EP1808733A1 - Procédés de toner - Google Patents

Procédés de toner Download PDF

Info

Publication number
EP1808733A1
EP1808733A1 EP06100387A EP06100387A EP1808733A1 EP 1808733 A1 EP1808733 A1 EP 1808733A1 EP 06100387 A EP06100387 A EP 06100387A EP 06100387 A EP06100387 A EP 06100387A EP 1808733 A1 EP1808733 A1 EP 1808733A1
Authority
EP
European Patent Office
Prior art keywords
toner
percent
latex
poly
resin
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.)
Granted
Application number
EP06100387A
Other languages
German (de)
English (en)
Other versions
EP1808733B1 (fr
Inventor
Raj D. Patel
Allan K. Chen
Cuong Vong
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.)
Xerox Corp
Original Assignee
Xerox Corp
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 Xerox Corp filed Critical Xerox Corp
Publication of EP1808733A1 publication Critical patent/EP1808733A1/fr
Application granted granted Critical
Publication of EP1808733B1 publication Critical patent/EP1808733B1/fr
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/0802Preparation methods
    • G03G9/0804Preparation methods whereby the components are brought together in a liquid dispersing medium
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/0821Developers with toner particles characterised by physical parameters
    • G03G9/0823Electric parameters
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/083Magnetic toner particles
    • G03G9/0837Structural characteristics of the magnetic components, e.g. shape, crystallographic structure
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/087Binders for toner particles
    • G03G9/08702Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08706Polymers of alkenyl-aromatic compounds
    • G03G9/08708Copolymers of styrene
    • G03G9/08711Copolymers of styrene with esters of acrylic or methacrylic acid
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/087Binders for toner particles
    • G03G9/08702Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08726Polymers of unsaturated acids or derivatives thereof
    • G03G9/08733Polymers of unsaturated polycarboxylic acids
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/087Binders for toner particles
    • G03G9/08775Natural macromolecular compounds or derivatives thereof
    • G03G9/08782Waxes
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/087Binders for toner particles
    • G03G9/08784Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08793Crosslinked polymers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/087Binders for toner particles
    • G03G9/08784Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08795Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/087Binders for toner particles
    • G03G9/08784Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08797Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/09Colouring agents for toner particles
    • G03G9/0902Inorganic compounds
    • G03G9/0904Carbon black

