US2965573A - Xerographic developer - Google Patents

Xerographic developer Download PDF

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US2965573A
US2965573A US732644A US73264458A US2965573A US 2965573 A US2965573 A US 2965573A US 732644 A US732644 A US 732644A US 73264458 A US73264458 A US 73264458A US 2965573 A US2965573 A US 2965573A
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component
developer
mixture
carrier
particles
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US732644A
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Robert W Gundlach
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Xerox Corp
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Xerox Corp
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/10Developers with toner particles characterised by carrier particles
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S101/00Printing
    • Y10S101/37Printing employing electrostatic force

Definitions

  • Fig. 1 illustrates cascade development in accordance with the present invention
  • Fig. 2 is an enlarged detail illustration of a section within 2--2 of Fig. 1.
  • a xerographic plate 11 comprising a photoconductive insulating layer 12 overlying a conductive backing member 13.
  • a charge pattern 15 comprising areas of charge and areas of no charge or areas of varying charge.
  • the charge is illustrated as positive, but as is known in the art, the charge may be negative or even positive and negative.
  • Cascading across the surface of plate 11 is a developer mix of developer 16 which deposits toner particles across the image bearing surface 12 in accordance with the image pattern. Developer 16 and its composition will be more thoroughly discussed hereinafter.
  • xerographic plate 12 it is to be realized and understood that there is no intention to be limited to a particular surface bearing the image pattern.
  • the developer and developing systems of this invention are, it is noted, most beneficial when the image surface overlies a conductive member. This is because this invention overcomes the effects of the conductive member.
  • comparable quality is obtained whether developing a backed or unbacked image bearing layer and accordingly, any insulating layer is intended to be included herein and xerograpln'c plate 11 is included herein only for illustrative purposes.
  • Fig. 2 Although the illustration of this figure is drawn somewhat to scale to attempt to represent the relationship of particle sizes, the representation is primarily for illustrative purposes and accordingly is somewhat diagrammatic in nature. It is further to be realized that in this figure there is captured for purposes of discussion the cascading particles during an instant of their movement across the image bearing surface.
  • developer mix 16 comprising carrier particles 17 (only some of which are numbered), toner particles 18 (again only some of which are numbered and filaments 20 (again only some of which are numbered) cascading across plate 11 comprising photoconductive insulating layer 12 overlying backing member 13.
  • Fig. 1 there exists acharge pattern 15 on the surface of image bearing layer 12.
  • Carrier 17 as is fully defined in US. Patent 2,618,551 comprises generally a granular carrier material which is of sufficient specific gravity such as glass, sand or steel beads to insure against adherence of the granular carrier material to the image bearing surface as the carrier cascades across the surface being developed.
  • the granular carrier should also have a desired triboelectric relationship to the toner material and if it is not inherent in the carrier material it may be coated or encased in a suitable covering to impart thereto these necessary properties.
  • the particle size of the carrier material should be in the range of from 20 to 200 mesh and preferably between the range of 30 to 100 mesh.
  • Toner 18 may comprise any of the known toners defined, for example, in the aforementioned US. patents and may consist, for example, of particles of pigmenting or coloring material encased in or surrounded by an insulating material which acquires by contact with the granular carrier material an electrostatic charge having a polarity opposite to that acquired by the granular material.
  • the coloring material as well as the toner material is fully described in U.S. Patent 2,638,416 and generally should be no larger than 20 microns and preferably is within the range of from 5 to microns average particle size.
  • the coloring material may be carbon or other suitable pigments and the insulating material may be a rosinmodified phenol-formaldehyde resin, such as known commercially as Amberol F-7l, manufactured by Rohm & Haas Company, The Resinous Products Division, Washington Square, Philadelphia 5, Pennsylvania, or asphaltum, or other suitable material.
  • a rosinmodified phenol-formaldehyde resin such as known commercially as Amberol F-7l, manufactured by Rohm & Haas Company, The Resinous Products Division, Washington Square, Philadelphia 5, Pennsylvania, or asphaltum, or other suitable material.
  • the pigmented electroscopic powder is prepared by first micronizing the resin material, such as Amberol F-7l, after which it is mixed with approximately 5% by weight of carbon black or other pigmenting material and the mixture ball-milled for about four hours in a ceramic jar with stone pellets. The mixture is then heated to a temperature of about 300 F. or to flowing viscosity and mixed for five minutes in order to encase the pigmenting particles with the Amberol F-7l. The mass is then permitted to cool, after which it is broken into small chunks and again micronized.
