can be grasped that each grain 19 is growing greatly.
  • FIG. 8 is a schematic view of the granular material in the magnetic phase formation stage in the carrier core material according to Comparative Example 3.
  • FIG. 9 is a schematic view of the granular material in the magnetic phase formation stage in the carrier core material according to the third embodiment.
  • the growth of the grains forming the magnetite phase 27 is not suppressed, but grows large, and as a result, a carrier core material with few crystal grain boundaries and a low degree of surface irregularities is produced. It is thought that it is done.
  • a reducing substance such as calcium acetate (Ca (CH 3 COO) 2 ) or an oxidizing property such as calcium nitrate (Ca (NO 3 ) 2 ). It is preferably composed of a substance having reducibility such as calcium acetate. With this configuration, it is presumed that the hematite phase does not remain and the hematite phase does not inhibit the growth of the magnetite phase.
  • a reducing agent such as carbon black to be added in the mixing step is compared with a reducing substance. It is good to add excessively. In Embodiments 4 to 6 described above, this is configured.
  • the surface property of the carrier core material was measured as follows. First, the surface roughness of the carrier core material was read using a laser microscope, and the surface roughness was analyzed. Specifically, using a laser microscope (LEXT OLS3000, manufactured by OLYMPUS Co., Ltd.), first, the image obtained with a 100 ⁇ objective lens is further magnified 5 times by digital zoom, The center was the center of the visual field, and the visual field was 26 ⁇ m ⁇ 19 ⁇ m. At this time, the output of the laser is 100, the capture speed is fast, and the lower limit position and the upper limit position of the capture are set manually at points where the in-focus points disappear in the confocal image. It was.
  • a laser microscope LEXT OLS3000, manufactured by OLYMPUS Co., Ltd.
  • the cross-sectional curve is a concavo-convex curve read
  • a roughness curve is a curve obtained by removing a waviness component longer than the wavelength set as the cut-off value ⁇ from the cross-sectional curve
  • a waviness curve Curves obtained by extracting a swell component longer than the wavelength set as the cut-off value ⁇ are shown.
  • Pz represents the maximum height of the cross-sectional curve
  • Rz represents the maximum height roughness
  • Wz represents the maximum height swell.
  • the minimum length was identified as 1% of the reference length.
  • the reference length indicates a 1/3 region at the center of the designated cross section.
  • the reference length is equal to the evaluation length in the case of a cross-sectional curve.
  • the value of SRa the value of 20 visual field measurement average is used.
  • the value of SRa for Comparative Example 1 is 0.838
  • the value of SRa for Comparative Example 2 is 0.920
  • the value of SRa for Comparative Example 3 is 0.886.
  • the value of SRa is 0.61
  • the value of SRa is 0.735
  • the value of SRa is 0. 724.
  • the value of SRa decreases as the addition amount of calcium acetate, which is a substance in which the water-soluble calcium salt has a reducing property, increases.
  • the SRa value is 0.764, for Example 5, the SRa value is 0.700, and for Example 6, the SRa value is 0.763. It is. In Examples 4 to 6, the value of SRa is low, Examples 4 and 6 are equivalent to Example 1, and Example 5 is a very low value.
  • the value of the surface property SRa is at least 0.800 or less. That is, the carrier core material according to one embodiment of the present invention has a length in the X direction within a curved cross-section when the particle surface of the carrier core material for an electrophotographic developer is observed with a laser microscope at a magnification of 500 times. Is L, the length in the Y direction in the cross-section curved surface is M, and the cross-section curved surface is f (x, y), the value of the surface property SRa expressed by the formula 1 is 0.800 or less. .
  • the value is smaller than 0.781 shown in Reference Example 1, and the value is 0.780 or less.
  • an electrophotographic developer carrier was prepared and evaluated.
  • the carrier core material was resin-coated by the following method.
  • a silicone resin (trade name: SR-2411, manufactured by Toray Dow Corning) was dissolved in toluene to prepare a coating resin solution. And it introduce
  • the calculation of the coat amount is obtained by the following formula.
  • Coating amount (% by weight) resin weight (g) ⁇ solid content concentration (% by weight) / core weight (g)
  • the carrier core material coated (coated) with this resin is placed in a hot-air circulating heating device, heated at 200 ° C. for 30 minutes to cure the coating resin, and the carrier for an electrophotographic developer according to Example 1 Got.
  • the same method was performed for Example 2 and the like to obtain a carrier for an electrophotographic developer.
  • FIG. 10 is an electron micrograph showing the appearance of the surface of the carrier according to Comparative Example 3.
