EP0559250B1 - Particules de support magnétiques - Google Patents

Particules de support magnétiques Download PDF

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Publication number
EP0559250B1
EP0559250B1 EP93200285A EP93200285A EP0559250B1 EP 0559250 B1 EP0559250 B1 EP 0559250B1 EP 93200285 A EP93200285 A EP 93200285A EP 93200285 A EP93200285 A EP 93200285A EP 0559250 B1 EP0559250 B1 EP 0559250B1
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EP
European Patent Office
Prior art keywords
magnetic
carrier
particles
carrier particles
toner
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.)
Expired - Lifetime
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EP93200285A
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German (de)
English (en)
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EP0559250A1 (fr
Inventor
Serge C/O Agfa-Gevaert N.V. Tavernier
Werner c/o Agfa-Gevaert N.V. Op de Beeck
Danny c/o Agfa-Gevaert N.V. Van Wunsel
Paul c/o Agfa-Gevaert N.V. Marksch
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Agfa Gevaert NV
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Agfa Gevaert NV
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Classifications

    • 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
    • G03G9/1088—Binder-type carrier
    • G03G9/10884—Binder is obtained other than by reactions only involving carbon-carbon unsaturated bonds
    • 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
    • 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
    • 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
    • G03G9/1088—Binder-type carrier
    • G03G9/10882—Binder is obtained by reactions only involving carbon-carbon unsaturated bonds

Definitions

  • the present invention relates to improvements in electrostatographic developing systems, structures and/or procedures, and embodies the use of an improved type of developing agent, which in combination with a specific type of developing unit and procedure leads to an appreciable improvement in the quality of images created from an electrostatic latent image.
  • the new type of developer offers a flexible design, and improved ease and accuracy in production, leading to reduced costs.
  • the invention relates to the specific design of the developer, being essentially a developer containing at least two components, one of them being ordinarily referred to as carrier particle, the other being referred to as toner particle.
  • the type of developer being referred to is commonly called the 2-component type developer.
  • the invention is more specifically concerned with the specific design of the magnetic carrier particles comprising a mixture of pigments (A) and (B) having different coercive force and with their use in a rotating core magnetic brush development process.
  • electrostatic latent image corresponding to either the original to be copied, or corresponding to digitized data describing an electronically available image, on a photoconductive member.
  • the electrostatic latent image is formed by image-wise discharge over styli towards a dielectric substrate.
  • the xeroprinting process such as disclosed e.g. in European Patent Application 0 243 934 involves image-wise exposing a photopolymer master, charging on a conductive support, toning with dry or liquid toner and transferring to another substrate.
  • the information building up the latent electrostatic image is presented in a binary way, i.e. presenting the image as a combination of white and black areas
  • other types of latent images are also gaining interest, more specifically those being composed by a scala of gray levels ranging from zero to full density. In the latter images both spatial and gray level information essentially contribute to the latent image.
  • Electrostatic latent images can be developed using a liquid developer consisting of a colloidal system of charged colloidal particles in an insulating liquid.
  • the latent image is developed with a finely divided developing material or toner to form a powder image which is then transferred onto a support sheet such as paper.
  • the support sheet bearing the toner powder image is subsequently passed through a fusing apparatus and is thereafter discharged out of the copying resp. printing machine as a final copy, resp. final print.
  • a latent electrostatographic image is formed on a suitable member, e.g. a photoconductive drum, secondly this latent image is developed to form a visually discernible image and transferred in a transfer station to a final hard copy.
  • a suitable member e.g. a photoconductive drum
  • One of the objectives set forth for the overall electrostatographic process is to provide an image on the final copy, resp. final print with the best possible quality.
  • Quality consequently comprises features such as uniform darkness of the image areas, background quality, clear delineation of lines, as well as overall resolution of the image.
  • the "quality" and more in particular the resolution of the latent electrostatographic image is determined by the accuracy of each of the following steps : first the conversion of the digitized data describing the electronically available image to an appropriate illumination pattern, secondly the illumination of the photoconductive drum by the laser or light emitting diode system; thirdly the resolution power and gradation characteristics of the photoconductive substrate present on the photoconductive drum.
  • the quality of the latent electrostatic images is determined by the contact exposure step, whereas the "original" can be either line work or half-toned images or screened images or combinations thereof.