  • the resin material such as Amberol F-7l
  • the pigmented electroscopic powder is then in condition for mixing with a granular carrier such as polymerized methyl methacrylate, having a melting point of approximately 257 F., known commercially as Lucite and manufactured by E. I. Du Pont de Nemours & Company, Wilmington, Delaware, or other material either conducting or insulating, provided the particles of granular material when brought in close contact with the electroscopic powder particles acquire a charge having an opposite polarity to that of the electroscopic powder particles, such that the electroscopic powder particles adhere to and surround the granular carrier particles.
  • a granular carrier such as polymerized methyl methacrylate, having a melting point of approximately 257 F., known commercially as Lucite and manufactured by E. I. Du Pont de Nemours & Company, Wilmington, Delaware, or other material either conducting or insulating
  • the granular carrier material is selected so that the particles acquire a charge having the same polarity as that of the photoconductive insulating layer of the plate on which the electrostatic image is produced, and an electrical attraction for the electroscopic powder particles considerably less than that of the charged areas of the plate and somewhat greater than the discharged areas of the plate.
  • the mixture of toner and carrier comprises 1 part toner mixed with from 20 to 200 parts carrier and preferably the mixture comprises 1 part toner to 50 to 120 parts carrier.
  • Filaments 20 are conductive strands and may comprise, for example, conductive wires, conductive strings or the like. Their length generally should be greater than 956 inch and the upper limit on length is generally about inch, but as will appear more clearly in the following discussion, greater lengths are also possible.
  • the preferred length for filaments 20 is between /8 and /2 inch, and for the typical range of material generally reproduced an average length of about A inch is preferred.
  • the diameter of filaments 20 may range from 1 to 20 mils and is preferably between 3 and 10 mils. Triboelectrically, filaments 20 should be opposed in polarity to the toner while like in polarity to the carrier or should charge the toner to the same polarity as the toner charge when the toner 18 is brought into physical contact with carrier 17.
  • Filament 20 should also be substantially neutral triboelectrically in respect to carrier 17.
  • filaments 20 may comprise Nichrome, steel, aluminum, copper, brass and particularly yellow brass, nickel, and the like.
  • the material chosen preferably should be a stable material which, for example, resists oxidation which might act to change its triboelectric relationship to toner 18 and carrier 17.
  • a particularly effective and the preferred filament material for a positive developer wherein the carrier material comprises a resin-coated bead and the toner material comprises, for example, the Amberol F-7l mixture described previously and the toner material becomes charged negatively in relation to the carrier material on mixing with the carrier material is Nichrome chopped strands.
  • a reversal mixture wherein the toner is charged positively in respect to the carrier comprises nickel-coated copper or copper strands which have been exposed to sulphur fumes at a high temperature.
  • filament particles 20 may be mixed with the carrier toner mixture in a ratio of from parts developer (carrier and toner) to 5 to parts filament and preferably the mixture may comprise 100 parts developer to 20 to 1.00 parts filaments.
  • the preferred developer mixture including filaments as illustrated in Fig. 2 comprises 49% carrier 17, 49% filament 20 and 2% toner 18.
  • the filament material being discussed may vary in length and diameter and that the amount of filament material mixed with a developer mix is dependent to some extent on these variables.
  • filament 20 comprises a long length such as /1 inch then a tendency exists for filaments 26 to cluster and there follows a flowing of the filaments 20 across image bearing surface 12 as a clustered group. When this occurs a raking of the image is observed.
  • This clustering and raking problem can be overcome to some extent by using large diameter filaments when employing long lengths in the filament material.
  • a further technique of avoiding the clustering effect is to employ a low percentage of filament 20 to developer mix somewhere, for example, in the range of 2% to 3%. If shorter lengths as, for example inch are used larger percentage ratios of filament to developer may be employed.
  • filament 20 also designated 21, it is to be observed, extends across a charged area as well as an uncharged area of image bearing surface 12. Since filament 21 is conductive, it, like any other conductor, has a supply of free electrons and while over both a charged and an uncharged area there is a flow within filament 21 controlled by the surrounding electric fields. There thus results polarization of charge within this filament so that negative charge appears over the positively charged areas of plate 11 and positive charge appears over the uncharged areas of plate 11. This member although polarized remains an equipotential member and thus presents a close- 1y spaced equipotential surface to the image bearing surface 12.
