EP0168748B1 - Suspension de développement pour l'électro-photographie et son procédé de fabrication - Google Patents

Suspension de développement pour l'électro-photographie et son procédé de fabrication Download PDF

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Publication number
EP0168748B1
EP0168748B1 EP85108465A EP85108465A EP0168748B1 EP 0168748 B1 EP0168748 B1 EP 0168748B1 EP 85108465 A EP85108465 A EP 85108465A EP 85108465 A EP85108465 A EP 85108465A EP 0168748 B1 EP0168748 B1 EP 0168748B1
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Prior art keywords
monomers
comonomers
copolymer
coor
hydrocarbon radical
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EP85108465A
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German (de)
English (en)
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EP0168748A3 (en
EP0168748A2 (fr
Inventor
Wolfgang Dr. Podszun
John Ir. Goossens
Carlhans Dr. Süling
Gunther Dr. Hoffarth
Wolfgang Dr. Richter
Herman Dr. Uytterhoeven
Walter Dr. De Winter
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/135—Developers with toner particles in liquid developer mixtures characterised by stabiliser or charge-controlling agents
    • G03G9/1355—Ionic, organic compounds
    • 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
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
    • G03G9/131—Developers with toner particles in liquid developer mixtures characterised by polymer components obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/001—Electric or magnetic imagery, e.g., xerography, electrography, magnetography, etc. Process, composition, or product
    • Y10S430/105—Polymer in developer

