US3850676A - Coated carrier particles for electrostatographic development - Google Patents

Coated carrier particles for electrostatographic development Download PDF

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US3850676A
US3850676A US00027114A US2711470A US3850676A US 3850676 A US3850676 A US 3850676A US 00027114 A US00027114 A US 00027114A US 2711470 A US2711470 A US 2711470A US 3850676 A US3850676 A US 3850676A
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percent
weight
carrier
polyphenylene oxide
resin
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R Hagenbach
R Madrid
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Priority to GB45221/67A priority Critical patent/GB1211863A/en
Priority to BE704917D priority patent/BE704917A/xx
Priority to FR124100A priority patent/FR1540694A/fr
Priority to DE19671597886 priority patent/DE1597886A1/de
Priority to NL6713821A priority patent/NL6713821A/xx
Application filed by Individual filed Critical Individual
Priority to US00027114A priority patent/US3850676A/en
Priority to US00242780A priority patent/US3857792A/en
Priority to US00244254A priority patent/US3849127A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
    • G03G9/1132—Macromolecular components of coatings
    • G03G9/1133—Macromolecular components of coatings obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
    • G03G9/1132—Macromolecular components of coatings
    • G03G9/1135—Macromolecular components of coatings obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
    • G03G9/1132—Macromolecular components of coatings
    • G03G9/1135—Macromolecular components of coatings obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/1136—Macromolecular components of coatings obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon atoms
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Definitions

