EP0280789A1 - Verfahren zur Herstellung von kugelförmigen Tonerteilchen - Google Patents

Verfahren zur Herstellung von kugelförmigen Tonerteilchen Download PDF

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Publication number
EP0280789A1
EP0280789A1 EP87200287A EP87200287A EP0280789A1 EP 0280789 A1 EP0280789 A1 EP 0280789A1 EP 87200287 A EP87200287 A EP 87200287A EP 87200287 A EP87200287 A EP 87200287A EP 0280789 A1 EP0280789 A1 EP 0280789A1
Authority
EP
European Patent Office
Prior art keywords
particles
resin particles
resin
dispersion
temperature
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.)
Withdrawn
Application number
EP87200287A
Other languages
English (en)
French (fr)
Inventor
Hendrik Hubert Sneyers
Eugeen Louis Van Goethem
Nikolaas Cyriel De Jaeger
Joannes Josephus Van Beek
Serge Martin Tavernier
Herman Jozef Uytterhoeven
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
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 Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP87200287A priority Critical patent/EP0280789A1/de
Publication of EP0280789A1 publication Critical patent/EP0280789A1/de
Withdrawn legal-status Critical Current

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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
    • G03G9/0802—Preparation methods
    • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
    • 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
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0902—Inorganic compounds
    • G03G9/0904—Carbon black