  • the "quality" of the latent electrostatographic image is predominantly determined by the accuracy of illumination of the photoconductive drum by the electro-optical system, wherein the optical quality of the mirrors, lenses, optical fibres, etc. used, as well as the solidity, sturdiness and lack of vibrations of the construction play a vital role.
  • the latent electrostatic image aside from pure line work or screened images, comprises in addition different electrostatic charge levels within the different pixels, hereinafter referred to as gray levels
  • gray levels it is not only necessary to use a developer with high resolving power, but it is also important to realise proportionality of the developed powder image with respect to said gray levels.
  • transition from different gray levels e.g. white to gray; gray to black, ...) should be reproduced in a "sharp" way, i.e. without smoothing out, edge enhancing and other effects.
  • a second disadvantage of the cited developing procedure is the limited toner particles delivery rate. Since the flow of the developer is laminar, only toner particles present on the top-section of the magnetic brush chains can participate in the development process. Hence to realise an appreciable print density, special actions are necessary, each having their particular limitations, such as a high toner concentration, resulting in a high carrier surface coverage, and/or the use of high speed of magnetic sleeve transport versus process speed, resulting in a sufficient delivery.
  • the first action results in limited lifetime of developer and background problems due to poorly charged toner particles.
  • the second action cannot be applied without limitation, as very high linear speeds arise, resulting in degradation of developer and high mechanical impact on the developed image, resulting in image quality degradation.
  • AC-field additional electrical alternating field
  • the action of the AC-field is to induce some mixing in the laminar brush flow and reducing transition effects and to enhance toner delivery.
  • the AC-field however also induces oscillatory behaviour of the brush influencing resolving power.
  • the dual component developer is based on a composite carrier particle combined with toner particles.
  • the composite carrier is prepared by combining magnetic pigments of the soft ferrite type with a binder resin.
  • the carrier particles exhibit a small amount of remanent behaviour, characterised in coercivity values ranging from about 3.98 to 19.92 kA/m (50 up to 250 Oe) depending on the exact nature of pigments used. From the data presented in the cited documents it becomes apparent that a major limitation arises from carrier loss from the brush towards the photoconductor for carrier diameters beneath 50 ⁇ m, in this way imposing a limitation on the softness of the brush as only larger particles can be used. In order to use economically achievable products, only broader size cuts can be used, increasing the average carrier particle size even further.
  • the improvement which is put forward resides in the use of magnetically hard carrier particles with a minimum of magnetisation in the magnetic field strength present above a pole position in the developing unit.
  • the size of the carrier definitely is smaller than 50 ⁇ m necessary to avoid carrier loss, and situates itself in the 5-45 ⁇ m average size range. High performance is reported.
  • the hard magnetic properties are necessary to resist to internally magnetic re-alignment as the moving poles of the core passes beneath the carrier particle. Accordingly the particle is forced to flip for inducing the desired transport, and mixing of the magnetic brush.
  • Transport cannot be realised with soft magnetic material.
  • a typical magnetic hysteresis curve is shown in the Kodak publication cited supra p. 105 showing indeed a material with a coercivity of 15.93-23.90 kA/m (200-300 Oe).
  • the transport increases strongly at higher coercivity. Apart from coercivity the induced moment is also important. A certain amount is put in the product by magnetisation prior to use. The magnetic moment stimulates the transport, and also reduces carrier loss.
  • Hard magnetic pigments have a limited magnetization value, which ideally have approximately an induced moment of 37.5 ⁇ T.m 3 /kg (30 emu/g) at 79.67 kA/m (1000 Oe).
  • a dilution occurs as a volume loading of more than 50 % is difficult to achieve. It hence results in an induced moment of the particle of at most 31.25 ⁇ T.m 3 /kg (25 emu/g) which comes rather close to the lower value for carrier loss.
  • JP-A 60 196 777 (see also Patent Abstracts of Japan vol 10, no 53 (p 433) (2110) 4 March 1986) a carrier for use in electrostatic charge developers is described, wherein the carrier bulk is composed of a mixture of large carrier particles (about 100 to 500 ⁇ m) consisting of a material having ⁇ 10 13 ⁇ .cm resistance and high coercive force of ⁇ 159.34 kA/m (2000 Oe) and small carrier particles (about 10 to 100 ⁇ m) consisting of an ordinary type of magnetic material having ⁇ 10 9 ⁇ .cm resistance and a coercive force of ⁇ 39.83 kA/m (500 Oe).