Definitions

  • a toner process comprised of heating a mixture of an acicular magnetite dispersion, a colorant dispersion, a wax dispersion, a first latex containing a crosslinked resin, and a second latex containing a resin free of crosslinking in the presence of a coagulant to provide aggregates, stabilizing the aggregates with a silicate salt dissolved in a base, and further heating said aggregates to provide coalesced toner particles.
  • a toner process comprised of a first heating of a mixture of an aqueous colorant dispersion, an aqueous latex emulsion, and an aqueous wax dispersion in the presence of a coagulant to provide aggregates, adding a base followed by adding an organic sequestering agent, and thereafter accomplishing a second heating, and wherein said first heating is below about the latex polymer glass transition temperature (Tg), and said second heating is about above the latex polymer glass transition temperature.
  • Tg latex polymer glass transition temperature
  • a toner process comprised of heating a mixture of an acicular magnetite dispersion, a colorant dispersion, a wax dispersion, a first latex containing a crosslinked resin, a second latex containing a resin substantially free of crosslinking, a coagulant and a complexing compound, and wherein the toner resulting possesses a shape factor of from about 120 to about 150.
  • a toner process comprising mixing a colorant dispersion comprising an acicular magnetite dispersion and a colorant with a latex containing a crosslinked resin, a latex containing a resin free of crosslinking, a wax dispersion, a resin, and a coagulant.
  • toner processes and more specifically, aggregation and coalescence processes. More specifically, the present invention relates in embodiments to methods for the preparation of toner compositions by a chemical process, such as emulsion/aggregation/coalescence, wherein latex particles are aggregated with a wax and a crosslinked gel wherein the gel or crosslinking value is, for example, from about 20 to about 55 percent as measured gravimetrically; colorants, and a magnetite in the presence of a coagulant like a polymetal halide, or alternatively a mixture of coagulants or flocculating agents; thereafter stabilizing the aggregates with an organic complexing agent or a chelating agent, such as ethylenediaminetetraacetic acid (EDTA) dissolved in a base, such as sodium hydroxide, and thereafter coalescing or fusing by heating the mixture above the resin Tg to provide toner size particles which when developed by an electrographic process generates documents suitable for magnetic image character.
  • a chemical process such as emulsion/
  • the chelating agent or compound allows the toner aggregates formed comprised, for example, of magnetite and metal coagulant ions like aluminum, for the formation of water soluble complexes which prevents or minimizes undesired interaction of magnetite or iron particles.
  • the point of zero charge (Pzc) of magnetite and its relationship to pH and to temperature is illustrated, for example, in copending application U.S. Serial No. 10/106,473 , Publication No. 20030180648 , the disclosure of which is totally incorporated herein by reference.
  • the Pzc can be altered and thereby also minimize the generation of charges which may interfere in the toner emulsion aggregation process.
  • a number of advantages are associated with the present invention in embodiments thereof including, for example, excellent toner hot offset, for example above about 210°C, and more specifically, from about 210°C to about 230°C; a toner fusing latitude of from about 20°C to about 40°C wherein fusing latitude refers to a temperature in which, when a developed image is fused, evidences substantially no offset either to the substrate that the image is fused on, referred to as "Cold" offset or an offset on the fuser roll referred to as the "Hot" offset; a minimum fixing temperature of, for example, about 170°C to about 195°C; and extended photoreceptor life since the toner fusing temperature can be below about 195°C, such as from about 175°C to about 190°C; stable, controllable and substantially predictable PCZ, (point of zero charge), and wherein the charge on the magnetite particles can be either positive or negative depending, for example, on the pH of the medium, that is when the pH is
  • Magnetic ink printing methods with inks containing magnetic particles are known.
  • U.S. Patent 3,998,160 the disclosure of which is totally incorporated herein by reference, that various magnetic inks have been used in printing digits, characters, or artistic designs on checks or bank notes.
  • the magnetic ink used for these processes can contain, for example, magnetic particles, such as a magnetite in a fluid medium, and a magnetic coating of ferric oxide, chromium dioxide, or similar materials dispersed in a vehicle comprising binders, and plasticizers.
  • MICR magnetic image character recognition information
  • the toners selected usually contain magnetites having specific properties, an important one of which is a high enough level of remanence or retentivity.
  • Retentivity is a measure of the magnetism left when the magnetite is removed from the magnetic field, that is, the residual magnetism.
  • toners with a high enough retentivity such that when the characters are read, the magnetites produce a signal strength of equal to greater than about 100 percent.
  • the signal level can vary in proportion to the amount of toner deposited on the document being generated, and signal strength of a toner composition can be measured by using known devices, including the MICR-Mate 1, manufactured by Checkmate Electronics, Inc.
  • Emulsion/aggregation/coalescing processes for the preparation of toners are illustrated in a number of Xerox patents, the disclosures of which are totally incorporated herein by reference, such as U.S. Patent 5,290,654 , U.S. Patent 5,278,020 , U.S. Patent 5,308,734 , U.S. Patent 5,370,963 , U.S. Patent 5,344,738 , U.S. Patent 5,403,693 , U.S. Patent 5,418,108 , U.S. Patent 5,364,729 , and U.S. Patent 5,346,797 ; and also of interest may be U.S.
  • the components and processes of these Xerox patents can be selected for the present invention in embodiments thereof.