  • This invention relates in general to imaging systems and, more particularly to improved developing materials, their manufacture and use.
  • latent image formation by uniformly charging the photoconductive layer and then exposing the layer to a light and shadow image, one may form the latent image by directly charging the layer in image configuration.
  • the powder image may be fixed to the photoconductive layer if elimination of the powder image transfer step is desired.
  • Other suitable means such as solvent or overcoating treatment may be substituted for the foregoing heat fixing step.
  • the toner particles are electrostatically deposited and secured to the charged portion of a latent image and are not deposited on the uncharged or background portion of the image.
  • Most of the tonerparticles accidentally deposited in the background areas are removed by the rolling carrier, due apparently, to thegreater electrostatic attraction between the toner and carrier than between the toner and the discharge background. The carrier and excess toner are then recycled. This technique is extremely good forthe development of line copy images.
  • the cascade technique is carried out in automatic machines.
  • small buckets on an endless belt conveyor scoop the developer material from a sump and convey it to a point above an electrostatic image-bearing surface where the developer mixture is allowed to fall and cascade or roll by gravity across the image-bearing surface.
  • the carrier beads along with any unused toner particles are then returned to the sump for recycling through the developing system.
  • Small quantities of toner are periodically added to the developer mixture to compensate for the toner depleted during the development process. This process is repeated for each copy produced in the machine and is ordinarily repeated many thousands of times during the usable life of the developer.
  • Carriers having coatings which tend to chip and otherwise separate from the carrier core must be frequently replaced thereby increasing expense and consuming time. Print deletion and poor print qualityoccur when carrier particles having damaged coatings are undeplaced. Fines and grit formed from carrier coating disintegration tend to drift and form unwanted deposits on critical machine parts. Many materials having high compressive and tensile strength either do not adhere well to the carrier core or do not possess the desired triboelectric characteristics. The triboelectric and flow characteristics of many carriers are adversely effected when relative humidity is high. For example, the triboelectric values of some carrier coatings fluctuate with changes in relative humidity and are not desirable for employment in xerographic systems, particularly in automatic machines which require carriers having stable predictable triboelectric values.
  • carrier triboelectric properties Another factor affecting the stability of carrier triboelectric properties is the susceptibility of carrier coatings to toner impaction.
  • the carrier particles When the carrier particles are employed in automatic machines and recycled through many cycles, the many collisions which occur between the carrier particles and other surfaces in the machine cause the toner particles carried on the surface of the carrier particles to be welded or otherwise forced into carrier coatings.
  • the gradual'accumulation of permanently attached toner material to the surface of the carrier particles causes a change in the triboelec tric value of the carrier particles and directly contributes to the degradation of copy quality by eventual destruction of the toner carrying capacity of the carrier.
  • many carrier coating materials are difficult to apply to carrier cores because they tend to form thin filaments rather than smooth continuous coatings.
  • novel electrostatographic developer materials including carrier cores coated with a composition comprising a polyphenylene oxide resin.
  • the resin component employed in the carrier coatings of this invention may comprise a polyphenylene oxide resin per se, or a polyphenylene oxide resin blended with one or more other resins.
  • the polyphenylene oxide resin coating may be employed in any suitable thickness.
  • the coating on the free flowing carrier particles is at leastabout 1 micron in thickness.
  • a coating having a thickness of at least about 2.5 microns is preferred because the carrier coating will then possess sufficient thickness to resist abrasion and prevent any pinholes which would adversely affect the triboelectric properties of the coated carrier particles.
  • the maximum coating thickness is generally determined by the amount of coating material capable of being coated on the core by any given coating technique which produces free flowing coated particles and which does not result in agglomeration.
  • a practical maximum coating thickness for large size cores is therefore about 20 microns.
  • a coating thickness of from about 3 to about 5 microns provides superior abrasion resistance and stable triboelectric properties. While not absolutely necessary, excellent abrasion resistance and stable triboelectric properties are generally achieved with a substantially smooth, continuous uniform coating of a polyphenylene oxide resin. However, superior abrasion resistance has been achieved with coatings which are neither uniform or continuous.
  • Any suitable linear polyphenylene oxide resin may be employed. These polyphenylene oxide resins have the general formula:
  • R and R" are each selected from the group consisting of H and alkyl radicals having a total of up to 12 carbon atoms in R and R and n is a positive integer of at least about 25.
  • the high molecular weight film-forming polyphenylene oxide resins employed in the carrier coatings of this invention are obtained by well known polymerization techniques such as the oxidative coupling of phenols. Oxidative coupling involves the reaction of oxygen with active hydrogens from different molecules to produce water and a dimer linked by an oxygen. In order to form polymers by the oxidative coupling technique, a polyphenylene oxide monomer must have at least two active hydrogens.
  • Optimum impaction resistance is obtained with a polyphenylene oxide resin formed by the copper catalyzed oxidation of 2,6dimethylphenol.
  • the resulting polymer has methyl groups at R and R" in the general formula set forth above.
  • any other suitable phenol may be used to produce useful resin carrier coatings.
  • Typical phenols include: phenol; Z-methylphenol; 2-propyl phenol; 2- isobutyl phenol; 2,6-diethyl phenol; 2,6-diisopropyl phenol; 2-ethyl- 6-methyl phenol; 2,5-dimethyl phenol; 3,5-dimethyl phenol; and the like.
  • Any suitable resin may be blended with a polyphenylene oxide resin to form the carrier coating materials of this invention.
  • These resins may include natural resins, modified natural resins or synthetic resins prepared by addition, condensation or any other technique proving suitable.
  • the polyphenylene oxide resin may be blended with other resins in any suitable amount. Generally to maintain the properties of the polyphenylene oxide resin as a coating it is present in the blend in at least the major proportion.
  • Typical natural and modified natural resins include: gum copal, gum sandarac, rosin, fossil resins, zein, ethyl cellulose, cellulose acetate, cellulose nitrate, gum nitrate, oxidized rosin, pentaerythritol esters of rosin and the like.