Definitions

  • the present invention relates to a toner composition for use in the developing of electrostatic charge patterns.
  • an electrostatic latent charge image is obtained with an electrophotographic material typically comprising a coating of a photoconductive insulating material on a conductive support. Said coating is given a uniform surface charge in the dark and is then exposed to an image pattern of activating electromagnetic radiation such as light or X-rays.
  • the charge on the photoconductive element is dissipated in the irradiated area to form an electrostatic charge pattern which is then developed with an electroscopic marking material.
  • the marking material or toner whether carried in an insulating liquid or in the form of a dry powder deposits on the exposed surface in accordance with either the charge pattern or the discharge pattern as desired. If the photoconductive element is of the reusable type, e.g. a selenium coated drum, the toner image is transferred to another surface such as paper and then fixed to provide a copy of the original.
  • electrostatic developers are available for use in developing electrostatic charge patterns.
  • the developer comprises carrier particles and electroscopic marking or toner particles electrostatically adhering thereto.
  • the carrier particles may comprise various materials and as the name implies, serve as a medium for carrying the electrostatically responsive marking particles to the charge pattern to be developed.
  • carrier-toner developers are dry developers known for use in magnetic brush development as described e.g. in US-P 3,003,462.
  • the common magnetic brush development technique involves the use of magnetic means associated with a developing mixture composed of magnetic carrier particles carrying a number of smaller electrostatically adhering toner particles.
  • the developer composition is maintained during the development cycle in a loose, brushlike orientation by a magnetic field surrounding, for example, a rotatable non-magnetic cylinder having a magnetic means fixedly mounted inside.
  • the magnetic carrier particles are attracted to the cylinder by the described magnetic field, and the toner particles are held to the carrier particles by virtue of their opposite electrostatic polarity.
  • the toner acquires an electrostatic charge of a sign opposite to that of the carrier material due to triboelectric charging derived from their mutual frictional interaction.
  • this brushlike mass of magnetic carrier with adhering toner particles is drawn across the photoconductive surface bearing the electrostatic image, the toner particles are electrostatically attracted to an oppositely charged latent image and form a visible toner image corresponding to the electrostatic image.
  • Toner powders of which the separate particles are solid and spherical, or substantially spherical, in shape are preferred not only because they have better flow properties but also have a higher mechanical resistance than powders consisting of irregularly shaped particles.
  • Spherical powders can be obtained by spraying a melt or solution of thermoplastic resin, in which colouring material, polarity control agent, electrically conductive material and/or magnetic material are, if so required, dissolved or dispersed.
  • this preparing method has the disadvantage that a complex apparatus is required and only a limited choice of thermoplastic resins has the required melt viscosity or solubility to apply these techniques.
  • thermoplastic resin particles or such particles impregnated with additive, and silica particles having sizes below 100 nanometer are dispersed in a carrier liquid in which liquid the resin of said resin particles does not dissolve, so as to form a dispersion containing less than 500 g of said resin particles per liter of carrier liquid and hydrophobic silica particles in a small but sufficient concentration to inhibit coagulation of said resin particles when softened; the dispersion is heated with stirring to a temperature at which said resin particles do not melt but soften and acquire a spherical or substantially spherical shape, and this temperature is maintained until substantially all the resin particles have become spherical or practically spherical in shape; the dispersion is then cooled down to a temperature at which the resin particles are no longer sticky and, finally, the resin particles are separated from the dispersion liquid, and dried.
  • the silica has to be hydrophobic to avoid changes in conductivity with relative humidity and to make a good adhering contact with the hydrophobic resins used in the toner particles.
  • the hydrophobization of silica requires a special technique for converting the free hydroxyl groups on its surface, e.g. by etherification with a halogen silane.
  • the amount of hydrophobic silica particles to be added to the dispersion is very small and, generally, ranges from 0.2 to 2.0 parts by weight per 100 parts by weight of resin particles it has an influence on the optical density of the powder.
  • the irregularly shaped resin particles, from which the present spheroidized particles are made according to the present invention are obtained in a conventional way by grinding the resin mass containing said magnetically attractable material to form a powder.
  • the introduction of the magnetically attractable material in the resin mass proceeds preferably by melting the thermoplastic resin and adding the magnetically attractable material thereto in finely divided state, cooling down the resin melt to a solidified mass, and finally grinding that mass to fine particles.
  • Suitable magnetically attractable materials are e.g. magnetic or magnetizable metals such as iron, cobalt and nickel and various magnetizable oxides, e.g. Fe2O3, Fe3O4 (magnetite) and CrO2.
  • Other useful materials are ferrites, e.g. these containing zinc, cadmium, barium and manganese in their structure.
  • various magnetic alloys e.g. permalloys and alloys of cobalt such as cobalt-nickel and the like or mixtures of any of these. Good results can be obtained with about 30 % to about 80 % by weight of magnetic material with respect to the resin binder.
  • the average particle size of the magnetic material is preferably in the range of 1 to 0.1 ⁇ m (size determined from electron micrographs). Spheroidal magnetite of that particle size is commercially available under the trade name BAYFERROX of Bayer AG - W. Germany.
  • the organic solvent used in the carrier liquid for carrying out the spheroidization is preferably an organic solvent completely miscible with water, e.g. ethanol, that may have a solvation action on the resin involved in the toner particle preparation. Solvation results in some solvent association with the resin by penetration of the solvent into the resin particle surface without dissolving the resin particle giving the resin particles an improved adherence with respect to the contacting colloidal carbon black.