Definitions

  • the invention relates to an improved electrostatographic suspension developer which contains an ionic copolymer to produce a positive toner charge, and to a process for producing the developer.
  • Dry and wet development methods are known for developing electrostatic images on electrostatographic recording materials.
  • the wet development processes using suspension developers are superior to the dry development processes in terms of edge definition and resolving power.
  • Suspension developers generally consist of a highly insulating carrier liquid, a pigment, a charge-determining substance (also called a control agent) and a polymer.
  • the carrier liquid preferably has a volume resistance of at least 10 9 ohm.cm and a dielectric constant below 3.
  • common pigments are azo dyes, xanthene dyes, phthalocyanine dyes, as described, inter alia, in DE-A-29 4 4 ? 1, but also triphenylmethane dyes , Acridine dyes or quinoline dyes. 'e used.
  • Carbon black pigments are preferably used as black pigments.
  • the primary function of the polymer is to impart sufficient steric stabilization to the pigment dispersion and to ensure that the pigment particles adhere or are fixed to the image carrier.
  • Numerous differently structured polymers can be used as components of electrostatographic suspension developers.
  • the use of statistical copolymers which are composed of less polar monomers (for example C 6 -C 20 -alkyl (meth) acrylate) and more polar monomers (for example aminomethacrylates or vinylpyrrolidone) has been widely described (for example DE-A- 19 27 592, DE-A-19 38 001, BE-A-784 367, JP-A-49 129 539 or JP-A-73 431 54).
  • the use of styrene-butadiene copolymers is also possible, for example DE-A-23 37 419, DE-A-24 52 499 or JP-A-73 290 72).
  • graft copolymers have also been used to build up suspension developers (for example DE-A-20 42 804, DE-A-21 03 045, DE-A-24 21 037, DE-A-25 32 281, DE-A-24 32 288, DE-A-29 35 287, GB-A-2 157 2343, GB-A-2 029 049 or US-A-40 33 890).
  • the polymers contain ionic groups, these can play a role in the build-up of the toner charge.
  • the charge of the toner particles is prevented by oil-soluble ionogenic compounds, e.g. by metal salts of organic acids with long aliphatic residues.
  • oil-soluble ionogenic compounds e.g. by metal salts of organic acids with long aliphatic residues.
  • carbon black pigments in liquid isoparaffin can be positively charged by organic phosphorus compounds (GB-A-1 151 141).
  • a negative charge build-up is possible by adding basic metal alkyl sulfonates (GB-A-1 571 401).
  • a disadvantage of the use of the known charge-determining substances is that the electrical properties of the liquid developers, such as conductivity and particle charge, are not stable when the concentration changes and are influenced to a large extent by traces of water (e.g. atmospheric humidity). Furthermore, liquid developers of this type generally show a high electrical conductivity of the dispersion medium, as a result of which the electrophoretic deposition of the toner particles is impaired.
  • the invention has for its object to provide an electrostatographic suspension developer with positive toner charge, high charge stability and low conductivity of the dispersion medium.
  • a suspension developer which contains a dispersed pigment and at least one copolymer in an electrically insulating carrier liquid with a volume resistance of at least 10 9 Ohm.cm and a dielectric constant below 3, characterized in that the coolant contains
  • Hydrocarbons, fluorocarbons or silicone oils can be used as the carrier liquid with a volume resistance of at least 10 9 ohm.cm and a dielectric constant below 3; preference is given to hydrocarbon-based liquids, for example aromatic hydrocarbons such as benzene, toluene or xylenes or aliphatic C 6 ⁇ C 15 hydrocarbons such as n-hexane, cyclohexane, n-heptane, n-octane or decalin. Mixtures of different hydrocarbons can also be used. Branched aliphatic hydrocarbons such as isodecane and isododecane are particularly suitable.
  • Suitable pigments are the black and color pigments mentioned above, which are usually used for suspension developers. Spirit black (CI No. 50415), aniline black (CI No. 50440), cyanine blue (CI No. 74250), brilliant carmine 6 B (CI 15850), real red (CI No. 15865), benzidine orange (CI 21110) are particularly suitable. or permanent yellow GR 52 (CI 21100). Carbon black (especially basic carbon black types), helio real blue HG (C.I. No. 74160), fanal rose B (C.I. No. 45160) and helio real yellow GRN (C.I. No. 21100) are particularly preferred.
  • the copolymer contains 0.1 to 80, preferably 0.5 to 50 and particularly preferably 2 to 20% by weight of polymerized cationic monomers (A).
  • hydrocarbon radicals mentioned can be linear or branched alkyl, aryl, arylalkyl or alkylaryl radicals.
  • Suitable cations are: Particularly preferred cations are derivatives of acrylic acid and methacrylic acid according to formulas VII and VIII in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above.
  • the ionic monomers are prepared from known starting compounds.
  • the ionic compound can be synthesized by direct reaction in the sense of an acid-base reaction.
  • the ionic monomer can be obtained from this aqueous reaction mixture in a high purity by extraction, toluene, isobutanol and mixtures of both solvents being particularly suitable extraction agents.
  • Quaternized compounds are generally synthesized in a two-stage process. In the first stage, the N, P or S compound on which the cation is based is quaternized using known methods.