  • Carrier particles having an average particle size between 100 and 500 ⁇ m impose a limitation on the softness of the brush.
  • carrier particles with that high average particle size it is impossible to make low weight carriers (perfectly embodied when using composite carrier materials), which is required in high speed copying systems.
  • a further object of the present invention is to provide a developer characterised by a high flowability.
  • magnetic carrier particles are provided suited for use in magnetic brush toner-carrier development of electrostatic charge patterns, each of said carrier particles incorporating a mixture of finely divided magnetic pigment particles dispersed in a resin binder, said mixture of magnetic pigment particles comprising a portion (A) of pigment particles having a coercive force of more than 23.9 kA/m (300 Oe) and an other portion (B) of magnetic pigment particles having a coercive force of less than 23.9 kA/m (300 Oe), the weight ratio of said portions (A) and (B) being in the range of 0.1 to 10.
  • said carrier particles contain in admixture magnetic pigment particles (A) having a coercive force of at least 39.83 kA/m (500 Oe), preferably at least 79.67 kA/m (1000 Oe), more preferably at least 239.00 kA/m (3000 Oe), and magnetic pigment particles (B) having a coercitive force of less than 23.90 kA/m (300 Oe).
  • A magnetic pigment particles having a coercive force of at least 39.83 kA/m (500 Oe), preferably at least 79.67 kA/m (1000 Oe), more preferably at least 239.00 kA/m (3000 Oe), and magnetic pigment particles (B) having a coercitive force of less than 23.90 kA/m (300 Oe).
  • the present invention further provides the use of these magnetic carrier particles according to claim 10.
  • the carrier material described supra is in fact a composite carrier containing both "soft” and “hard” magnetic pigments.
  • a clear description of magnetic materials, classification behaviour etc. is presented in numerous publications as for example Uhlmann 5th edition, Vol. A-16, p. 1 e.a.
  • soft magnetic pigments a variety of materials can be used, which comprise magnetic metal pigments such as fine powder, Fe powder, other metals and/or alloys, as well as magnetic oxide pigments both pure iron-based, such as magnetite, mixed iron oxide, etc. and mixed oxide magnetic pigments, commonly referred to as ferrite of the soft type which can be represented by the general formula : M 1-x 1+x (1-y) Fe 2x 1+x (1-y) Oy wherein M denotes at least one atom selected from the group consisting of divalent, monovalent or trivalent ions such as Mn, Mi, Co, Mg, Ca, Zn and Cd, furtheron doped with monovalent or trivalent ions.
  • the pigments referred to as soft are characterized by a coercivity of at most 23.90 kA/m (300 Oe), as found by applying the procedure described below.
  • the coercivity of a magnetic material is the minimum external magnetic force necessary to reduce the remanence Br to zero while it is held stationary in the external field, and after the material has been magnetically saturated, i.e. the material has been permanently magnetized.
  • a variety of apparatus and methods for the measurement of the coercivity of the carrier particles according to our invention can be employed.
  • a Princeton Applied Research Model 155 Vibrating Sample Magnetometer available from Princeton Applied Research Co., Princeton, N.J., is used to measure the coercivity of powder particle samples.
  • the powder was mixed with a nonmagnetic polymer powder (90 percent magnetic powder : 10 percent polymer by weight).
  • the mixture was placed in a capillary tube, heated above the melting point of the polymer, and then allowed to cool to room temperature.
  • the filled capillary tube was then placed in the sample holder of the magnetometer and a magnetic hysteresis loop of induced magnetism (in ⁇ T.m 3 /kg (emu/gm)) versus external field (in kA/m or Oersted units) was plotted. During this measurement, the sample was exposed to an external field of 0 to 637.35 kA/m (0 to 8000 Oersted).
  • a maximum, or saturated magnetic moment, Bsat When a powdered material is magnetically saturated and immobilized in an applied magnetic field H of progressively increasing strength, a maximum, or saturated magnetic moment, Bsat, will be induced in the material. If the applied field H is further increased, the moment induced in the material will not increase any further. When the applied field, on the other hand, is progressively decreased through zero, reversed in applied polarity and thereafter increased again, the induced moment B of the powder will ultimately become zero and thus be on the threshold of polarity reversal in induced moment.