  • filament 21 Since the negative charged area of filament 21 is positioned over the positive charged area of image bearing surface 12 strong electrostatic lines of force exist between the positive charges and filament 21 and thus lines of force extend directly outward from the surface of plate 11. There follows particle deposition in accordance with linesof force as disclosed previously and there results particle deposition in accordance with the charge pattern. It is noted that areas of filament 21 over uncharged areas of image bearing surface 12 are positive with respect to the image bearing surface and thus there follows a tendency to avoid particle deposition on the image bearing surface in these areas. Acc0rdingly, filament 21 when positioned as illustrated in Fig. 2 acts first to cause particle deposition in accordance with the charge on the surface being developed as well as to prevent deposition in areas of background thus producing background-free high quality copy.
  • filament 20 also designated 22
  • this filament is positioned over an uncharged area. Being over an uncharged area it is in a neutral condition and will tend to have no real effect on whether particles deposit or do not deposit on the surface of image bearing layer 12. In fact it will act as any carrier particle.
  • filament 20 also designated 23 it is seen that this particle is in physical contact with filament 20, also designated 25, which is in contact with filament 20, also designated 26, which is in contact with filment 20, also designated 27, which is in contact with filament 20, also designated 21. Since these filaments are conductive and are in contact, filament 23 will assume a slightly positive relationship in respect in respect to the uncharged area of photoconductive insulating layer 12 over which it is now positioned. This will aid also in preventing background deposition.
  • Fig. 2 illustrates a brief moment in the flow of the cascading developer 16 across plate 11 and that a moment later this contact relationship between various filament particles is likely to be broken and a moment later it may be made anew with other particles, etc. Accordingly, there is a continuing change of filament reltaionship to the surface being developed, but as this change takes place and as the developer mixer moves across the surface of the plate, developrnent electrode effects through the flowing filaments are extended to all areas of the plate to a substantially average level and result in a uniform high quality image developed in accordance with the charge pattern. It is also to be noted that control of the developed image may be exercised through control of the developer mixture.
  • the length of filament chosen is selected because of its bridging capabilities.
  • probability of bridging from the broad area of charge to the uncharged area is greater thereby effecting particle deposition in the central zone more readily than if shorter filaments are employed. This may also be accomplished, however, if a larger percentage of the smaller particles are incorporated into the developer mix.
  • toner particles 18 also adhere in a releasable fashion to filament 20. This is because of the triboelectric relationship between the toner particle 18 and the filament 20, and adherence between toner particle 18 and filament 20 in no way detracts from the quality of the image developed.
  • filament 20 is after all of the same triboelectric relationship to the toner as the carrier material and accordingly can act as the carrier material.
  • a problem, however, which has been present to date employing filament 20 as both filament 20 and carrier 17 is the tendency for the developer mixture to rake the surface being developed.
  • the developed image occasionally includes a streaked pattern as if raked whenthe carrier is omitted; whereas, with a developer mixture employing a carrier material 17 this pattern is avoided.
  • the carrier material is beneficial in providing the wheels to cause the entire developer mixture 16 to roll across the surface being developed without dragging or raking as it apparently occasionally does without carrier 17.
  • developer mixtures according to this invention also include carrier 17, and carrier 17 may be composed of the same material as filament 20.
  • carrier material 17 may not present in the developer mixture, then the developer mixture may comprise 1 part toner 18, to 20-200 parts filament and preferably 1 part toner to 50-120 parts filament.
  • filaments 20 added to xerographic cascade developers in accordance with this invention should comprise a good electrical conductor having a substantially neutral triboelectric relationship to the carrier and the same triboelectric relationship to the toner as the carrier has to the toner and. should be in strip, chopped wire or filament-like form whereby conductive bridging of an area over the surface being developed can readily take place.
  • a xerographic developer for electrostatic latent images comprising, in mixture, a first component comprising granular carrier particles having a size range of from 20 to 200 mesh, a second component comprising filamentary electrically conductive particles having a length in the range of from about ,6 inch to about /1 inch and having diameters in the range of about from 1 to 20 mils, and a third component comprising pigmented toner powder particles no larger than about 20 microns, each of said first and said second components being triboelectrically different from said third component and each having a triboelectric relationship of like polarity with respect to said third component and said second component having a substantially neutral triboelectric relationship with respect to said first component, a developer mixture comprising one part of said third componeat to 20 to 200 parts of said first component and the first and third component mixture comprising about parts to about 5 to 150 parts of said second component.