  • Typical synthetic resins include polymers, copolymers, terpolymers and other polymeric structures and modified polymeric structures including, for example, polyolefins such as polyethylene, polypropylene, chlorinated polyethylene, and chlorosulfonated polyethylene; polyvinyl and polyvinylidine compounds such as polystyrene, polymethylstyrene, polymethyl methacrylate, polyacrylic acid, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ethers and polyvinyl ketones; fluorocarbons such as polytetrafluoroethylene,
  • polyvinylfluoride polyvinylidenefluoride and polychlorotrifluoroethylene
  • polyamides such as polycaproloctamo and polyhexamethylene adipamide
  • polyesters such as polyethylene terephthalate
  • polyurethanes polysulfides
  • polycarbonates epoxies such as the condensation reaction product of epichlorohydrin with any one of a bisphenol A, resorcinol, hydroquinone and ethylene glycol
  • phenolic resins such as phenol formaldehyde, phenol furfural and resorcinol formaldehyde;
  • amino aldehydes such as urea formaldehyde and mela-- mine formaldehyde; and mixtures thereof.
  • These addition reaction products have a weight average molecular weight of at least about 5,000.
  • organosilicon terpolymers are preferred additives because the resulting blend possesses especially good triboelectric stability and synergistic resistance to toner impaction.
  • a solid copolymer addition reaction product may be obtained from about 99.5 to about 50 percent, by weight, of an unsaturated silicon free organic compound and from about 0.5 to about 50 percent, by weight, of the above described polymerizable organomore than one organic group is attached to the silicon atom, only one of the organic groups need be unsaturated to enter into a polymerization reaction with other unsaturated monomers.
  • compounds such as dimethyl vinyl chloro silanes are suitable.
  • these unsaturated groups need not be identical.
  • vinyl allyl silicon chlorides and bromides may be employed.
  • Partially condensed siloxanes in the liquid state having reactive unsaturated organic groups attached to a silicon atom may be employed as a terpolymer reactant.
  • Suitable silicon free monomers or prepolymers with which the above organosilicon compounds are particularly adapted to react to form the polymeric organosilicon resin additives of this invention include the unsaturated compounds which normally form resinous polymers by addition type polymerization. Monomers or prepolymers containing the unsaturation in a nonbenzoid group may be employed, such unsaturated monomers or prepolymers include those having ethylenic or acetylenic linkage.
  • olefins diolefins, acetylenes and their derivatives, particularly derivatives having substituents such as halogen, alkyl, aryl, unsaturated alicyclic and other types of substitu ent groups including, for example, nitrile or nitro groups.
  • the unsaturated organic monomers containing the unsaturation in a non-benzoid group also include unsaturated hydrocarbons, aliphatic carbocyclic, and heterocyclic compounds including unsaturated alcohols, aldehydes, ketones, quinones, acids, acid anhydrides, esters, nitriles or nitro compounds.
  • Typical unsilicon composition are included.
  • the solid terpolymer comprises from about 5 to about 94.5 percent, by weight, of an unsaturated silicon free organic compound, from about 94.5 to about 5 percent, byweight, of an unsaturated silicon free organic compound-different from the first mentioned silicon free compound and from about 0.5 to about percent, by weight, of one of the above described polymerizable organosilicon compounds.
  • Theunsaturated organic group attached to the silicon atom contains the unsaturation in a non-benzoid group and is preferably anunsaturated hydrocarbon group.
  • Typical unsaturated organic groups include: vinyl, chlorvinyl, divinyl, distyryl, allyl, diallyl, triallyl, allyl phenyl, dimethyl allyl and methacryloxypropyl groups.
  • Typical hydrolyzable groups include: ethoxy, methoxy, chloro, bromo, propoxy, acetoxy and amino groups.
  • Examples of typical unsaturated organo silanes having hydrolyzable groups attached to a silicon atom include: vinyl triethosy silane, vinyl trimethoxy silane, vinyl-tris, (beta-methoxyethoxy), silane, gammamethacryloxypropyltrimethoxy silane, vinyl trichlorosilane, vinyl triacetoxy silane, divinyl dichloro silane, and dimethyl vinyl chloro silane.
  • Suitable corresponding polymerizable hydrolysis products and the corresponding siloxanes may be substituted for the foregoing saturated monomers include: ethylene, propylene, butenes, isobutylene, pentenes, hexenes, methyl .methacrylate, methyl acrylate, vinylchloride, vinylidene chloride, acrylonitrile, chlorovinyl acetate, styrene, butadene, chloroprene, cyclopentadene, divinyl, benzene, cyclohexadiene, ethyl methacrylate, vinyl acetate, vinyl toluene, acetylene, phenylacetylene, ethylvinyl benzene, allyl chloride, allyl benzene, maleic anhydride, ethyl acrylate, diethylmaleate, butyl acrylate, butyl methacrylate, isobutyl meth
  • polymerization of the unsaturated organosilicon and unsaturated silicon free unsaturated compounds are effected with any suitable free-radical initiator or catalyst capable of polymerizing the monomers or prepolymers.
  • radical initiators or catalysts include: alkyl peroxides, such as tert-butyl hydroperoxide, and di-tert-butyl peroxide; acyl and aroyl peroxides, such as dibenzoyl peroxide, perbenzoic acid, dilauroy peroxide, perlauric 0 polyphenylene oxide resin is therefore generally at least present in the major amount in resin blends.
  • alkyl peroxides such as tert-butyl hydroperoxide, and di-tert-butyl peroxide
  • acyl and aroyl peroxides such as dibenzoyl peroxide, perbenzoic acid, dilauroy peroxide, perlauric 0
  • polyphenylene oxide resin is therefore generally at least present in the major amount in resin blends.
  • an exception to this general rule has been found with combinations of polyphenylene oxide resins with the organosilicon terpolymers described above. As illustrated in the Examples below
  • the carrier coatings of this invention contain thermosetting resins blended with a polyphenylene oxide resin
  • the blending should be effected while the thermosetting resin is in a monomeric or partially polymerized stage.
  • Polymerization of the thermosetting monomer or partially polymerized prepolymer may be completed in situ after the blend is applied to a carrier core. In situ polymerization may be effectuated by any well known technique as by application of heat. If a thermosetting resin prepolymer is employed, the prepolymer should be in a liquid or thermoplastic stage so that uniform blending of the prepolymer as a melt or in a solvent solution will be facilitated.
  • additives such as plasticizers, reactive resins, dyes, pigments, wetting agents, and mixtures thereof may be mixed with the resin coating of this invention.
  • hydrolysis of the hydrolyzable groups attached to the silicon atoms may be promoted by pre-treating the carrier core with any suitable hydrolyzing medium such as .a dilute solution of acetic acid or by mixing the hydrolyzing material with the organosilicon polymer prior to the coating operation.
  • any suitable well known coated or uncoated carrier material may be employed as the core of the carriers of this invention.
  • Typical carrier materials include sodium chloride, ammonium chloride, aluminum potassium chloride, Rochelle salt, sodium nitrate, potassium chlorate, granular zircon, granular silicon, methyl methacrylate, glass, silicon dioxide, flintshot, iron, steel, ferrite, nickel, carborundum and mixtures thereof.