  • U.S. Patent 5,922,501 illustrates a process for the preparation of toner comprising blending an aqueous colorant dispersion and a latex resin emulsion, and which latex resin is generated from a dimeric acrylic acid, an oligomer acrylic acid, or mixtures thereof and a monomer; heating the resulting mixture at a temperature about equal, or below about the glass transition temperature (Tg) of the latex resin to form aggregates; heating the resulting aggregates at a temperature about equal to, or above about the Tg of the latex resin to effect coalescence and fusing of the aggregates; and optionally isolating the toner product, washing, and drying.
  • Tg glass transition temperature
  • the present invention provides:
  • a feature illustrated herein relates to the provision of a toner with a number of the advantages illustrated herein, and more specifically, a complexing compound coated magnetite containing toner for Magnetic Ink Character Recognition (MICR) processes by, for example, selecting specific magnetites that provide an acceptable readability signal by a check reader, and wherein the resulting toners possess a sufficient magnetic signal, desirable melt fusing, hot offset, and fusing latitude temperatures, and which toners also contain a gel or a crosslinked resin.
  • MICR Magnetic Ink Character Recognition
  • a process for the preparation of a MICR toner wherein resins, pigment and wax are aggregated in the presence of a coagulant, such as polymetal halides or polymetal sulfosilicate, to provide toner size aggregates which can then be stabilized, for example with substantially no increase in size, by introducing an organic complexing or chelating compound in the presence of a base and further heating to provide toners with narrow particle size distribution.
  • a coagulant such as polymetal halides or polymetal sulfosilicate
  • aspects of the present invention relate to a toner process comprised of heating a mixture of an acicular magnetite dispersion, a colorant dispersion, a wax dispersion, a first latex containing a crosslinked resin, and a second latex containing a resin substantially free of or free of crosslinking in the presence of a coagulant to provide aggregates, stabilizing the aggregates with an organic complexing or chelating compound dissolved in a base, and further heating the aggregates to provide coalesced toner particles; a toner process comprised of heating a mixture of an acicular magnetite dispersion, a colorant dispersion, a first latex containing a crosslinked resin, and a second latex containing a resin free of crosslinking in the presence of a coagulant; above the latex resin Tg adding a complexing compound salt dissolved in a base, and further heating said aggregates to provide coalesced toner particles; a process comprising heating a mixture of magnetite,
  • the resin or polymer selected for the process of the present invention can be prepared by a number of known methods such as, for example, emulsion polymerization, including semicontinuous emulsion polymerization methods, and the monomers utilized in such processes can be selected from, for example, styrene, acrylates, methacrylates, butadiene, isoprene, acrylonitrile; monomers comprised of an A and a B monomer wherein from about 75 to about 95 percent of A and from about 5 to about 25 percent of B is selected, wherein A can be, for example, styrene, and B can be, for example, an acrylate, methacrylate, butadiene, isoprene, or an acrylonitrile; and optionally, acid or basic olefinic monomers, such as acrylic acid, methacrylic acid, beta carboxy ethyl acrylate, acrylamide, methacrylamide, quaternary ammonium halide of dialkyl or trialkyl
  • the presence of acid or basic groups in the monomer or polymer resin is optional, and such groups can be present in various amounts of from about 0.1 to about 10 percent by weight of the polymer resin.
  • Chain transfer agents such as dodecanethiol or carbon tetrabromide, can also be selected when preparing resin particles by emulsion polymerization.
  • Other processes of obtaining resin particles of, for example, from about 0.01 micron to about 1 micron in diameter can be selected like polymer microsuspension process, such as those illustrated in U.S. Patent 3,674,736 , the disclosure of which is totally incorporated herein by reference, polymer solution microsuspension process, such as disclosed in U.S. Patent 5,290,654 , the disclosure of which is totally incorporated herein by reference, mechanical grinding process, or other known processes; and toner processes wherein the resin possesses a crosslinking percentage of from about 1 to about 50 or from about 1.5 to about 30.
  • Colorants include dyes, pigments, and mixtures thereof, colorant examples being illustrated in a number of the copending applications referenced herein, and more specifically, which colorants include known colorants like black, cyan, red, blue, magenta, green, brown, yellow, mixtures thereof, and the like.
  • Various known colorants, such as pigments, selected for the processes of the present invention and present in the toner in an effective amount of, for example, from about 1 to about 25 percent by weight of toner, and more specifically, in an amount of from about 3 to about 10 percent by weight include, for example, carbon black like REGAL 330 ® ; REGAL 660 ® ; phthalocyanine Pigment Blue 15, Pigment Blue 15.1, Pigment Blue 15.3, Pigment Green 7, Pigment Green 36, Pigment Orange 5, Pigment Orange 13, Pigment Orange 16, Pigment Orange 36, Pigment Red 122, Pigment Red 53.1, Pigment Red 48.1, Pigment Red 48.2, Pigment Red 49.1, Pigment Red 49.2, Pigment Red 22, Pigment Red 185, Pigment Red 188, Pigment Red 210, Pigment Red 238, Pigment Red 170, Pigment Red 23, Pigment Red 81.2, Pigment Red 81.3, Pigment Red 57, Pigment Red 17, Pigment Red 169, Pigment Violet 19, Pigment Violet 23, Pigment Violet 3, Pigment Violet 27, Pigment
  • colored pigments that can be selected are cyan, magenta, or yellow pigments, and mixtures thereof.
  • magentas examples include, for example, 2,9-dimethyl-substituted quinacridone and anthraquinone dye identified in the Color Index as Cl 60710, Cl Dispersed Red 15, diazo dye identified in the Color Index as Cl 26050, Cl Solvent Red 19, and the like.