  • water-miscible solvents that give useful results are : methanol, isopropanol, methylethyl ketone, acetone, methyl glycol, tetrahydrofuran, dioxane and dimethyl formamide.
  • the colloidal carbon is dispersed already in the carrier liquid before the addition of the resin particles having irregular shape, whereupon the temperature of the obtained dispersion is raised to soften the resin particles and this temperature is maintained until the desired quantity of colloidal carbon black has been deposited onto the resin particles having acquired a spherical shape.
  • the dispersing of the carbon black proceeds preferably with the aid of an anionic dispersing agent.
  • Preferred colloidal carbon is carbon black having an average particle size of 10 nm to 100 nm.
  • the particle size is calculated from the specific surface area determined by volumetric nitrogen adsorption based on the theory of Brunauer, Emmett and Teller [ref. J. Am. Chem. Soc. 60 , 309-319 (1938)].
  • carbon black examples include lamp black, channel black, and furnace black e.g. SPEZIALSCHWARZ IV (trade-name of Degussa Frankfurt/M, W.Germany) and VULCAN XC 72 and CABOT REGAL 400 (trade-names of Cabot Corp. High Street 125, Boston, U.S.A.).
  • SPEZIALSCHWARZ IV trade-name of Degussa Frankfurt/M, W.Germany
  • VULCAN XC 72 and CABOT REGAL 400 trade-names of Cabot Corp. High Street 125, Boston, U.S.A.
  • the magnetic or magnetizable material may be used in combination with carbon black to improve the optical density of the toner and/or to control its conductivity.
  • the carbon black is used, e.g. in an amount of 3 to 10 %, preferably 5 %, by weight calculated on the total weight of toner.
  • the optimal mixing temperature is determined by experiments and is normally in the range of 80 to 110°C.
  • the solid mass obtained is crushed and ground e.g. in a hammer mill followed by a jet-mill to an average particle size of 1 to 50 ⁇ m.
  • the fraction having an average particle size from 3 to 30 ⁇ m is e.g. separated by air sifter and used as such for spheroidization according to the present invention.
  • the toner particles may further contain a polarity control agent or conductivity controlling agent.
  • Conductivity is effectively controlled with carbon black.
  • Polarity is controlled e.g. with nigrosine dyestuff and nigrosine dyestuff modified with higher fatty acid as described e.g. in United Kingdom Patent Specification 1,253,­573 providing negative triboelectric chargeability and chromium complexed azo dyestuffs providing positive triboelectric chargeability.
  • Resins or resin mixtures suited for use in the toner preparation according to the present invention have preferably a softening point between 50 °C and 130 °C, more preferably between 80 °C and 110 °C.
  • resins are polystyrene, copolymers of styrene with allyl alcohol, copolymers of styrene with C1-C4-alkyl acrylates and/or methacrylates, polyvinyl chloride, copolymers of vinyl chloride with vinyl acetate, polyacrylate esters, polymethacrylate esters, polyamides and polyester resins and modified polyester resins, e.g. a propoxylated bisphenol A-fumaric acid polyester.
  • modified polester resins The preparation of said modified polester resins is described in United Kingdom Patent Specification 1,373,220 and its use in xerographic toners is described in US-P 4,271,249.
  • suitable resins are polymers derived from methyl-1-pentene as the main component and are described in US-P 4,529,680 relating to the production of mono-component magnetic toner suited for use in pressure fixation.
  • the resins used in the toner particles may be mixed with some amount of natural or synthetic wax within the range of compatibility.
  • the toner prepared according to the present invention is particularly suited for use as single-component magnetic toner having good flowing properties for application in magnetic brush developing techniques.
  • the spheroidized toner particles are mixed with a flow improving means such as microbeads of a fluorinated polymer and/or colloidal silica particles.
  • the flow improving means is used e.g. in an amount of 0.05 to 1 % by weight with respect to the toner.
  • colloidal silica has been described for that purpose in the United Kingdom Patent Specification 1,438,110.
  • AEROSIL 300 (trade mark of Degussa, Frankfurt (M) W.Germany for colloidal silica having a specific surface area of 300 sq.m/g is used.
  • the specific surface area can be measured by a method described by Nelsen and Eggertsen in "Determination of Surface Area Adsorption Measurements by Continuous Flow Method", Analytical Chemistry, Vol. 30, No. 8 (1958) 1387-1390.
  • Suitable fluorinated polymer beads for improving the flowing properties of the toner as well as of the carrier particles are described in the United States Patent Specification 4,187,329.
  • a preferred fluorinated polymer for said use is poly(tetrafluoroethylene) having a particle size of 3 to 4 um and melting point of 325-329°C.
  • Such poly(tetrafluoroethylene) is sold under the trade name HOSTAFLON TF-VP-9202 by Farbwerke Hoechst A.G. W. Germany.
  • An other fluorinated polymer useful for that purpose is polyvinylidene fluoride having an average particle size of 5 um sold under the trade name KYNAR RESIN 301 by Pennwalt Corp. - Plastic div. England.
  • the colloidal silica and at least one of said fluorinated polymers are preferably mixed with the toner in a proportion of 0.15% to 0.075 % by weight respectively.
  • the toner obtains thereby a reduced tendency to form a film on the xerographic plates or drums that have e.g. a vapour-deposited coating of a photoconductive Se-As alloy on a conductive substrate e.g. aluminium.
  • the solidified mass was ground in a hammer mill to obtain coarse particles sizing about 500 ⁇ m, whereupon a more fine grind was obtained in a jet mill yielding irregularly shaped magnetic particles of an average diameter of 23 um.
  • the thus obtained spheroidized particles are separated from residual carbon black and solvent by cascading the obtained dispersion over an inclined plate having strong permanent magnets underneath.
  • the layer of magnetic particles adhering to said plate is thoroughly washed with running water while maintaining the magnetic attraction force.
  • the thus obtained particles were used successivefully as single-component magnetic toner in magnetic brush development.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Developing Agents For Electrophotography (AREA)
EP87200287A 1987-02-24 1987-02-24 Verfahren zur Herstellung von kugelförmigen Tonerteilchen Withdrawn EP0280789A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP87200287A EP0280789A1 (de) 1987-02-24 1987-02-24 Verfahren zur Herstellung von kugelförmigen Tonerteilchen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP87200287A EP0280789A1 (de) 1987-02-24 1987-02-24 Verfahren zur Herstellung von kugelförmigen Tonerteilchen