  • Many of the foregoing and other typical carriers are described by L. E. Walkup in U.S. Pat. No. 2,618,551; L. E. Walkup et al. in U.S. Pat. No. 2,638,416 and E. N. Wise in U.S. Pat. No. 2,618,552.
  • An ultimate coated carrier particle diameter between about 40 microns to about 600 microns is preferred because the carrier particles then possess sufficient density and inertia to avoid adherence to the electrostatic latent images during the cascade development process. Adherence of the carrier beads to an electrostatographic drum is undesirable because of the fonnation of deep scratches on the drum surface during the image transfer and drum cleaning steps, particularly when cleaning is accomplished by a web cleaner such as the web disclosed by W. P. Graff, Jr., et al. in U.S. Pat. No. 3,186,838.
  • polymeric carrier coating materials containing polyphenylene oxide resins and blends thereof may be due to many factors.
  • the unusually low water absorption properties of the polyphenylene oxide resins contribute to the stable triboel'ectric properties thereof.
  • the high resistance of the carrier coatings to toner impaction may be at least partly due to the high tensile strength and heat resistance exhibited by polyphenylene oxide resins, particularly blends of polyphenylene oxide resins with organosilicon terpolymers.
  • the polyphenylene oxide coatings of this invention adhere well to the carrier cores tested and are also highly resistant to chipping, and flaking.
  • the polyphenylene oxide resin coating compositions may be applied to a carrier core by any conventional method such as spraying, dipping, fluidized bed coating, brushing, and the like.
  • the polyphenylene oxide resins or blends thereof may be applied as a powder, dispersion, solution, emulsion, or hot melt.
  • any suitable solvent may be employed. Solvents having relatively low boiling points are preferred because less energy and time is required to remove the solvent subsequent to application of the coating to the carrier core.
  • Typical solvents include the halogenated aliphatics such as chloroform and 1,2- dichloro ethane; aromatic hydrocarbons such as toluene and o-chlorobenzene; and the like. Any suitable coating thickness may be employed.
  • the carrier coating should be sufficiently thick to resist flaking and chipping.
  • the quantity of resin to be applied to the carrier cores depends upon the density and the surface area presented by the carrier cores. Typical coating weights include from about 20 to about 1,000 grams of coating material per pounds of flintshot carrier cores haivng an average diameter of about 600 microns.
  • Typical toner materials include: cumaroneindene resin, asphaltum, phenolformaldehyde resins, rosin-modified phenolformaldehyde resins, methacrylic resins, polystyrene resins, polypropylene resins, epoxy resins, polyethylene resins and the like.
  • Typical toner materials are disclosed by H. E. Copley in U.S. Pat. No. 2,659,670; R. B. Landrigan in U.S. Pat. No. 2,753,308; M. A. Insalaco in U.S. Pat. No. 3,079,342 and C. F. Carlson in U.S. Pat. Reissue No. 25,136.
  • EXAMPLE I A control sample containing 1 part colored toner particles having an average particle size of about 10 to about 12 microns and about 99 parts coated carn'er particles available in the Xerox 813 Developer sold by the Xerox Corporation, Rochester, New York is cascaded across an electrostatic image-bearing surface. The resulting developed image is transferred by electrostatic means to a sheet of paper whereon it is fused by heat. The residual powder is removed from the electrostatic imaging surface by a cleaning web of the type disclosed by W. P. Graff, Jr., et al. in U.S. Pat. No. 3,186,838. After the copying process is repeated 8,000 times, the developer mix is examined for the presence of carrier coating chips and flakes. Numerous carrier chips and flakes are found in the developer mix.
  • EXAMPLE II A coating solution containing about 20 grams, by weight, of polyphenylene oxide resin, PPO Grade C- 1001 resin sold by the General Electric Company, Pittsfield, Massachusetts, dissolved in about 100 parts chloroform and 175 parts dichloro benzene is sprayed onto glass beads having an average diameter of about 600 microns. About 20 grams of polyphenylene oxide resin is applied to about pounds of glass carrier cores. After drying, the developing procedure of Example I is repeated with the foregoing coated carriers substituted for the Xerox 813 carrier particles'An examination of the developer mix after test termination reveals substantially no carrier coating chips or flakes.
  • EXAMPLE III A coating solution about grams, by weight, of a v resin blend comprising about 85 percent polyphenylene oxide resin and about 15 percent of an organosilicon terpolymer resin consisting essentially of the addition polymerization reaction product between about 15 parts sytrene, about 85 parts methyl methacrylate and about 5 parts of vinyl triethoxy silane dissolved in toluene is sprayed onto glass beads having an average diameter of about 600 microns. About 10 grams .of resin blend is applied to about 5 pounds of glass carrier cores. After drying, the developing procedure of Example I is repeated with the foregoing coated carrier substituted for the Xerox 813 carrier particles, an examination of the developer mix after test termination reveals substantially no carrier coating chips or flakes.
  • EXAMPLE IV A control sample containing one part pigmented resin toner particles having an average particle size of about 10 to about 12 microns and about 99 parts coated carrier particles available in the Xerox 813 Developer sold by the Xerox Corporation, Rochester,
  • Example VI The milling procedure described in Example V is continued until the cumulative milling time is about 240 hours. Upon termination of the milling, no chips or flakes are found. Examination of the carrier surfaces reveals complete impaction.
  • EXAMPLE Vll Glass carrier cores having an average diameter of about 600 microns are spray coated with a coating solution comprising about 10 percent, by weight, of a resin blend comprising about 85 percent polyphenylene oxide resin, PPO PR5311 resin sold by the General Electric Co., and about 15 percent of an organosilicon terpolymer resin consisting essentially of the addition polymerization reaction product between about 15 parts styrene, about 85 parts methyl methacrylate and about 5 parts vinyl triethoxy silane. About 20 grams of the resin blend is applied to about 5 pounds of glass cores. After drying, the milling procedure of Example IV is repeated with the foregoing coated carrier particles substituted for the Xerox 813 carrier particles. A slight amount of toner impaction is first observed after a milling time of about 144 hours. No chips or flakes are found.
  • Example VIII The milling procedure described in Example VII is continued until the cumulative milling time is about 240 hours. Upon termination of the milling, no chips or flakes are found. Examination of the carrier surfaces reveals almost complete toner impaction.