  • cyans that may be selected include copper tetra(octadecyl sulfonamido) phthalocyanine, x-copper phthalocyanine pigment identified in the Color Index as CI 74160, CI Pigment Blue, and Anthrathrene Blue, identified in the Color Index as CI 69810, Special Blue X-2137, and the like; while illustrative examples of yellows that may be selected are diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a monoazo pigment identified in the Color Index as Cl 12700, Cl Solvent Yellow 16, a nitrophenyl amine sulfonamide identified in the Color Index as Foron Yellow SE/GLN, Cl Dispersed Yellow 33, 2,5-dimethoxy-4-sulfonanilide phenylazo-4'-chloro-2,5-dimethoxy acetoacetanilide, Yellow 180 and Permanent Yellow FGL, wherein the colorant
  • Organic dye examples include known suitable dyes, reference the Color Index, and a number of U.S. patents.
  • Organic soluble dye examples, preferably of a high purity, for the purpose of color gamut are Neopen Yellow 075, Neopen Yellow 159, Neopen Orange 252, Neopen Red 336, Neopen Red 335, Neopen Red 366, Neopen Blue 808, Neopen Black X53, Neopen Black X55, wherein the dyes are selected in various suitable amounts, for example from about 0.5 to about 20 percent by weight, and more specifically, from about 5 to about 20 weight percent of the toner.
  • Colorants may include pigment, dye, mixtures of pigment and dyes, mixtures of pigments, mixtures of dyes, and the like.
  • Crosslinked resin examples with crosslinking values as illustrated herein, and yet more specifically, of, for example, from about 25 to about 80, and more specifically, from about 30 to about 65 percent, and which resins are selected in various amounts, such as from about 1 to about 20, and more specifically, from about 5 to about 10 weight percent based on the weight percentages of the remaining toner components, include the resins illustrated herein, which resins are crosslinked by known crosslinking compounds, such as divinyl benzene.
  • anionic surfactants examples include, for example, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates, abitic acid, available from Aldrich, NEOGEN RKTM, NEOGEN SCTM from Kao, DOWFAXTM obtained from Dow Chemicals, ABEXTM obtained from Rhodia, and the like.
  • An effective concentration of the anionic surfactant generally employed is, for example, from about 0.01 to about 10 percent by weight, and preferably from about 0.1 to about 5 percent by weight of monomers used to prepare the toner polymer resin.
  • nonionic surfactants that can be selected for the processes illustrated herein and that may be, for example, included in the resin latex dispersion are, for example, polyvinyl alcohol, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy) ethanol, available from Rhodia as IGEPAL CA-210 ® , IGEPAL CA-520 ® , IGEPAL CA-720 ® , IGEPAL CO-890 ® , IGEPAL CO-720 ® , IGEPAL CO-
  • a suitable amount of cationic surfactant can be selected, such as from about
  • Examples of a complexing compound that can be selected are those that are suitable, such as ethylenediamine tetraacetic acid; diethylenetriamine pentacetic acid; nitrilotriacetic acid; the corresponding salts of the aforementioned, such as the alkali metal salts like sodium, potassium, calcium, and the like, and which complexing compound can be mixed with soap, water, and the like. Also, in embodiments, biodegradable compounds of the complexing compounds illustrated can also be selected.
  • organic complexing compounds or agents include ethylene diamine tetraacetic acid (EDTA), gluconal, sodium gluconate, potassium and sodium citrate, nitrotriacetate (NTA) salt, GLDA (commercially available L-glutamic acid N,N diacetic acid) humic and fulvic acids, maltol and ethyl-maltol, peta-acetic and tetraacetic acids; the corresponding salts of the aforementioned, such as the alkali metal salts like sodium, potassium, calcium, and the like. and
  • Counterionic coagulants selected for the processes illustrated herein can be comprised of organic, or inorganic components, and the like.
  • the ionic surfactant of the resin latex dispersion can be an anionic surfactant
  • the counterionic coagulant can be a polymetal halide or a polymetal disulfo compound (PASS).
  • Coagulants that can be included in amounts of, for example, from about 0.05 to about 10 weight percent include polymetal halides, polymetal disulfo compounds, divalent or multivalent salts optionally in combination with cationic surfactants, and the like.
  • Inorganic cationic coagulants include, for example, polyaluminum chloride (PAC), polyaluminum sulfates (PASS), aluminum sulfate, zinc sulfate, or magnesium sulfate.
  • the coagulant is in embodiments present in an aqueous medium in an amount of from, for example, about 0.05 to about 10 percent by weight, and more specifically, in an amount of from about 0.075 to about 2 percent by weight.
  • the coagulant may also contain minor amounts of other components, such as for example nitric acid.
  • the coagulant is usually added slowly while continuously subjecting the mixture resulting to high shear, for example, by stirring with a blade at about 3,000 to about 10,000 rpm, and preferably about 5,000 rpm, for about 1 to about 120 minutes.
  • a high shearing device for example an intense homogenization device, such as the in-line IKA SD-41, may be used to ensure that the coagulant is homogeneous and uniformly dispersed.
  • waxes examples include those as illustrated herein, such as those of the aforementioned copending applications, polypropylenes and polyethylenes commercially available from Allied Chemical and Petrolite Corporation, wax emulsions available from Michaelman Inc. and the Daniels Products Company, EPOLENE N-15TM commercially available from Eastman Chemical Products, Inc., VISCOL 550-PTM , a low weight average molecular weight polypropylene available from Sanyo Kasei K.K., and similar materials.
  • Examples of functionalized waxes are amines, amides, for example AQUA SUPERSLIP 6550TM, SUPERSLIP 6530TM available from Micro Powder Inc., fluorinated waxes, for example POLYFLUO 190TM, POLYFLUO 200TM, POLYFLUO 523XFTM, AQUA POLYFLUO 411TM, AQUA POLYSILK 19TM, POLYSILK 14TM available from Micro Powder Inc., mixed fluorinated, amide waxes, for example MICROSPERSION 19TM also available from Micro Powder Inc., imides, esters, quaternary amines, carboxylic acids or acrylic polymer emulsions, for example JONCRYL 74TM, 89TM, 130TM, 537TM, and 538TM, all available from SC Johnson Wax; chlorinated polypropylenes and polyethylenes available from Allied Chemical and Petrolite Corporation and SC Johnson Wax.
  • the amounts of the wax selected in embodiments is, for example, from about 3.5