  • the quaternization reaction is preferably carried out at temperatures from 0 to 90 ° C. in the presence of organic solvents. It is advantageous to add known polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether or 2,6-di-tert-butyl-p-methylphenol at this stage.
  • the quaternized compound is reacted with an alkali salt of the desired anion in aqueous solution.
  • the isolation of the ionic monomers can in turn advantageously be carried out by extraction with the solvents mentioned above.
  • the preferred synthetic route for the copolymers is the radical polymerization of the ionic monomers.
  • the polymerization can be initiated using conventional radical formers such as peroxides and preferably azo compounds.
  • Redox polymerization for example using a peroxide / amine system, or photopolymerization is also possible.
  • Suitable comonomers (B) are in principle all free-radically polymerizable, olefinically unsaturated compounds, in particular the known vinyl and vinylidene compounds.
  • examples include: (meth) acrylic acid and its derivatives such as (meth) acrylic esters with C i to C 24 hydrocarbon radicals in the alcohol part, (meth) acrylic acid amide, (meth) acrylonitrile, vinyl esters such as vinyl acetate, vinyl propionate, vinyl aromatics such as Styrene or a-methylstyrene, also dienes such as butadiene and isoprene, and halogen-containing monomers such as vinyl chloride and vinylidene chloride.
  • Preferred comonomers are (meth) acrylic acid esters with at least one C i to C 24 hydrocarbon radical in the alcohol part and styrene. Mixtures of different monomers are also very suitable. Good installation rates are achieved above all if (meth) acrylic acid esters are used as comonomers, at least in part. Copolymers which are not crosslinked or crosslinked by using polyfunctional monomers such as, for example, ethylenedimethylacrylate or divinylbenzene can be built up.
  • the copolymer not only charges the dispersed pigment, but also increases the dispersion stability of the pigment dispersion by steric shielding.
  • Comonomers which improve the dispersant properties of the copolymer are, for example, vinyl or vinylidene monomers with a C e to C 24 hydrocarbon radical, in particular (meth) acrylic acid ester with C 6 to C 24 hydrocarbon radicals in the alcohol part ; eg stearyl methacrylate, lauryl methacrylate or 2-ethylhexyl methacrylate, these comonomers preferably being used in amounts of 10 to 70% by weight (based on the copolymer): in this case it is advantageous to combine the comonomers mentioned here with those with C i - bis Combine C s hydrocarbon residues.
  • the copolymer can be synthesized in the absence of the pigment by known processes, such as bulk, solution, precipitation, suspension or emulsion polymerization.
  • the copolymer is synthesized in the presence of the dispersed pigment, the copolymer formed at least partially forming a firm physical or chemical bond with the pigment.
  • the pigment is in shape a non-aqueous 0.5 ⁇ 40% by weight dispersion.
  • Aromatic and aliphatic hydrocarbons such as, for example, benzene, toluene, xylene, linear and branched Cg-C, 5- alkanes and cyclohexane or decalin, are primarily suitable as the dispersing medium.
  • a polymerization process is preferred in which the pigment dispersion, which may optionally contain a stabilizing agent, is mixed with the ionic monomers and comonomers and the polymerization is initiated as a starting component by means of a radical generator.
  • Soluble, high molecular weight compounds such as homopolymers or copolymers of (meth) acrylic acid esters, for example a 1: 1 copolymer of isobutyl methacrylate and lauryl methacrylate, can be used as stabilizers.
  • Copolymers with a proportion of 0.1-10% by weight of copolymerized monomers with -OH, -COOH, -NH 2 , -NHR, -NR 2 groups, such as 2-hydroxyethyl methacrylate, (meth) are also very suitable.
  • Particularly suitable stabilizers are block copolymers, for example styrene-stearyl methacrylate block copolymers or mercaptan-modified styrene-butadiene block copolymers (DE-A 34 12 085).
  • the polymerization reaction can be carried out according to a "batch process".
  • the monomers and the starting component are added to the pigment dispersion all at once and the reaction is initiated by increasing the temperature. In this way, a largely uniform polymer shell is produced.
  • the monomers and the starting components are metered in during the polymerization (feed process).
  • This embodiment opens up a number of technically very interesting possibilities. You can e.g. change the monomer composition over the dosing period to achieve special effects. It has proven to be advantageous to add the above-mentioned suitable comonomers without the addition of ionic monomers at the beginning of the metering period and to add the ionic monomers in a mixture with further comonomers only after a polymerization conversion of 10 to 50%.
  • the starting component is also advantageously metered in over the reaction period.
  • Solid starting components are expediently dissolved in solvents or monomers.
  • the copolymer is used in amounts of 10 to 300, preferably 10 to 100% by weight, based on pigment.
  • polymeric additives can be used to prepare the suspension developer according to the invention, for example to increase the dispersion stability or to improve the adhesive and fixing properties of the dispersed pigment.
  • the above-mentioned stabilizers based on soluble high-molecular compounds are primarily suitable for increasing the dispersion stability.
  • Suitable fixing substances are resins which are compatible with the binder of the photoconductive recording material, e.g. with the binder of a photoconductive zinc oxide layer, so that good adhesion of the generated image to the substrate is obtained after development.