  • EXAMPLE IX Glass carrier cores having an average diameter of about 600 microns are spray coated with a coating solution comprising about 10 percent, by weight, of a resin blend comprising about percent polyphenylene oxide resin and about 25 percent of an organosilicon terpolymer resin consisting essentially of the addition polymerization reaction product between about 50 parts styrene, about parts methyl methacrylate and about 5 parts vinyl triethoxy silane. About 20 grams of the resin blend is applied to about 5 pounds of glass cores. After drying, the milling procedure of Example IV is repeated with the foregoing coated carrier particles substituted for the Xerox 813 carrier particles. A slight amount of toner impaction is first observed after a milling time of about 192 hours. No chips or flakes are found.
  • Example x- The milling procedure described in Example IX is continued until the cumulative milling time is about 240 hours. Upon termination of the milling, no chips or flakes are found. Examination of the carrier surfaces reveals only slight toner impaction.
  • EXAMPLE x1- Glass carrier cores having an average diameter of about 600 microns are spray coated with a coating solution comprising 10 percent, by'weight, of aresin blend comprising about 50 percent polyphenylene oxide resin and about 50 percent of an organosilicon terpolymer resin consisting essentially of the'addition polymerization reaction product between about 15 parts styrene, about 85 parts methyl metacrylateand about 5 parts vinyl triethoxy silane. About 20 grams of the resin blend is applied to about 5 pounds of glass cores. After drying, the milling procedure of Example IV is repeated with the foregoing coated carrier particles substituted for the Xerox 813 carrier particles. A slight amount of toner impaction is first observed after a milling time of about 96 hours. No chips or flakes are found.
  • Example XII The milling procedure described in Example XI is continued until the cumulative milling time is about 192 hours. Upon termination of the milling, no chips or flakes are found. Examination of the carrier surfaces reveals almost complete toner impaction.
  • EXAMPLE XIII Glass carrier cores having an average diameter of about 600 microns are spray coated with a coating solution comprising about 10 percent, by weight, of an organosilicon terpolymer resin consisting essentially of the addition polymerization reaction product between about 15 parts styrene, about 85 parts methyl methacrylate and about parts vinyl triethoxy silane. About 20 grams of the resin is applied to about 5 pounds of glass cores. After drying, the milling procedure of Example IV is repeated with the foregoing coated carrier particles substituted for the Xerox 813 carrier particles. A slight amount of toner impaction is first ob served after a milling time of about 96 hours. No chips or flakes are found.
  • Example XIV The milling procedure described in Example XIII is continued until the cumulative milling time is about 192 hours. Upon termination of the milling, no chips or flakes are found. Examination of the carrier surfaces reveals complete toner impaction.
  • EXAMPLE XV Steel carrier cores having an average diameter of about 250 microns are spray coated with a coating solution comprising about 15 percent, by weight, of a resin blend comprising about 90 percent polyphenylene oxide resin NORYL resin sold by the General Electric Company, and about percent of an organosilicon terpolymer resin consisting essentially of the addition polymerization reaction product between about 50 parts styrene, about 50 parts isobutyl methacrylate and about 5 parts gamma-methacryloxypropyltrimethoxy silane. About 20 grams of the resin blend is applied to about pounds of steel cores. After drying, the mill ing procedure of Example IV is repeated with the foregoing coated carrier particles substituted for the Xerox 813 carrier particles. A slight amount of toner impaction is first observed after a milling time of about 144 hours. No chips or flakes are found.
  • EXAMPLE XVI Flintshot carrier cores having an average diameter of about 600 microns are spray coated with a coating solution comprising about percent, by weight, of a resin blend comprising about 90 percent polyphenylene oxide resin and about 10 percent of polycarbonate resin. About 35 grams of the resin blend is applied to about 5 pounds of flintshot cores. After drying, the milling procedure of Example IV is repeated with the foregoing carrier particles substituted for the Xerox 813 carrier particles. A slight amount of toner impaction is first observed after a milling time of about 240 hours. No chips or flakes are found.
  • Iron carrier cores having an average diameter of about 500 microns are spray coated with a coating solution comprising about 10 percent, by weight, of a resin blend comprising about percent polyphenylene oxide resin and about 25 percent of ethylenevinylacetate copolymer resin. About 20 grams of the resin blend is applied to about 10 pounds of iron cores. After drying, the milling procedure of Example IV is repeated with the foregoing coated carrier particles substituted for the Xerox 813 carrier particles. A slight amount of toner impaction is first observed after a milling time of about 144 hours. No chips or flakes are found.
  • a carrier particle for electrostatographic developer mixtures comprising a particulate core surrounded by a thin outer layer, said thin outer layer comprising from about 1 to about 20 microns in thickness of a blend of a polyphenylene oxide resin and a solid terpolymer of (1) from about 5 to about 94.5 percent, by weight of an unsaturated silicon free organic compound (2) from about 94.5 to about 5 percent, by weight of an unsaturated silicon free organic compound different from the compound of (1) and (3) from about 0.5 to about 50 percent, by weight of a polymerizable organosilicon compound selected from the group consisting of silanes, silanols, and siloxanes having from one to three hydrolyzable groups and an organic group attached directly to a silicon atom containing less than 8 carbon atoms and an unsaturated carbon to carbon linkage, the weight ratio of said polyphenylene oxide to said terpolymer being from about :10 to about 25:75.
  • a carrier particle for electrostatographic developer mixtures comprising a particulate core surrounded by a thin outer layer, said thin outer layer comprising from about 1 to about 20 microns in thickness of a blend of a polyphenylene oxide resin and a solid terpolymer of l from about 5 to about 94.5 percent, by weight, of a styrene composition, (2) from about 94.5 to about 5 percent, by weight, of a composition selected from the group consisting of acrylate and methacrylate esters and (3) from about 0.5 to about 50 percent, by weight, of a polymerizable organosilicon composition selected from the group consisting of organosilanes, silanols, and siloxanes having from one to three hydrolyzable groups and an organic group attached directly to a silicon atom containing less than 8 carbon atoms and an unsaturated carbon to carbon linkage, the weight ratio of said polyphenylene oxide to said terpolymer being from about 90:10 to about 25:75.
  • a carrier particle for electrostatographic developer mixtures comprising a particulate core surrounded by a thin outer layer, said thin outer layer comprising from about 1 to about 20 microns in thickness of a blend of a solid polyphenylene oxide resin'and a solid linear addition terpolymer of (1) from about to about 94.5 percent, by weight, of a styrene composition, (2) from about 94.5 to about 5 percent, by weight, of a methacrylate composition selected from the group consisting of methyl, ethyl, propyl, and butyl methacrylate and (3) from about 0.5 to about 50 percent, by