Publications (1)

Publication Number Publication Date
EP0280789A1 true EP0280789A1 (de) 1988-09-07

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP87200287A Withdrawn EP0280789A1 (de) 1987-02-24 1987-02-24 Verfahren zur Herstellung von kugelförmigen Tonerteilchen

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993016415A1 (en) * 1992-02-14 1993-08-19 Research Laboratories Of Australia Pty. Ltd. Spheroidal particles useful for electrostatography
EP0797122A1 (de) * 1996-03-21 1997-09-24 Dainippon Ink And Chemicals, Inc. Herstellungsverfahren für elektrophotographische Toner
WO2002001301A1 (en) * 2000-06-23 2002-01-03 Dsm N.V. A process for the preparation of toner particles
US6808197B2 (en) 1989-07-14 2004-10-26 Tip Engineering Group, Inc. Preweakened automotive interior trim piece for covering an air bag installation in an automotive vehicle
EP1664937A4 (de) * 2003-09-18 2009-10-21 Australia Res Lab Markierungsflüssigkeitsverfahren der herstellung und dadurch hergestelltes produkt
US10376961B2 (en) 2013-08-12 2019-08-13 United Technologies Corporation Powder spheroidizing via fluidized bed

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3166510A (en) * 1957-08-07 1965-01-19 Burroughs Corp Electrographic printing ink, process for the manufacture thereof, and method of electrostatic printing therewith
FR2317687A1 (fr) * 1975-07-07 1977-02-04 Oce Van Der Grinten Nv Poudre d'agent de virage pour le developpement d'images electrostatique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3166510A (en) * 1957-08-07 1965-01-19 Burroughs Corp Electrographic printing ink, process for the manufacture thereof, and method of electrostatic printing therewith
FR2317687A1 (fr) * 1975-07-07 1977-02-04 Oce Van Der Grinten Nv Poudre d'agent de virage pour le developpement d'images electrostatique

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6808197B2 (en) 1989-07-14 2004-10-26 Tip Engineering Group, Inc. Preweakened automotive interior trim piece for covering an air bag installation in an automotive vehicle
US7919036B2 (en) 1989-07-14 2011-04-05 John W. Bauer, Jr., legal representative Process for producing a preweakened automotive interior trim piece for covering an air bag installation in an automotive vehicle
WO1993016415A1 (en) * 1992-02-14 1993-08-19 Research Laboratories Of Australia Pty. Ltd. Spheroidal particles useful for electrostatography
US5609979A (en) * 1992-02-14 1997-03-11 Research Laboratories Of Australia Pty Ltd. Spheroidal particles useful for electrostatography
US7572122B2 (en) 1994-10-31 2009-08-11 John W. Bauer, Jr., legal representative Apparatus for producing a preweakened automotive interior trim piece for covering an air bag installation in an automotive vehicle
EP0797122A1 (de) * 1996-03-21 1997-09-24 Dainippon Ink And Chemicals, Inc. Herstellungsverfahren für elektrophotographische Toner
US5843614A (en) * 1996-03-21 1998-12-01 Dainippon Ink And Chemicals, Inc. Manufacturing method for toner used in electrophotography
WO2002001301A1 (en) * 2000-06-23 2002-01-03 Dsm N.V. A process for the preparation of toner particles
EP1664937A4 (de) * 2003-09-18 2009-10-21 Australia Res Lab Markierungsflüssigkeitsverfahren der herstellung und dadurch hergestelltes produkt
EP2472333A1 (de) * 2003-09-18 2012-07-04 Xeikon IP BV Methode zur Herstellung elektrostatographischer Toner und elektrostatographischer Toner
US10376961B2 (en) 2013-08-12 2019-08-13 United Technologies Corporation Powder spheroidizing via fluidized bed

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