  • suitable resins are esters of hydrogenated rosin and long-oil oil, "rosin-modified phenol-formaldehyde resin, pentaerythritol esters of rosin, glycerol esters of hydrogenated rosin, ethyl cellulose, various alkyd resins, polyacrylic and polymethacrylic resin, polystyrene, poly (vinyl acetate). Specific examples of such resins can be found in the literature on electrostatographic suspension developers, e.g. in BE-PS 699 157 and in GB-A-1 151 141.
  • the suspension developers according to the invention can be prepared using conventional dispersion methods. Good results are achieved using ball mills, bead mills, colloid mills and high-speed stirrers. It may be advantageous to first produce a mixture of the pigment, the polymer and the other polymeric additives, for example by melting in a kneader, and to disperse this mixture in the carrier liquid in a second process step.
  • a stable dispersion is generally obtained directly, so that an additional dispersion step can be dispensed with. It is expedient first of all to prepare a toner concentrate from carrier liquid, pigment and polymer with a content of 5 to 50% by weight, preferably 10 to 25% by weight, of solid, which is adjusted to the use concentrations of 0.05 to by adding further carrier liquid 2%, preferably 0.1 to 1%, is diluted.
  • N, N-diethylaminoethyl acrylate are dissolved in 100 ml of deionized water and mixed with 100 ml of 1N HCl and 50 mg of hydroquinone. 59.2 g of diisooctyl sulfate succinate are then added with stirring at room temperature.
  • the ionic monomer formed is 100 ml a mixture of equal parts of isobutanol and toluene extracted and isolated by evaporation of the solvent.
  • 2-methacryloxyethyl-dimethylammonium-1,2,3,4,5-pentaisotridecyloxycarbonylcyclopentadienid is formed as a green oil; 5.45 g (quantitative).
  • a copolymer is prepared from 2 g of ionic monomer from Example 3, 9 g of styrene and 9 g of lauryl methacrylate.
  • the suspension developer is filled into an electrophoresis cell with 2 planar electrodes, each with a surface area of 20 cm 2 and an electrode spacing of 0.15 cm.
  • the electrical current that occurs when a voltage of 500 V is applied for 0.5 s is measured.
  • the integral of the current over the period of 0.5 s is the Q, value.
  • O T is a measure of the charge on the toner particles.
  • the deposition of the toner particles (blackening) on the negative electrode (cathode) shows that they are positively charged.
  • the charge stability of the toner particles was checked by measuring O T1 immediately after the liquid developer was prepared and Q T2 after 7 days of storage:
  • Example 6 was repeated using 5 g of the copolymer from Example 5 and 5 g of carbon black pigment with a BET surface area of 90 m 2 / g:
  • 80 g of carbon black pigment with a BET surface area of 30 m 2 fg are mixed with 20 g of a copolymer of equal parts of lauryl methacrylate and isobutyl methacrylate with a molecular weight of 120,000 and dispersed in 100 isododecane using a ball mill.
  • 250 g of the dispersion obtained are transferred to a stirred reactor and heated to 80 ° C.
  • 250 mg of azoisobutyronitrile are first added with stirring, and immediately after that a solution of 75 g of toluene, 7.5 g of lauryl methacrylate, 7.5 g of isobutyl methacrylate, 5 g of divinylbenzene and 5 g of the ionic monomer from Examples 1 and 100 is added over a period of 60 minutes mg of azoisobutyronitrile evenly metered in.
  • the dispersion is kept under stirring for 1 hour at 80 ° C. and 3 hours at 90 ° C.
  • the dispersion is centrifuged for cleaning using a cup centrifuge; the solid formed is isolated and redispersed in 250 g of pure isododecane using a shaker. This process is repeated once. The dispersion is then adjusted to 0.4% by weight solids with the addition of further isododecane and tested: Average particle size: 314 nm
  • 100 g of the dispersion obtained are diluted with 150 g of isododecane, transferred to a stirred reactor and heated to 80.degree. 250 mg of azoisobutyronitrile and then the solution are metered in uniformly over a period of 30 minutes with stirring.
  • solution II is metered in.
  • the dispersion is kept at 80 ° C. for 1 hour and at 90 ° C. for 3 hours with further stirring.
  • the dispersion is centrifuged for cleaning using a cup centrifuge, the solid formed is isolated and redispersed in 250 g of pure isododecane using a shaker. This process is repeated once. The dispersion is then adjusted to 0.4% by weight of solid by adding further isododecane and tested. average particle size: 780 nm
  • Example 9 is repeated using the ionic monomer from Example 2.
  • Example 5 is repeated using the ionic monomer from Example 1.
  • solution II is metered in.
  • the dispersion is kept at 80 ° C. for 1 hour and at 90 ° C. for 3 hours with further stirring.
  • the dispersion is centrifuged using a cup centrifuge, the solid formed is isolated and redispersed in 300 g of pure isododecane. This process is repeated one time. The dispersion is then adjusted to a solids content of 0.4% and added by adding further isododecane. average particle size: 825 nm
  • a dispersion is prepared in a ball mill from 4 g of carbon black pigment with a BET surface area of 30 m 2 / g, 1 g of a copolymer made from 85% isobutyl methacrylate and 15% stearyl methacrylite with a molecular weight Mw of 170,000 and in 45 g of isododecane.
  • the dispersion is diluted to 0.4% solids, mixed with 80 mg of zinc (2-butyl) octyl phosphate (preparation according to GB-PS 1 151 141) and tested.
  • the table shows that the suspension developers according to the invention have no conductivity of the carrier liquid.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Liquid Developers In Electrophotography (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (8)