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
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US00027114A 1966-10-11 1970-04-09 Coated carrier particles for electrostatographic development Expired - Lifetime US3850676A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
GB45221/67A GB1211863A (en) 1966-10-11 1967-10-04 Improvements in or relating to electrostatographic carriers
BE704917D BE704917A (enrdf_load_stackoverflow) 1966-10-11 1967-10-10
DE19671597886 DE1597886A1 (de) 1966-10-11 1967-10-11 Traegerstoff fuer elektrostatographische Entwicklerstoffmischungen
NL6713821A NL6713821A (enrdf_load_stackoverflow) 1966-10-11 1967-10-11
FR124100A FR1540694A (fr) 1966-10-11 1967-10-11 Véhicule pour des mélanges révélateurs électrostatographiques
US00027114A US3850676A (en) 1966-10-11 1970-04-09 Coated carrier particles for electrostatographic development
US00242780A US3857792A (en) 1966-10-11 1972-04-10 An electrostatic developer mixture with a coated carrier
US00244254A US3849127A (en) 1966-10-11 1972-04-12 Electrostatographic process in which coated carrier particles are used

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US58573966A 1966-10-11 1966-10-11
US00027114A US3850676A (en) 1966-10-11 1970-04-09 Coated carrier particles for electrostatographic development
US00244254A US3849127A (en) 1966-10-11 1972-04-12 Electrostatographic process in which coated carrier particles are used