  • a xerographic developer for electrostatic latent images comprising, in mixture, a first component comprising granular carrier particles in' the size range of about from 30 to 100 mesh, a second component comprising filamentary electrically conductive particles having lengths in the range of from about A; to /zinch and having diameters in the range of from about 3 to 10 mils, and a third component comprising: pigmented toner powder particles in the range of about.
  • each of said first and said second components being triboelectrically different from said third component and each having a triboelectric relationship of like polarity with respect to said third component and said second component having a substantially neutral triboelectric relationship with respect to said first component, one part of said third component being mixed with 50 to parts of said first component and 100 parts of the mixture of said first component and said third component being mixed with 20 to 100 parts of said second component.
  • a developer for electrostatic latent images comprising, in mixture, a first component comprising filamentary electrically conductive particles having a length in the range of from about ,6 to inch and having diameters in the range of from about 1 to 20 mils, and a second component comprising pigmented toner powder particles no larger than about 20 microns, said first and said secnd components being admixed one part of said second component to about 20 to 200 parts of said first component, said first and said second components being triboelectrically diiferent from each other to cause said second component to electrostatically adhere to said first component when said first and said second components are admixed and said triboelectric relationship being of an intensity to allow said second component to be released to an electrostatic charge pattern when said mixture of said first and said second component are cascaded across an electrostatic image bearing surface.
  • a developer for electrostatic latent images comprising, in mixture, a first component comprising filamentary electrically conductive particles having an average length of about A inch and having diameters in the range of from about 3 to 10 mils, and a second component comprising pigmented toner powder particles in the size range of from about 5 to microns, said first and said second components being admixed one part of said second component to 50 to 120 parts of said first component, said first and said second components being triboelectrically different from each other to cause said second component to adhere to said first component when said first and said second components are admixed and said triboelectric relationship being of an intensity to allow said second component to be released to an electrostatic charge pattern when said mixture of said first and said second component are cascaded across an electrostatic image bearing surface.
  • a xerographic developer for electrostatic images comprising, in mixture, a first component comprising granular carrier particles having a size range of from about 30 to about 100 mesh, a second component comprising filamentary electrically conductive particles having a length of about inch to about /2 inch and having a diameter in the range of from about 3 to about 10 mils, and a third component comprising pigmented toner particles in the range between about 5 to about 10 microns, said components being admixed one part of said third component to 50 to parts of said first component and the third and first component mixture being admixed with said second component in a ratio of 100 parts of the mixture of the third and first components to 20 to 100 parts of said second component.
  • a developer for electrostatic latent images comprising, in mixture, a first component comprising granular carrier particles having a size range of from 20 to 200 mesh, a second component comprising filamentary particles of yellow brass having a length in the range of about inch to about inch and having a diameter in the range of about 1 to 20 mils, and a third component comprising pigmented toner particles no larger than about 20 microns, each of said first and said second components being triboelectrically different from said third component and each having a triboelectric relation of like polarity with respect to said third component and said second component having a substantially neutral triboelectric relationship with respect to said first component, said developer comprising a toner carrier mixture in mixture with yellow brass, said toner carrier mixture comprising one part toner to 20 to 200 parts carrier, and said developer comprising about 100 parts of said toner carrier mixture in mixture with about 5 to parts filamentary particles of yellow brass.
  • a xerographic developer for electrostatic latent images comprising, in mixture, a first component comprising granular carrier particles having a size range of from 20 to 200 mesh, a second component comprising filamentary electrically conductive particles having a length of from about inch to about inch and having a diameter in the range from about 1 to 20 mils, and a third component comprising pigmented toner powder particles no larger than about 20 microns, said mixture comprising one part toner to 20 to 200 parts carrier and the toner carrier mixture comprising about 100 parts to about 5 to 150 parts filamentary particles.

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Description

Dec. 20, 1960 R. w. GUNDLACH XEROGRAPHIC DEVELOPER Filed May 2, 1958 mm mm mm mm Q kw u \w INVENTOR. Robert W. Gundlach ihg g Q QQ United States aten XEROGRAPHIC DEVELOPER Robert W. Gundlach, Spencerport, N.Y., assignor to Haloid Xerox Inn, Rochester, N.Y., a corporation of New York Filed May 2, 1958, Ser. No. 732,644
17 Claims. (Cl. 252-621) This invention relates ot image development of electro static charge patterns.
In order to simplify understanding of this invention it will be exemplified with the art of xerography wherein an electrostatic latent image is formed as through direct charge deposition or exposure of a photosensitive member to a light pattern or the like on an insulating layer 'toner, across the image bearing surface for selective deposition of the toner on the surface in accordance with the charge pattern. Suitable developer mixtures and a full disclosure of their method of use are presented in Us. Patents 2,618,551, 2,618,552, issued on November 18, 1952, and in US. Patent 2,638,416, issued May 12, 1953.