  • the value of the applied field H necessary to bring about the decrease of the remanence, Br, to zero is called the coercivity Hc of the material.
  • the described soft magnetic pigments of the present invention exhibit a coercivity of less than 23.90 kA/m (300 Oersted) when magnetically saturated, preferably a coercivity of at most 15.93 kA/m (200 Oersted) and most preferably a coercivity of at most 7.96 kA/m (100 Oersted).
  • the hard magnetic pigments then show a coercivity of at least 23.90 kA/m (300 Oe), preferably at least 79.67 kA/m (1000 Oe), and more preferably at least 239.00 kA/m (3000 Oe).
  • magnetic materials having coercivity levels of 239 kA/m and 478.02 kA/m (3000 and 6000 Oersted) have been found useful; there appears to be no theoretical reason why higher coercivity levels would not be useful.
  • the carrier particles of this invention exhibit an induced magnetic moment B of at least 25 ⁇ T.m 3 /kg (20 emu/gm), based on the weight of the carrier, when present in a field of 79.67 kA/m (1000 oersted), after full magnetisation.
  • Useful hard magnetic materials include hard ferrites and gamma ferric oxide.
  • the hard ferrite are represented by a similar composition as cited above, whereby specific ions such as Ba, Pb, or Sr are used as disclosed in US Patent No. 3,716,630.
  • both magnetic pigment types (A) and (B) can have any shape, but should have a size at most half of the size of the final carrier, preferably one tenth. Moreover sferoidal, cubic like amorphous shape is preferred as better realisation of the final binder/pigment compound can be realised. Needle shaped pigments indeed may show damage due to shear forces during the mixing process. Both magnetic pigment types (A) and (B) used inn the present invention may have a different average particle size as described in EP-A-0 289 663 as to further enhance the homogeneity of the carrier particles.
  • the carrier particles according to the present invention comprise a binder resin.
  • the binder resin used with the magnetic pigment is selected to provide the required mechanical and electrical properties. It should (1) adhere well to the magnetic pigment, (2) facilitate formation of strong, smooth-surfaced particles and (3) preferably possess sufficient difference in triboelectric properties from the toner particles with which it will be used to insure the proper polarity and magnitude of electrostatic charge between the toner and carrier when the two are mixed.
  • the binder resin can be organic, or inorganic, such as a binder composed of glass, metal, silicone resin or the like.
  • an organic material is used such as a natural or synthetic polymeric resin or a mixture of such resins having appropriate mechanical properties.
  • Appropriate monomers include, for example, vinyl monomers such as alkyl acrylates and methacrylates, styrene and substituted styrenes, basic monomers such as vinyl pyridines, etc. Copolymers prepared with these and other vinyl monomers such as acidic monomers, e.g., acrylic or methacrylic acid, can be used.
  • copolymers can advantageously contain small amounts of polyfunctional monomers such as divinylbenzene, glycol dimethacrylate, triallyl citrate and the like.
  • Condensation polymers such as polyesters, polyamides or polycarbonates can also be employed.
  • Preparation of composite carrier particles according to this invention may involve the application of heat to soften thermoplastic material or to harden thermosetting material; evaporative drying to remove liquid vehicle; the use of pressure, or of heat and pressure, in molding, casting, extruding, etc., and in cutting or shearing to shape the carrier particles; grinding, e.g., in a ball mill to reduce carrier material to appropriate particle size; and sifting operations to classify the particles.
  • the powdered magnetic material is dispersed in a dope or solution of the binder resin.
  • the solvent may then be evaporated and the resulting solid mass subdivided by grinding and screening to produce carrier particles of appropriate size.
  • emulsion or suspension polymerization is used to produce uniform carrier particles of excellent smoothness and useful life.
  • thermoplastification and melt-homogenisation of the binder and pigments are preferred.
  • a binder resin with some hydrophilic components is preferred.
  • the binder resin containing hydrophilic functional groups is e.g. of the type described in Pat.No. 4,600,675, wherein the hydrophilic groups are preferably at least partly carboxylic acid groups present in an amount sufficient to provide resins with an acid value, also called acid number, in the range of 5 to 250 mg/g.
  • Preferred resins are copolymers of styrene with unsaturated acids such as acrylic acid and methacrylic acid and alkyl esters thereof.