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US3850676A true US3850676A (en) 1974-11-26

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US00027114A Expired - Lifetime US3850676A (en) 1966-10-11 1970-04-09 Coated carrier particles for electrostatographic development
US00244254A Expired - Lifetime US3849127A (en) 1966-10-11 1972-04-12 Electrostatographic process in which coated carrier particles are used

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US00244254A Expired - Lifetime US3849127A (en) 1966-10-11 1972-04-12 Electrostatographic process in which coated carrier particles are used

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US (2) US3850676A (enrdf_load_stackoverflow)
BE (1) BE704917A (enrdf_load_stackoverflow)
DE (1) DE1597886A1 (enrdf_load_stackoverflow)
GB (1) GB1211863A (enrdf_load_stackoverflow)
NL (1) NL6713821A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4129136A (en) * 1976-08-25 1978-12-12 Rank Xerox Limited Rejuvenating electrostatographic carrier particles
EP0021851A1 (en) * 1979-07-02 1981-01-07 Xerox Corporation Electrostatographic toner composition
US5102769A (en) * 1991-02-04 1992-04-07 Xerox Corporation Solution coated carrier particles
US5543224A (en) * 1994-04-11 1996-08-06 Mita Industrial Co., Ltd. High molecular electret film
US20060292478A1 (en) * 2005-06-22 2006-12-28 Xerox Corporation Carrier composition
SG152053A1 (en) * 2001-06-28 2009-05-29 Sabic Innovative Plastics Ip Moldable poly(arylene ether) thermosetting compositions, methods, and articles