Although the cascade system of image development is the accepted commercial technique to visualize an electrostatic latent image, it inherently does not fully develop large solid areas and frequently there results in the developed image what is generally referred to as the halo effect. Image development with the halo effect and lacking in solid area coverage is today understood to be due to the fact that particle deposition takes place in accordance with electrostatic lines of force rather than as directly controlled by the charge pattern being developed. Considering, for a moment, a large area of charge and realizing that lines of force do not cross and follow the direction of greatest potential gradient to an opposite pole, it can be realized that the charges on the outer edges are terminals for lines of force which extend outward from the surface of the plate and possibly to the next adjacent uncharged area on the surface of the plate. These lines of force near edges of the large areas of charge when developed with a proper developer material can result in particle deposition on the charges of the charge terminal end of the lines of force, thus properly reflecting the pattern. However, at the central zone of the large area of charge the lines of force tend to extend inward through the image bearing member and since development is development of the lines of force, little or no development takes place. One technique of combatting this difficulty is to employ a development electrode or a closely spaced equipotential surface which causes the lines of force to extend outward from the image bearing surface toward the equipotential surface thus causing particles to deposit accurately as a reflection of the original image. The electrode, however, in order to be effective must be close and frequently as, for example, in automatic xerographic machines including cascade developing systems, the narrowness of the gap cannot be maintained "ice without sacrifice in such areas as speed in output or damage to the image bearing surface or member.
Now, in accordance with the present invention, there is disclosed new improved concepts of image development of electrostatic charge patterns. These concepts when employed improve the developed image by fully developing large areas of charge and by avoiding the halo effect. Further, these new concepts when applied in machines do not place limitations, as did known developers and developing systems, on other operational steps. As a further matter and in accordance with this invention a new and improved developer material is disclosed.
Accordingly, it is an object of this invention to define novel methods of image development to visualize electrostatic image patterns.
It is a further object of this invention to improve image development in "the art of xerography.
It is a still further object of this invention to improve developer materials of the cascade variety.
It is yet a further object of this invention to define new xerographic developer materials.
Additional objects and advantages of the present invention will be more readily apparent in view of the following disclosure and description especially when read in conjunction with the accompanying drawing.
In the drawing:
Fig. 1 illustrates cascade development in accordance with the present invention; and
Fig. 2 is an enlarged detail illustration of a section within 2--2 of Fig. 1.
Referring now to Fig. 1, there is illustrated a xerographic plate 11 comprising a photoconductive insulating layer 12 overlying a conductive backing member 13. On the surface of the photoconductive insulating layer 12 is a charge pattern 15 comprising areas of charge and areas of no charge or areas of varying charge. In this figure the charge is illustrated as positive, but as is known in the art, the charge may be negative or even positive and negative. Cascading across the surface of plate 11 is a developer mix of developer 16 which deposits toner particles across the image bearing surface 12 in accordance with the image pattern. Developer 16 and its composition will be more thoroughly discussed hereinafter.
Although there is illustrated in this figure a xerographic plate 12 it is to be realized and understood that there is no intention to be limited to a particular surface bearing the image pattern. The developer and developing systems of this invention are, it is noted, most beneficial when the image surface overlies a conductive member. This is because this invention overcomes the effects of the conductive member. However, comparable quality is obtained whether developing a backed or unbacked image bearing layer and accordingly, any insulating layer is intended to be included herein and xerograpln'c plate 11 is included herein only for illustrative purposes.
In order to more fully understand development in accordance with this invention reference is now had to Fig. 2. Although the illustration of this figure is drawn somewhat to scale to attempt to represent the relationship of particle sizes, the representation is primarily for illustrative purposes and accordingly is somewhat diagrammatic in nature. It is further to be realized that in this figure there is captured for purposes of discussion the cascading particles during an instant of their movement across the image bearing surface. Thus, there is illustrated developer mix 16 comprising carrier particles 17 (only some of which are numbered), toner particles 18 (again only some of which are numbered and filaments 20 (again only some of which are numbered) cascading across plate 11 comprising photoconductive insulating layer 12 overlying backing member 13. As in accordance with the description in Fig. 1 there exists acharge pattern 15 on the surface of image bearing layer 12.