  • FIG. 11 is an electron micrograph showing the appearance of the surface of the carrier according to Example 3.
  • FIG. 12 is a schematic view showing, in a line, an approximate boundary portion of the coating resin application region in the appearance of the surface of the carrier core material according to Comparative Example 3 shown in FIG. 10.
  • FIG. 13 is a schematic view showing a rough boundary portion of the coating resin application region with lines in the appearance of the surface of the carrier core material according to the third embodiment shown in FIG.
  • FIG. 10 and FIG. 11 show a case where the image is enlarged 2000 times.
  • 12 and 13 are illustrated based on the electron micrographs shown in FIGS. 10 and 11, respectively, from the viewpoint of easy understanding.
  • FIG. 12 and FIG. 13 show regions where the coating resin is coated with dots.
  • the raw material containing calcium is mixed as a solution.
  • the present invention is not limited thereto, and may be mixed in a powder state.
  • the carrier core material for an electrophotographic developer, the manufacturing method thereof, the carrier for an electrophotographic developer, and the electrophotographic developer according to the present invention are effectively used when applied to a copying machine or the like that requires high image quality. Is done.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

La présente invention concerne un procédé permettant de produire un matériau de noyau de support destiné à des développateurs électrophotographiques, ledit matériau de noyau de support étant principalement composé d'une composition de noyau qui est représentée par la formule générale ZxCayFe3-x-yO4 (dans laquelle 0 ≤ x ≤ 1, 0 < y ≤ 1, et Z représente au moins un métal sélectionné dans le groupe comprenant Mg, Mn, Ti, Cu, Zn, Sr et Ni). Le procédé de production d'un matériau de noyau de support destiné à des développateurs électrophotographiques selon la présente invention comprend : une étape de mélange dans laquelle une matière première contenant du fer et une matière première contenant du calcium sont mélangées; une étape de granulation dans laquelle le mélange ainsi obtenu est granulé après l'étape de mélange; et une étape de cuisson dans laquelle le matériau pulvérulent granulé obtenu par l'étape de granulation est cuit à une température prédéfinie, ce qui permet de former une phase magnétique. Dans ce contexte, la matière première contenant du calcium, qui est mélangée à l'étape de mélange, est une matière première qui contient un sel de calcium hydrosoluble.
PCT/JP2012/072070 2012-08-30 2012-08-30 Procédé permettant de produire un matériau de noyau de support destiné à des développateurs électrophotographiques, matériau de noyau de support destiné à des développateurs électrophotographiques, support destiné à des développateurs électrophotographiques, et développateurs électrophotographiques WO2014033881A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60134249A (ja) * 1983-12-22 1985-07-17 Fuji Elelctrochem Co Ltd 静電複写用フエライトキヤリア材
JP2006259294A (ja) * 2005-03-17 2006-09-28 Dowa Mining Co Ltd 電子写真現像剤用キャリア芯材および電子写真現像剤用キャリア粉並びにそれらの製造方法
JP2012076955A (ja) * 2010-09-30 2012-04-19 Dowa Electronics Materials Co Ltd フェライト粒子並びにそれを用いた電子写真現像用キャリア及び電子写真用現像剤
WO2012049900A1 (fr) * 2010-10-15 2012-04-19 Ｄｏｗａエレクトロニクス株式会社 Matériau de noyau de support pour révélateur électrophotographique, support pour révélateur électrophotographique, et révélateur électrophotographique
JP2012144401A (ja) * 2011-01-14 2012-08-02 Dowa Electronics Materials Co Ltd フェライト粒子並びにそれを用いた電子写真現像用キャリア及び電子写真用現像剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60134249A (ja) * 1983-12-22 1985-07-17 Fuji Elelctrochem Co Ltd 静電複写用フエライトキヤリア材
JP2006259294A (ja) * 2005-03-17 2006-09-28 Dowa Mining Co Ltd 電子写真現像剤用キャリア芯材および電子写真現像剤用キャリア粉並びにそれらの製造方法
JP2012076955A (ja) * 2010-09-30 2012-04-19 Dowa Electronics Materials Co Ltd フェライト粒子並びにそれを用いた電子写真現像用キャリア及び電子写真用現像剤
WO2012049900A1 (fr) * 2010-10-15 2012-04-19 Ｄｏｗａエレクトロニクス株式会社 Matériau de noyau de support pour révélateur électrophotographique, support pour révélateur électrophotographique, et révélateur électrophotographique
JP2012144401A (ja) * 2011-01-14 2012-08-02 Dowa Electronics Materials Co Ltd フェライト粒子並びにそれを用いた電子写真現像用キャリア及び電子写真用現像剤

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