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* Cited by examiner, † Cited by third party
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US4209550A (en) * 1976-01-19 1980-06-24 Xerox Corporation Coating carrier materials by electrostatic process
US4068017A (en) * 1976-07-30 1978-01-10 Addressograph Multigraph Corporation Coated carrier particles for use in electrophotographic process
JPS5941663B2 (ja) * 1979-07-20 1984-10-08 住友化学工業株式会社 樹脂組成物の製造法
EP0650099B1 (en) * 1993-10-15 2000-08-23 Canon Kabushiki Kaisha Carrier for electrophotography, two-component type developer, and image forming method
JPH07181743A (ja) * 1993-12-24 1995-07-21 Kao Corp 電子写真用キャリア及びその製造方法
CA2151988C (en) 1994-06-22 2001-12-18 Kenji Okado Carrier for electrophotography, two component-type developer and image forming method

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US2857290A (en) * 1955-09-21 1958-10-21 Ibm Electroferrographic printing process and apparatus therefor
US2874063A (en) * 1953-03-23 1959-02-17 Rca Corp Electrostatic printing
US2890968A (en) * 1955-06-02 1959-06-16 Rca Corp Electrostatic printing process and developer composition therefor
US2919247A (en) * 1954-12-23 1959-12-29 Haloid Xerox Inc Tripartite developer for electrostatic images
US3239465A (en) * 1958-05-12 1966-03-08 Xerox Corp Xerographic developer
US3383435A (en) * 1965-01-06 1968-05-14 Gen Eiectric Company Blend of a polyphenylene ether and a styrene resin
US3526533A (en) * 1966-08-10 1970-09-01 Xerox Corp Coated carrier particles
US3954751A (en) * 1973-01-02 1976-05-04 Basf Aktiengesellschaft Continuous production of cyanuric acid

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Publication number Priority date Publication date Assignee Title
US2874063A (en) * 1953-03-23 1959-02-17 Rca Corp Electrostatic printing
US2919247A (en) * 1954-12-23 1959-12-29 Haloid Xerox Inc Tripartite developer for electrostatic images
US2890968A (en) * 1955-06-02 1959-06-16 Rca Corp Electrostatic printing process and developer composition therefor
US2857290A (en) * 1955-09-21 1958-10-21 Ibm Electroferrographic printing process and apparatus therefor
US3239465A (en) * 1958-05-12 1966-03-08 Xerox Corp Xerographic developer
US3383435A (en) * 1965-01-06 1968-05-14 Gen Eiectric Company Blend of a polyphenylene ether and a styrene resin
US3526533A (en) * 1966-08-10 1970-09-01 Xerox Corp Coated carrier particles
US3954751A (en) * 1973-01-02 1976-05-04 Basf Aktiengesellschaft Continuous production of cyanuric acid

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4129136A (en) * 1976-08-25 1978-12-12 Rank Xerox Limited Rejuvenating electrostatographic carrier particles
EP0021851A1 (en) * 1979-07-02 1981-01-07 Xerox Corporation Electrostatographic toner composition
US5102769A (en) * 1991-02-04 1992-04-07 Xerox Corporation Solution coated carrier particles
US5543224A (en) * 1994-04-11 1996-08-06 Mita Industrial Co., Ltd. High molecular electret film
SG152053A1 (en) * 2001-06-28 2009-05-29 Sabic Innovative Plastics Ip Moldable poly(arylene ether) thermosetting compositions, methods, and articles
US20060292478A1 (en) * 2005-06-22 2006-12-28 Xerox Corporation Carrier composition
US7419755B2 (en) 2005-06-22 2008-09-02 Xerox Corporation Carrier composition

Also Published As

Publication number Publication date
US3849127A (en) 1974-11-19
DE1597886A1 (de) 1970-10-01
GB1211863A (en) 1970-11-11
NL6713821A (enrdf_load_stackoverflow) 1968-04-16
BE704917A (enrdf_load_stackoverflow) 1968-02-15

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