  • the solids content of the resin latex dispersion is not particularly limited, thus the solids content may be from, for example, about 10 to about 90 percent.
  • the colorants such as carbon black, in some instances they are available in the wet cake or concentrated form containing water, and can be easily dispersed utilizing a homogenizer or simply by stirring or ball milling, attrition, or media milling.
  • pigments are available only in a dry form whereby dispersion in water is effected by microfluidizing using, for example, a M-110 microfluidizer or an agitzer, and passing the pigment dispersion from about 1 to about 10 times through a chamber by sonication, such as using a Branson 700 sonicator, with a homogenizer, ball milling, attrition, or media milling with the optional addition of dispersing agents such as the aforementioned ionic or nonionic surfactants.
  • sonication such as using a Branson 700 sonicator
  • the pH is increased, for example, from about 2 to about 3 to about 7 to about 8; from about 2 to about 2.8 to about 7 to about 7.5 by the addition of a suitable pH agent of, for example, sodium hydroxide to provide for the stabilization of the aggregated particles and to prevent/minimize the toner size growth and loss of GSD during further heating, for example, raising the temperature about 10°C to about 50°C above the resin Tg.
  • the complexing compound provides for a coating thereof on the magnetite particles thereby lowering the Pzc of the magnetite such that during the coalescence where the pH of the mixture reduced to below about 5 and preferably about 4.5, the fusion of the aggregates can be accomplished by using an acid.
  • pH reducing agents include, for example, nitric acid, citric acid, sulfuric acid or hydrochloric acid, and the like.
  • the toner particles formed by processes illustrated herein possess, for example, an average volume diameter of from about 0.5 to about 25, and more specifically, from about 1 to about 10 microns, and narrow GSD characteristics of, for example, from about 1.05 to about 1.25, or from about 1.15 to about 1.25 as measured by a Coulter Counter.
  • the toner particles also possess an excellent shape factor, for example, of 135 or less wherein the shape factor refers, for example, to the measure of toner smoothness and toner roundness where a shape factor of about 100 is considered spherical and smooth without any surface protrusions, while a shape factor of about 150 is considered to be rough in surface morphology and the shape is like a potato.
  • the toner particles illustrated herein may also include known charge additives in effective amounts of, for example, from about 0.1 to about 5 weight percent, such as alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Patents 3,944,493 ; 4,007,293 ; 4,079,014 ; 4,394,430 and 4,560,635 , the disclosures of which are totally incorporated herein by reference, and the like.
  • charge additives in effective amounts of, for example, from about 0.1 to about 5 weight percent, such as alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Patents 3,944,493 ; 4,007,293 ; 4,079,014 ; 4,394,430 and 4,560,635 , the disclosures of which are totally incorporated herein by reference, and the like.
  • Surface additives that can be added to the toner compositions after washing or drying include, for example, metal salts, metal salts of fatty acids, colloidal silica, metal oxides, mixtures thereof and the like, which additives are usually present in an amount of from about 0.1 to about 2 weight percent, reference U.S. Patents 3,590,000 ; 3,720,617 ; 3,655,374 and 3,983,045 , the disclosures of which are totally incorporated herein by reference.
  • Specific additives include zinc stearate and AEROSIL R972 ® available from Degussa Chemical, and each present in an amount of from about 0.1 to about 2 percen, which can be added during the aggregation process or blended into the formed toner product, calcium stearate and the like.
  • Developer compositions can be prepared by mixing the toners obtained with the process of the present invention with known carrier particles, including coated carriers, such as steel, ferrites, and the like, reference U.S. Patents 4,937,166 and 4,935,326 , the disclosures of which are totally incorporated herein by reference, for example from about 2 percent toner concentration to about 8 percent toner concentration.
  • a latex emulsion (i) comprised of polymer particles generated from the emulsion polymerization of styrene, butyl acrylate and beta carboxy ethyl acrylate (Beta CEA) was prepared as follows.
  • a surfactant solution of 434 grams of DOWFAX 2A1TM (anionic emulsifier -55 percent active ingredients) and 387 kilograms of deionized water was prepared by mixing these components for 10 minutes in a stainless steel holding tank. The holding tank was then purged with nitrogen for 5 minutes before transferring the mixture into a reactor. The reactor was then continuously purged with nitrogen while being stirred at 100 RPM. The reactor was then heated to 80°C.
  • seeds refer, for example, to the initial emulsion latex added to the reactor prior to the addition of the initiator solution while being purged with nitrogen.
  • the above initiator solution was then slowly charged into the reactor forming about 5 to about 12 nanometers of latex "seed" particles. After 10 minutes, the remainder of the emulsion was continuously fed using metering pumps.
  • the resulting isolated product was comprised of 40 weight percent of submicron, 0.5 micron diameter resin particles of styrene/butylacrylate/beta CEA suspended in an aqueous phase containing the above surfactant.
  • the molecular properties resulting for the resin latex were M w (weight average molecular weight) of 35,000, M n of 10,600 as measured by a Gel Permeation Chromatograph, and a midpoint Tg of 55.8°C, as measured by a Differential Scanning Calorimeter where the midpoint Tg is the halfway point between the onset and the offset Tg of the polymer.
  • a crosslinked latex emulsion comprised of polymer particles generated from the emulsion polymerization of styrene, butyl acrylate and beta carboxy ethyl acrylate (p) CEA was prepared as follows.