1. Révélateur électrostatographique en suspension contenant un pigment dispersé dans un liquide de support isolant électriquement possédant une résistivité d'au moins 109 Ohm.cm et une constante diélectrique inférieure à 3 et au moins un copolymère, caractérisé en ce que le copolymère se compose de
A. des monomères cationiques contenant des groupes ammonium, phosphonium ou sulfonium et dont les anions répondent aux formules générales
Figure imgb0053
Figure imgb0054
dans lesquelles
Z représente ―SO3 ⊖ ou
Figure imgb0055
R2 et R3 représentent un reste hydrocarboné avec 1 à 18 atomes de carbone et
R6 un reste hydrocarboné avec 6 à 24 atomes de carbone,
R7 un des groupes ―COOR6 ou ―SO2R6,
R8 et R9 sont identiques ou différents et représentent -CN, -N02, un halogène, -COOR ou -S02R,
R10 représente R6 ou ―COOR6,
R11 -CN ou -COOR,
R11, R13, R14 sont identiques ou différents et représentent un atome d'hydrogène, les groupes-CN,-R ou -COOR, et
R représente un reste hydrocarboné avec 1 à 24 atomes de carbone, et
B. des composés à insaturation oléfinique susceptibles de polymérisation radicalaire, comme comonomères.
2. Révélateur en suspension selon la revendication 1, caractérisé en ce que les cations des monomères (A) répondent aux formules générales
Figure imgb0056
Figure imgb0057
Figure imgb0058
Figure imgb0059
Figure imgb0060
Figure imgb0061
dans lesquelles
R, représente un atome d'hydrogène ou un groupe CH3,
R2 un reste hydrocarboné avec 1 à 18 atomes de carbone,
R3 et R4 sont identiques ou différents et représentent un reste hydrocarboné avec 1 à 18 atomes de carbone, ou représentent ensemble un cycle à 5 ou 6 chaînons,
R5 représente un atome d'hydrogène ou un reste hydrocarboné avec 1 à 18 atomes de carbone,
Figure imgb0062
ou
Figure imgb0063
et
Y représente l'atome nécessaire pour compléter un cycle hétérocyclique à 5 ou 6 chaînons.
3. Révélateur en suspension selon la revendication 1, caractérisé en ce que les comonomères (B) sont des composés de vinyle ou de vinylidène du groupe comportant les esters d'acide (méth)acrylique avec des restes hydrocarbonés en Ci à C24 dans la partie alcool, l'amide d'acide(méth)acrylique, le nitrile d'acide(meth)acrylique, l'acétate de vinyle, le propionate de vinyle, le styrène, l'a-méthylstyrène, le butadiène, l'isoprène, le chlorure de vinyle, le chlorure de vinylidène, le diméthacrylate d'éthylène, le divinylbenzène, le méthacrylate de stéaryle, le méthacrylate de lauryle et le méthacrylate de 2-éthylhexyle.
4. Révélateur en suspension selon la revendication 3, caractérisé en ce qu'une partie des comonomères (B) est un ester d'acide (méth)acrylique avec 6 à 24 atomes de carbone dans la partie alcool.
5. Révélateur en suspension selon la revendication 1, caractérisé en ce que la parte de monomères (A) dans le copolymère est de 0,1 à 80% en poids, de préférence 0,5 à 50% en poids.
6. Procédé pour la fabrication d'un révélateur électrostatographique en suspension selon la revendication 1, caractérisé en ce que l'on polymérise les monomères (A) avec les comonomères (B) en présence du pigment dans un hydrocarbure aliphatique ou aromatique avec les propriétés du liquide de support comme milieu de dispersion, et qu'on obtient ainsi une dispersion appropriée comme révélateur en suspension contenant le copolymère pigmenté.
7. Procédé selon la revendication 6, caractérisé en ce que les monomères (A) et (B) de la dispersion du pigment dans le milieu de dispersion sont ajoutés dans un procédé avec afflux, dans lequel on ajoute, dans une première phase de polymérisation, uniquement les comonomères (B) et dans une seconde phase de polymérisation, les monomères (A) dans le mélange avec une quantité supplémentaire des comonomères (B).
8. Procédé selon les revendications 6 et 7, caractérisé en ce que l'hydrocarbure utilisé comme milieu de dispersion contient un copolymère séquencé de styrène-méthacrylate de stéaryle ou un copolymère séquencé de styrène-butadiène modifié au mercaptan, comme agent de stabilisation.
EP85108465A 1984-07-17 1985-07-09 Suspension de développement pour l'électro-photographie et son procédé de fabrication Expired - Lifetime EP0168748B1 (fr)