  • Further polyester resins such as those produced by condensation reaction of a polyol or mixture of polyols, e.g. ethylene glycol, triethylene glycol and an alkoxylated bisphenol, especially bisphenol A, i.e. [2,2-bis(4-hydroxyphenyl)-propane], with a dicarboxylic acid or mixture of dicarboxylic acids, e.g.
  • binder resins for the purpose of the present invention.
  • a particularly useful polyester binder is derived from fumaric acid that is polycondensed with an ethoxylated "bisphenol A", i.e. ethoxylated 2,2-bis(4-hydroxyphenyl)propane.
  • toner comprising as a binder a polyester resin obtained from a diol or mixture of diols represented by the following general formula : wherein R represents an ethylene or propylene group, x and y are independent numbers such that the average value of their sum is 2 to 7; and a polycarboxylic acid or a derivative thereof, which is a mixture of a dicarboxylic acid or a C 1-6 alkyl ester thereof and a tri- or polycarboxylic acid or an acid anhydride thereof, the content of said tri- or polycarboxylic acid or acid anhydride being from 30 to 80 mol % of the acids.
  • Particularly suitable styrene allyl alcohol copolymers have a hydroxyl content of 5.4 to 6 % by weight and a molecular weight in the range of 1,500 to 2,400 and are sold under the trade names RJ 100 and RJ 101 of Monsanto U.S.A.
  • the styrene allyl alcohol copolymers are preferably used in amount of 10 to 20 % by weight with respect to the total binder content of the carrier particles.
  • the magnetic carrier particles according to the present invention can be produced by dispersing the magnetic powders in the resin binder melt, allowing the molten dispersion to solidify and crushing and milling the obtained solid. By wind sifting or sieving particles sizing in the range of 35 to 150 ⁇ m are separated.
  • the magnetic powders are incorporated in the binder in combination with carbon black controlling in that way the specific resistivity of the carrier particles.
  • a suitable amount of carbon black is in the range of 0.2 to 5 % by weight with respect to the magnetic powders.
  • flow enhancing agents can be melt-mixed within the carrier composition yielding a carrier particle surface provided with small spacer particles, that are optionally embedded therein after the milling process.
  • Suitable flow improving agents are e.g. colloidal silica and Al 2 O 3 -particles of sub- ⁇ m (micron) particle size.
  • Another way to improve the flowing properties is by producing carrier particles having a spherical or spheroidal shape.
  • Such can proceed by spraying a melt or according to a heating-dispersion technique described in U.S.Pat.No. 4,345,015.
  • carrier particles obtained by crushing are dispersed in a carrier liquid in which the resin binder does not dissolve in the presence of colloidal hydrophobic silica in a concentration to inhibit coagulation of the particulate material when heat-softening the resin binder; the dispersion is heated with stirring to a temperature at which the resin of the particles softens but does not melt and the particles acquire a spherical or spheroidal shape and the dispersion is then cooled down to a temperature at which the resin binder of the particles is no longer sticky, and finally the carrier particles are separated, e.g.
  • hydrophobic colloidal silica generally ranges from 0.2 to 2.0 parts by weight per 100 parts by weight of carrier particles and has no detrimental influence on triboelectric properties, and further promotes flowing properties as explained above by being partially embedded in the carrier surface.
  • the toner for use in combination with carrier particles of the present invention can be selected from a wide variety of materials, including both natural and synthetic resins and charge controlling agents as disclosed e.g. in U.S.Pat.Nos. 4,076,857 and 4,546,060.
  • the carrier particles of the present invention may be used in combination with a starter and replenisher toner of different average grain size as described e.g. in published EP-A 0248119.
  • the shape of the toner particles can be irregular, as is the case in ground toners, or spheroidal. Spheroidization may proceed by spray-drying or the heat-dispersion process disclosed in U.S.Pat.No. 4,345,015.
  • the tribo-electrical modeling between carrier and toner can be done by changing the toner formulation and/or the coating of carrier by different processes such as fluidized bed spray drying, chemical vapour deposition methods, etc.
  • the addition of charge controlling agents to the carrier composition during the preparation is an obvious method, which arises from the typical design of the carrier itself.
  • the developers as described above can be used as such, although, it is preferred to premagnetise the carrier or developer to a certain degree, in order to realise a permanent magnetic dipole moment within each carrier bead, which will afterwards react on the alternating magnetic field obtained by having the magnetic core of the developing unit rotate. It is preferred from the production way however to magnetize in saturation.