  • a surfactant solution of 4.08 kilograms of NEOGENTM RK (anionic emulsifier) and 78.73 kilograms of deionized water was prepared by mixing these components for 10 minutes in a stainless steel holding tank. The holding tank was then purged with nitrogen for 5 minutes before transferring the resulting mixture into the above reactor. The reactor was then continuously purged with nitrogen while the contents were being stirred at 100 RPM. The reactor was then heated up to 76°C, and held there for a period of 1 hour.
  • monomer emulsion was prepared in the following manner. 47.39 Kilograms of styrene, 25.52 kilograms of butyl acrylate, 2.19 kilograms of ⁇ -CEA, 0.729 kilogram of divinyl benzene (DVB) crosslinking agent, 1.75 kilograms of NEOGENTM RK (anionic surfactant), and 145.8 kilograms of deionized water were mixed to form an emulsion.
  • One (1) percent of the emulsion was then slowly fed into the reactor while the reactor was being purged with nitrogen containing the aqueous surfactant phase at 76°C to form "seeds". The initiator solution was then slowly charged into the reactor and after 40 minutes the remainder of the emulsion was continuously fed in using metering pumps over a period of 3 hours.
  • the temperature was held at 76°C for an additional 4 hours to complete the reaction. Cooling was then accomplished and the reactor temperature was reduced to 35°C.
  • the product was collected into a holding tank. After drying, the resin latex onset Tg was 53.5°C.
  • the resulting latex was comprised of 25 percent crosslinked resin, 72.5 percent water and 2.5 percent anionic surfactant.
  • the resin had a ratio of 65:35:3 pph:1 pph of styrene:butyl acrylate: ⁇ -CEA:DVB.
  • the mean particle size of the gel latex was 50 nanometers as measured on disc centrifuge, and the resin in the latex possessed a crosslinking value of 25 percent as measured by known gravimetric methods.
  • the aqueous wax dispersion utilized in the following Examples was generated using waxes available from Baker-Petrolite (1) P725 polyethylene wax with a low molecular weight M w of 725, and a melting point of 104°C, or (2) P850 wax with a low molecular weight of 850 and a melting point of 107°C and NEOGEN RKTM as an anionic surfactant/dispersant.
  • the wax particle diameter size was determined to be approximately 200 nanometers, and the wax slurry was a solid loading of 30 percent (weight percent throughout).
  • the pigment dispersion obtained from Sun Chemicals, was an aqueous dispersion containing carbon black (REGAL 330 ® ), an anionic surfactant, 2 percent, and 79 percent water.
  • MAGNOX B2550TM acicular magnetite composed of 21 percent FeO and 79 percent Fe 2 O 3 having a particle size of about 0.6 micron X 0.1 micron was added to 600 grams of water containing 1.3 grams of a 20 percent aqueous anionic surfactant (NEOGEN RKTM) to which 85 grams of an 18 percent carbon black REGAL 330 ® solution were added.
  • the resultant mixture was then polytroned or homogenized at a speed of 5,000 rpm, for 3 minutes, to provide a pigment dispersion.
  • a dispersion of submicron polyethylene P 850 wax particles (30 percent solids) followed by the addition of 320 grams of the above prepared anionic latex A comprised of submicron latex particles (40 percent solids) of styrene/butylacrylate/beta CEA, and 64 grams of the cross linked latex B of styrene/butylacrylate/divinyl benzene beta CEA (25.5 percent solids) while polytroned at a speed of 5,000 rpm for a period of 5 minutes 300 grams of water were added to reduce the viscosity of the resulting blend to which then was added an aqueous PAC (polyaluminum chloride) solution comprised of 3.1 grams of a 10 percent solids placed in 25 grams of 0.3M nitric acid.
  • aqueous PAC polyaluminum chloride
  • the resulting blend was then heated to a temperature of 50°C while stirring for a period of 100 minutes to obtain a particle size of 5.3 micron with a GSD of 1.20.
  • 140 Grams of the above prepared noncrosslinked latex (Latex A) were then added to the aggregate mixture, and followed by stirring at 50°C for 130 minutes to provide a particle size of 5.9 microns and a GSD of 1.20.
  • the aggregate mixture was then stabilized from further growth by introducing 10.5 grams of a basic mixture of EDTA powder dissolved in sodium hydroxide and containing 30 percent solids thereby changing the pH of the mixture from a value of 2.6 to 4.5, followed by adding 4 percent of sodium hydroxide to arrive at a pH of about 7.
  • the mixture was then heated to 93°C during which the pH decreased to 6.5. After 10 minutes at 93°C the particle size measure was 6.2 with a GSD of 1.20. After 60 minutes the pH was reduced to 4.7. The particle size measure was 6.4 with a GSD of 1.22. The mixture was then further heated for a period of 600 minutes at a pH of 4.7 and the particle size obtained was 6.4 microns with a GSD of 1.20. The resultant mixture was cooled and the toner obtained was washed 4 times with water and dried on the freeze dryer. The resulting toner was comprised of 25 percent magnetite, 57.1 percent noncrosslinked resin, 5 percent crosslinked resin, 4.4 percent carbon black, and 8.5 percent wax.
  • the charge of the toner was 19.8 microC/g as measured against the FC076 carrier, similar to the control or the comparative toner.
  • the development of the resulting toner as a function of development voltage under various throughput conditions illustrated that the toner performance was stable to aging under various throughputs of printing.
  • the target MICR signal of 120 percent of the nominal (nominal being 100 percent) was achieved at a development voltage of 250.
  • the toner was then evaluated in a Xerox Corporation DC 265 engine and toner development as a function of voltage did not change at different throughputs conditions, for example the development at time zero, and that after 1,000 prints including under zero throughput conditions (xerographic stress case) at a given voltage indicated little toner aging.
  • the above toner when fused in a Xerox Corporation DC 265 xerographic engine possessed a MFT (melt fusing temperature) of 187°C and a HOT offset temperature greater than about 210°C, (for example, about an estimated 214°C) the optimum temperature that could be measured by the temperature detector used.
  • the shape factor of the toner was 125 where a SF of 100 is considered very smooth and spherical in shape; a SF of 145 is considered irregular in shape with a rough morphology; and a SF of 125 is considered a potato shape with a smooth surface.