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DE3426256 1984-07-17
DE19843426256 DE3426256A1 (de) 1984-07-17 1984-07-17 Elektrostatographischer suspensionsentwickler und verfahren zu seiner herstellung

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EP0168748A2 EP0168748A2 (fr) 1986-01-22
EP0168748A3 EP0168748A3 (en) 1988-03-09
EP0168748B1 true EP0168748B1 (fr) 1990-12-05

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Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2590895B2 (ja) * 1987-07-16 1997-03-12 富士ゼロックス株式会社 現像剤用キャリア
US4855396A (en) * 1988-08-05 1989-08-08 Eastman Kodak Company Polyesters containing covalently bound quaternary phosphonium salts
US4837392A (en) * 1988-08-05 1989-06-06 Eastman Kodak Company Dry electrostatographic developer containing toner particles comprising a vinyl addition polymer containing a covalently bound quaternary phosphonium salt
US4837394A (en) * 1988-08-05 1989-06-06 Eastman Kodak Company electrostatographic toner particle comprising a polyester containing a covalently bound quaternary phosphonium salt
US4837391A (en) * 1988-08-05 1989-06-06 Eastman Kodak Company Dry electrostatographic developer containing toner particles comprising a vinyl addition polymer containing a covalently bound quaternary phosphonium salt
US4837393A (en) * 1988-08-05 1989-06-06 Eastman Kodak Company Electrostatographic toner particle comprising a polyester containing a covalently bound quaternary phosphonium salt
JP2587277B2 (ja) * 1988-09-12 1997-03-05 富士写真フイルム株式会社 印刷版用液体現像剤
US5035972A (en) * 1989-10-31 1991-07-30 E. I. Du Pont De Nemours And Company AB diblock copolymers as charge directors for negative electrostatic liquid developer
US5130221A (en) * 1990-03-07 1992-07-14 Dximaging Salts of acid-containing ab diblock copolymers as charge directors for positive-working electrostatic liquid developers
US5457002A (en) * 1994-08-23 1995-10-10 Lexmark International, Inc. Carrier fluid for liquid electrophotographic toner
US5876887A (en) * 1997-02-26 1999-03-02 Xerox Corporation Charge generation layers comprising pigment mixtures
US7247379B2 (en) * 1997-08-28 2007-07-24 E Ink Corporation Electrophoretic particles, and processes for the production thereof
US7002728B2 (en) * 1997-08-28 2006-02-21 E Ink Corporation Electrophoretic particles, and processes for the production thereof
US6771183B2 (en) * 2000-07-03 2004-08-03 Kodiak Technologies, Inc. Advanced thermal container
US7230750B2 (en) 2001-05-15 2007-06-12 E Ink Corporation Electrophoretic media and processes for the production thereof
US20100148385A1 (en) * 2001-05-15 2010-06-17 E Ink Corporation Electrophoretic media and processes for the production thereof
JP4188091B2 (ja) * 2001-05-15 2008-11-26 イー インク コーポレイション 電気泳動粒子
US20090009852A1 (en) * 2001-05-15 2009-01-08 E Ink Corporation Electrophoretic particles and processes for the production thereof
DE102009048542A1 (de) * 2009-10-07 2011-04-21 Clariant International Ltd. Leicht dispergierbare Pigmentzubereitung auf Basis von C.I. Pigment Yellow 155
WO2018092902A1 (fr) * 2016-11-21 2018-05-24 キヤノン株式会社 Révélateur liquide pouvant durcir

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50147722A (fr) * 1974-05-17 1975-11-27
US4229513A (en) * 1979-05-29 1980-10-21 Eastman Kodak Company Liquid electrographic developers containing polymeric quaternary salts
DE3371423D1 (en) * 1983-01-20 1987-06-11 Agfa Gevaert Nv Liquid developer for development of electrostatic images

Also Published As

Publication number Publication date
DE3426256A1 (de) 1986-01-23
JPS6139058A (ja) 1986-02-25
EP0168748A3 (en) 1988-03-09
DE3580798D1 (de) 1991-01-17
US4639403A (en) 1987-01-27
EP0168748A2 (fr) 1986-01-22

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