  • magentic properties it could be envisaged to magnetise not in saturation; a procedure which is more critical in production as not each particle possibly receives the same treatment.
  • a better method is to use the benefit of the flexible design, in ratio of hard and soft pigment, and the concentration, to induce the appropriate magnetic behaviour by the full magnetization.
  • the developer will be preferentially used in combination with a rotating magnetic core developing device for magnetic brush development.
  • the magnetic development unit used in our experiments consists of a multipolar magnetic core, showing 12 poles, having each 0.068 T (680 Gauss) top field on a pole position, with sinusoidal field.
  • the diameter is 29.3 mm.
  • a sleeve, diameter 31.4 mm in aluminium material is positioned concentrically.
  • a blading knive is positioned at a clearing distance of 0.5 mm.
  • the magnetic development unit is positioned opposite to a photoconductor with a clearance of 600 ⁇ m.
  • the speed of rotation for the core was 1500 rpm countercurrently, for the shell 80 rpm concurrently with the photoconductor running at 10 cm/sec.
  • the photoconductor base plate was set at ground potential, the photoconductor having no net charge.
  • the DC voltage ranged from - 300 Volt, causing development since a negative toner polarity was used, up to + 400 Volt, causing carrier loss by carrier by development.
  • the amount deposited on the photoconductor was measured as a fingerprint of material and process.
  • the flow of magnetised material was measured.
  • Image quality was controlled by developing a real image, containing as well lines, black areas, screened- and gray level- images, and transition zones.
  • the obtained particles were magnetically characterized after melting to a solid mass after magnetisation.
  • a coercivity of 21.91 kA/m (275 Oe) was measured, remanence, magnetisation of 22.5 ⁇ T.m 3 /kg (18 emu/g), a saturation magnetisation of 90 ⁇ T.m 3 /kg (72 emu/g) and magnetic induction at 79.67 kA/m (1000 Oe) of 75 ⁇ T.m 3 /kg (60 emu/g).
  • the carrier was magnetised up to saturation.
  • a developer was realised by admixing a fine polyester-based toner with particle size 4,7 ⁇ m (average by volume) determined by Coulter Counter.
  • the developer contained 14 % toner expressed to carrier in weight by weight.
  • the toner charge was - 18 ⁇ c/g as determined by blow-off methods.
  • the developer was loaded in the developing unit described above and good transport was observed under the cited experimental conditions.
  • the amount of carrier on the development roller was 28.5 mg/sq.cm.
  • the development characteristics were excellent yielding at said development gap of 0.6 mm on a photoconductor of the organic type (16 ⁇ m thickness) and at a process speed of 10 cm/sec a developed transmission toner density of 0.75 at -100 V bias and of 1.45 at -200 bias voltage. Carrier loss occured at + 275 V bias potential or higher. This implies a broad operating window to obtain excellent background free images.
  • the resolution was excellent as well as the homogenity and the transition edges.
  • the flowability of the developer was determined by the above described method and yielded a flowability of 22.
  • Example 1 was repeated with the exception that the soft magnetic pigment was replaced by a soft ferrite material having an average particle size of 1-2 ⁇ m, and coercivity of 1.19 kA/m (15 Oe) when magnetically saturated, a remanence of 2.5 ⁇ T.m 3 /kg (2 emu/g) and saturation magnetisation of 93.75 ⁇ T.m 3 /kg (75 emu/g) and having a chemical composition of Mn x Fe y O Z .
  • the binder resin was used for 12 parts, the described soft pigment for 52 parts, the hard pigment for 36 parts.
  • the carrier After preparation the carrier showed a coercivity of 150 oersted after saturation magnetisation, a remanence of 15.0 ⁇ T.m 3 /kg (12 emu/g), a saturation magnetisation of 93.75 ⁇ T.m 3 /kg (75 emu/g), and a magnetic induction at 79.67 kA/m (1000 Oe) of 62.5 ⁇ T.m 3 /kg (50 emu/g).
  • the carrier was magnetized upto saturation and combined with a toner composition identical to example 1, except that the average particle size was 5.92 ⁇ m, and the developer was containing 8 % of toner particles with respect to carrier particles w/w.