  • MAGNOX B2550TM acicular magnetite composed of 21 percent FeO and 79 percent Fe 2 O 3 having a particle size of about 0.6 micron X 0.1 micron was added to 600 grams of water containing 1.3 grams of 20 percent aqueous anionic surfactant (NEOGEN RKTM) to which 85 grams of an 18 percent carbon black REGAL 330 ® solution were added.
  • the resultant mixture was then polytroned or homogenized at a speed of 5,000 rpm for 3 minutes to provide a pigment dispersion.
  • a dispersion of submicron polyethylene P 850 wax particles 30 percent solids followed by the addition of 320 grams of the anionic Latex A comprised of submicron latex particles (40 percent solids) of styrene/butylacrylate/beta CEA, and 64 grams of the crosslinked Latex B of styrene/butylacrylate/divinyl benzene beta CEA (25.5 percent solids) while polytroned at a speed of 5,000 rpm for a period of 5 minutes 300 grams of water were added to reduce the viscosity of the resulting blend to which was then added an aqueous PAC solution comprised 3.1 grams of 10 percent solids placed in 25 grams of 0.3M nitric acid.
  • the resulting blend was then heated to a temperature of 50°C while stirring for a period of 100 minutes to obtain a particle size of 5.5 microns with a GSD of 1.21.
  • 140 Grams of the above noncrosslinked latex (Latex A) were then added to the aggregate mixture and stirred at 50°C for 120 minutes to provide a particle size of 6 microns and a GSD of 1.20.
  • the aggregate mixture was then stabilized from further growth by introducing 13.4 grams of a basic mixture of EDTA powder dissolved in sodium hydroxide containing 30 percent solids to change the pH of the mixture from value of 2.6 to 4.9, followed by adding 4 percent sodium hydroxide resulting in a pH of about 70.
  • the mixture was then heated to 93°C during which the pH decreased to 6.5.
  • the particle size measured was 6.1 with a GSD of 1.20.
  • the pH was reduced to 4.6 by adding 4 percent nitric acid.
  • the particle size measured was 6.3 with a GSD of 1.21.
  • the mixture was then further heated for a period of 600 minutes at a pH of 4.6 and the particle size obtained was 6.4 microns with a GSD of 1.20.
  • the resultant mixture was cooled and the toner obtained was washed 4 times with water and dried on the freeze dryer.
  • the resulting toner was comprised of 25 percent magnetite, 57.1 percent noncrosslinked resin, 5 percent crosslinked resin, 4.4 percent carbon black, and 8.5 percent wax.
  • the shape factor of this toner was 126.
  • the charge of the toner was -17 microC/g measured against a carrier comprised of a ferrite carrier coated with a polymer mixture of butylmethylmethacrylate/methylmethylacrylate or preferably the carrier of the Xerox Corporation Docutech 2240 machine.
  • MAGNOX B2550TM acicular magnetite composed of 21 percent FeO and 79 percent Fe 2 O 3 having a particle size of about 0.6 micron X 0.1 micron were added to 600 grams of water containing 1.3 grams of 20 percent aqueous anionic surfactant (NEOGEN RKTM) to which 85 grams of an 18 percent carbon black REGAL 330 ® solution were added.
  • the resultant mixture was then polytroned or homogenized at a speed of 5,000 rpm for 3 minutes to provide a pigment dispersion.
  • a dispersion of submicron polyethylene P 850 wax particles (30 percent solids) followed by the addition of 320 grams of the anionic Latex A comprised of submicron latex particles (40 percent solids) of styrene/ butylacrylate/beta CEA, and 64 grams of the crosslinked Latex B of styrene/butylacrylate/divinyl benzene beta CEA (25.5 percent solids) while polytroned at a speed of 5,000 rpm for a period of 5 minutes. 300 Grams of water were added to reduce the viscosity of the resulting blend to which was then added an aqueous PAC solution comprised of 3.1 grams of 10 percent solids placed in 25 grams of 0.3M nitric acid.
  • the resulting blend was then heated to a temperature of 50°C while stirring for a period of 100 minutes to obtain a particle size of 5.4 microns with a GSD of 1.19.
  • 140 Grams of the above noncrosslinked latex (Latex A) were then added to the aggregate mixture and stirred at 50°C for 120 minutes to provide a particle size of 5.8 microns and a GSD of 1.20.
  • the aggregate mixture was then stabilized from further growth by introducing 16 grams of a basic mixture of EDTA powder dissolved in sodium hydroxide containing 30 percent solids to change the pH of the mixture from a value of 2.6 to 4.5, followed by adding 4 percent sodium hydroxide resulting in a pH of about 7.
  • the mixture was then heated to 93°C during which the pH decreased to 6.3.
  • the particle size measure was 6.3 with a GSD of 1.20.
  • the pH was reduced to 4.5 by adding 4 percent nitric acid.
  • the particle size measured was 6.3 with a GSD of 1.21.
  • the mixture was then further heated for a period of 600 minutes at a pH of 4.5 and the particle size obtained was 6.4 microns with a GSD of 1.20.
  • the resultant mixture was cooled and the toner obtained was washed 4 times with water and dried on the freeze dryer.
  • the resulting toner was comprised of 25 percent magnetite, 57.1 percent noncrosslinked resin, 5 percent crosslinked resin, 4.4 percent carbon black, and 8.5 percent wax.
  • the shape factor for this toner was 124.
  • the dry toner charge triboelectric was -16.4 microC/g as measured against a carrier comprised of a ferrite carrier coated with a polymer mixture of butylmethylmethacrylate/methylmethylacrylate or preferably the carrier of the Xerox Corporation Docutech 2240 machine.
  • a comparative toner (T 2239) was prepared in a similar manner as the above Examples and where sodium hydroxide was used as a stabilizer instead of EDTA resulting in a particle size of 6.8 microns with a GSD of 1.23.
  • the pH of the mixture was allowed to drift to below 6.8 during the ramping of the temperature to 93°C.
  • the coalesce pH was reduced to a pH of 5.8 in stages over a period of 2 hours and the mixture resulting heated for a period of 10 hours.
  • the resulting particle size was 7.6 microns with a GSD of 1.27.
  • the charge of this toner against the carrier was 15.1 microC/g.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Developing Agents For Electrophotography (AREA)
EP20060100387 2006-01-16 2006-01-16 Procédés de toner Expired - Fee Related EP1808733B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US4610906A 2006-01-16 2006-01-16

Publications (2)

Publication Number Publication Date
EP1808733A1 true EP1808733A1 (fr) 2007-07-18
EP1808733B1 EP1808733B1 (fr) 2009-11-11

Family

ID=37903485

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20060100387 Expired - Fee Related EP1808733B1 (fr) 2006-01-16 2006-01-16 Procédés de toner

Country Status (2)

Country Link
EP (1) EP1808733B1 (fr)
DE (1) DE602006010318D1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1898264A2 (fr) 2006-09-05 2008-03-12 Xerox Corporation Compositions de toner
WO2009053688A2 (fr) * 2007-10-26 2009-04-30 Fujifilm Imaging Colorants Limited Améliorations apportées à ou liées à des toners fabriqués à partir de latex
EP4063411A1 (fr) * 2021-03-26 2022-09-28 FUJIFILM Business Innovation Corp. Adhésif sensible à la pression, toner de développement d'images à charge électrostatique, procédé de fabrication d'adhésif sensible à la pression, procédé de fabrication de toner de développement d'images à charge électrostatique, et produit lié

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020187415A1 (en) 2001-06-11 2002-12-12 Xerox Corporation Toner coagulant processes
EP1349012A2 (fr) * 2002-03-25 2003-10-01 Xerox Corporation Procédé pour la préparation de toner
US6767684B1 (en) * 2003-01-29 2004-07-27 Xerox Corporation Toner processes
US20040265729A1 (en) 2003-06-25 2004-12-30 Xerox Corporation Toner processes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020187415A1 (en) 2001-06-11 2002-12-12 Xerox Corporation Toner coagulant processes
EP1349012A2 (fr) * 2002-03-25 2003-10-01 Xerox Corporation Procédé pour la préparation de toner
US6767684B1 (en) * 2003-01-29 2004-07-27 Xerox Corporation Toner processes
US20040265729A1 (en) 2003-06-25 2004-12-30 Xerox Corporation Toner processes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1898264A2 (fr) 2006-09-05 2008-03-12 Xerox Corporation Compositions de toner
EP1898264A3 (fr) * 2006-09-05 2009-12-23 Xerox Corporation Compositions de toner
US7794911B2 (en) 2006-09-05 2010-09-14 Xerox Corporation Toner compositions
US8142970B2 (en) 2006-09-05 2012-03-27 Xerox Corporation Toner compositions
WO2009053688A2 (fr) * 2007-10-26 2009-04-30 Fujifilm Imaging Colorants Limited Améliorations apportées à ou liées à des toners fabriqués à partir de latex
WO2009053688A3 (fr) * 2007-10-26 2009-09-24 Fujifilm Imaging Colorants Limited Améliorations apportées à ou liées à des toners fabriqués à partir de latex
US8435711B2 (en) 2007-10-26 2013-05-07 Fujifilm Imaging Colorants Limited Toners made from latexes
EP4063411A1 (fr) * 2021-03-26 2022-09-28 FUJIFILM Business Innovation Corp. Adhésif sensible à la pression, toner de développement d'images à charge électrostatique, procédé de fabrication d'adhésif sensible à la pression, procédé de fabrication de toner de développement d'images à charge électrostatique, et produit lié

Also Published As

Publication number Publication date
EP1808733B1 (fr) 2009-11-11
DE602006010318D1 (de) 2009-12-24

Similar Documents

Publication Publication Date Title
US7282314B2 (en) Toner processes
US6617092B1 (en) Toner processes
US7214463B2 (en) Toner processes
US6656657B2 (en) Toner processes
US6942954B2 (en) Toner processes
US6656658B2 (en) Magnetite toner processes
US6627373B1 (en) Toner processes
US7037633B2 (en) Toner processes
US6767684B1 (en) Toner processes
US7358021B2 (en) Hybrid toner processes
US6582873B2 (en) Toner coagulant processes
CA2585599C (fr) Compositions de toner
US6936396B2 (en) Toner processes
CA2496059C (fr) Composes de toner
EP1666977B1 (fr) Compositions de toner
US8475985B2 (en) Magnetic compositions
US20030180648A1 (en) Toner processes
US6984480B2 (en) Toner processes
US7833684B2 (en) Toner compositions
EP1808733B1 (fr) Procédés de toner
US20070111129A1 (en) Toner compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20080118

AKX Designation fees paid

Designated state(s): DE FR GB

17Q First examination report despatched

Effective date: 20090325

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602006010318

Country of ref document: DE

Date of ref document: 20091224

Kind code of ref document: P

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20100812

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20151224

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20151222

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20151217

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602006010318

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20170116

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20170929

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170801

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170116