  • the charge was -18 ⁇ C/g; transport was observed with a high magnetic brush loading of 43.3 mg/sq.cm.
  • the carrier loss starts up from +365 V bias potential.
  • the toner density realised at - 100 V developing potential was 0.64, at -200 V it was 1.24. Good image quality was observed.
  • the flowability measured as described above corresponded to 22.
  • Example 2 was repeated except that to 12 parts of the binder resin, 88 parts of the soft pigment was added and no hard pigment.
  • the magnetic properties were measured and yielded a coercivity of 1.19 kA/m (15 Oe) after magnetisation up to saturation, a remanence of 2.5 ⁇ T.m 3 /kg (2 emu/g) and saturation magnetisation of 87.5 ⁇ T.m 3 /kg (70 emu/g) and a magnetic induction of 62.5 ⁇ T.m 3 /kg (50 emu/g) at 79.67 kA/m (1000 Oe).
  • a developer similar to that described in example 2 was realised. The flowability of the developer was high and corresponded to 15.
  • Example 2 was repeated except that for 20 parts of the binder, 80 parts of the hard pigment was used and no soft pigment.
  • the carrier was found to have a coercivity of 294.78 kA/m (3700 Oe) after full magnetisation, a remanence of 37.5 ⁇ T.m 3 /kg (30 emu/g), a saturation magnetisation of 75.0 ⁇ T.m 3 /kg (60 emu/g) and magnetic induction at 79.67 kA/m (1000 Oe) of 43.75 ⁇ T.m 3 /kg (35 emu/g).
  • Good transport was found in the developing unit with a brush coverage of 71 mg/sq.cm.
  • Example 1 was repeated except that the soft magnetic component was replaced by a 2 ⁇ m size soft ferrite pigment with coercivity of 1.19 kA/m (15 Oe), a remanence of 2.5 ⁇ T.m 3 /kg (2 emu/g) and saturation magnetisation of 93.75 ⁇ T.m 3 /kg (75 emu/g) and that the hard magnetic pigment was replaced by a strontium and ferrit pigment with 2 ⁇ m size, coercivity of 197.58 kA/m (2480 Oe), remanence of 25.0 ⁇ T.m 3 /kg (20 emu/g), saturation magnetisation of 51.25 ⁇ T.m 3 /kg (41 emu/g).
  • the soft magnetic component was replaced by a 2 ⁇ m size soft ferrite pigment with coercivity of 1.19 kA/m (15 Oe), a remanence of 2.5 ⁇ T.m 3 /kg (2 emu/g) and saturation magnetisation
  • the composition was 14 parts of binder resin, 29 parts of soft magnetic pigment, 57 parts of hard magnetic pigment. After preparation a coercivity of 47.80 kA/m (600 Oe) after full magnetisation was observed, a remanence of 27.5 ⁇ T.m 3 /kg (22 emu/g), a saturation magnetisation of 82.5 ⁇ T.m 3 /kg (66 emu/g) and magnetic induction of 52.5 ⁇ T.m 3 /kg (42 emu/g) at 79.67 kA/m (1000 Oe). A behaviour similar to that described in example 1 was found. However, a small decrease in flowability was observed corresponding to a figure of 23 measured as described above.
  • Example 2 was repeated with 11 parts of binder resin, 44.5 parts of soft magnetic pigment and 44.5 parts of hard magnetic pigment. After preparation a coercivity of 24.70 kA/m (310 Oe) after full magnetisation was observed, a remanence of 23.75 ⁇ T.m 3 /kg (19 emu/g), magnetic induction of 77.5 ⁇ T.m 3 /kg (62 emu/g) at 79.67 kA/m (1000 Oe) and saturation magnetisation of 105.0 ⁇ T.m 3 /kg (84 emu/g). A similar behaviour as described in example 2 was found.
  • the toner density realised at -100 V developing potential was 0.53 at -200 V it was 0.8.
  • the carrier loss starts up from 275 V bias potential.
  • the flowability measured as described above corresponded to 22.
  • the toner charge as determined by conventional blow-off methods amounted to - 19.8 ⁇ C/g.

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

Claims (10)

  1. Des particules magnétiques de support granuleux utilisables pour le développement de toner-support granuleux à brosse magnétique de motifs à charges électrostatiques, chacune de ces particules de support incorporant un mélange de particules de pigment magnétiques finement divisées et dispersées dans un liant résineux, ce mélange de particules de pigment magnétiques comprenant une portion (A) de particules de pigment ayant une force coercitive supérieure à 23,90 kA/m ( 300 Oe) et une autre portion (B) de particules de pigment ayant une force coercitive inférieure à 23,90 kA/m ( 300 Oe), le rapport pondéral de ces portions (A) et (B) se situant entre 0,1 et 10.
  2. Des particules magnétiques de support granuleux selon la revendication 1, caractérisées en ce que ce mélange de particules de pigment magnétiques comprend une portion (A) ayant une force coercitive d'au moins 79,67 kA/m ( 1000 Oe) et une portion (B) ayant une force coercitive inférieure à 23,90 kA/m (300 Oe).
  3. Des particules magnétiques de support granuleux selon la revendication 1, caractérisées en ce que ce mélange de particules de pigment magnétiques comprend une portion (A) ayant une force coercitive supérieure à 23,90 kA/m (300 Oe) et une portion (B) ayant une force coercitive de 15,93 kA/m (200 Oe) au maximum.
  4. Des particules magnétiques de support granuleux selon la revendication 1, caractérisées en ce que ce mélange de particules de pigment magnétiques comprend une portion (A) ayant une force coercitive d'au moins 79,67 kA/m (1000 Oe) et une portion (B) ayant une force coercitive de 15,93 kA/M (200 Oe) au maximum.
  5. Des particules magnétiques de support granuleux selon l'une des revendications précédentes, caractérisées en ce que ces particules ont une dimension moyenne de grain qui se situe entre 15 et 150 µm (micron), un moment d'induction d'au moins 25,0 µT.m3/kg (20 emu/g) dans un champ appliqué de 79,67 kA/m (1000 Oe) et une rémanence d'au moins 6,25 µT.m3/kg (5 emu/g).
  6. Des particules magnétiques de support granuleux selon l'une des revendications de 1 à 5, caractérisées en ce que ces particules de pigment magnétiques ont une dimension moyenne de grain qui varie de 0,05 à 10 µm (micron).
  7. Des particules magnétiques de support granuleux selon une des revendications précédentes, caractérisées en ce que le rapport de ces particules de pigment magnétiques au liant résineux est au moins 25 pourcents volumétriques.
  8. Des particules magnétiques de support granuleux selon une des revendications précédentes, caractérisées en ce que le rapport pondéral de la portion (A) de ces particules de pigment magnétiques et de la portion (B) se situe entre 0,25 et 4.
  9. Des particules magnétiques de support granuleux selon une des revendications précédentes, caractérisées en ce que le rapport pondéral de la portion (A) de ces particules de pigment magnétique et de la portion (B) se situe entre 0,33 et 3.
  10. L'usage de particules magnétiques de support granuleux selon l'une des revendications précédentes dans un procédé de développement à brosse magnétique à noyau rotatif.
EP93200285A 1992-02-29 1993-02-04 Particules de support magnétiques Expired - Lifetime EP0559250B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP93200285A EP0559250B1 (fr) 1992-02-29 1993-02-04 Particules de support magnétiques

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Application Number Priority Date Filing Date Title
EP92200591 1992-02-29
EP92200591 1992-02-29
EP93200285A EP0559250B1 (fr) 1992-02-29 1993-02-04 Particules de support magnétiques

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EP0559250B1 true EP0559250B1 (fr) 1997-05-07

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Publication number Priority date Publication date Assignee Title
JP3397229B2 (ja) * 1997-03-27 2003-04-14 戸田工業株式会社 球状複合体粒子粉末及び該粒子粉末からなる電子写真用磁性キャリア

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JPS60147749A (ja) * 1984-01-11 1985-08-03 Hitachi Metals Ltd 電子写真用フエライトキヤリア
JPS60196777A (ja) * 1984-03-21 1985-10-05 Hitachi Metals Ltd 静電荷像現像剤用キヤリア
DE3780036T2 (de) * 1987-04-24 1993-06-09 Agfa Gevaert Nv Magnetische traegerteilchen.
JP2623601B2 (ja) * 1987-10-06 1997-06-25 富士ゼロックス株式会社 キャリヤ
JPH0274955A (ja) * 1988-09-12 1990-03-14 Canon Inc 電子写真現像剤用キャリア

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