In comparison to prior art techniques of image development there has been added to developer mix 16 filaments 20. Carrier 17, as is fully defined in US. Patent 2,618,551 comprises generally a granular carrier material which is of sufficient specific gravity such as glass, sand or steel beads to insure against adherence of the granular carrier material to the image bearing surface as the carrier cascades across the surface being developed. The granular carrier should also have a desired triboelectric relationship to the toner material and if it is not inherent in the carrier material it may be coated or encased in a suitable covering to impart thereto these necessary properties. Generally the particle size of the carrier material should be in the range of from 20 to 200 mesh and preferably between the range of 30 to 100 mesh.
Toner 18 may comprise any of the known toners defined, for example, in the aforementioned US. patents and may consist, for example, of particles of pigmenting or coloring material encased in or surrounded by an insulating material which acquires by contact with the granular carrier material an electrostatic charge having a polarity opposite to that acquired by the granular material. The coloring material as well as the toner material is fully described in U.S. Patent 2,638,416 and generally should be no larger than 20 microns and preferably is within the range of from 5 to microns average particle size.
The coloring material may be carbon or other suitable pigments and the insulating material may be a rosinmodified phenol-formaldehyde resin, such as known commercially as Amberol F-7l, manufactured by Rohm & Haas Company, The Resinous Products Division, Washington Square, Philadelphia 5, Pennsylvania, or asphaltum, or other suitable material.
The pigmented electroscopic powder is prepared by first micronizing the resin material, such as Amberol F-7l, after which it is mixed with approximately 5% by weight of carbon black or other pigmenting material and the mixture ball-milled for about four hours in a ceramic jar with stone pellets. The mixture is then heated to a temperature of about 300 F. or to flowing viscosity and mixed for five minutes in order to encase the pigmenting particles with the Amberol F-7l. The mass is then permitted to cool, after which it is broken into small chunks and again micronized.
The pigmented electroscopic powder is then in condition for mixing with a granular carrier such as polymerized methyl methacrylate, having a melting point of approximately 257 F., known commercially as Lucite and manufactured by E. I. Du Pont de Nemours & Company, Wilmington, Delaware, or other material either conducting or insulating, provided the particles of granular material when brought in close contact with the electroscopic powder particles acquire a charge having an opposite polarity to that of the electroscopic powder particles, such that the electroscopic powder particles adhere to and surround the granular carrier particles. The granular carrier material is selected so that the particles acquire a charge having the same polarity as that of the photoconductive insulating layer of the plate on which the electrostatic image is produced, and an electrical attraction for the electroscopic powder particles considerably less than that of the charged areas of the plate and somewhat greater than the discharged areas of the plate.
Generally the mixture of toner and carrier comprises 1 part toner mixed with from 20 to 200 parts carrier and preferably the mixture comprises 1 part toner to 50 to 120 parts carrier.
Filaments 20 are conductive strands and may comprise, for example, conductive wires, conductive strings or the like. Their length generally should be greater than 956 inch and the upper limit on length is generally about inch, but as will appear more clearly in the following discussion, greater lengths are also possible. The preferred length for filaments 20 is between /8 and /2 inch, and for the typical range of material generally reproduced an average length of about A inch is preferred. The diameter of filaments 20 may range from 1 to 20 mils and is preferably between 3 and 10 mils. Triboelectrically, filaments 20 should be opposed in polarity to the toner while like in polarity to the carrier or should charge the toner to the same polarity as the toner charge when the toner 18 is brought into physical contact with carrier 17. Filament 20 should also be substantially neutral triboelectrically in respect to carrier 17. Typically, filaments 20 may comprise Nichrome, steel, aluminum, copper, brass and particularly yellow brass, nickel, and the like. The material chosen preferably should be a stable material which, for example, resists oxidation which might act to change its triboelectric relationship to toner 18 and carrier 17. A particularly effective and the preferred filament material for a positive developer wherein the carrier material comprises a resin-coated bead and the toner material comprises, for example, the Amberol F-7l mixture described previously and the toner material becomes charged negatively in relation to the carrier material on mixing with the carrier material is Nichrome chopped strands. A reversal mixture wherein the toner is charged positively in respect to the carrier comprises nickel-coated copper or copper strands which have been exposed to sulphur fumes at a high temperature. When employing both carrier particles 17 and toner particles 18, filament particles 20 may be mixed with the carrier toner mixture in a ratio of from parts developer (carrier and toner) to 5 to parts filament and preferably the mixture may comprise 100 parts developer to 20 to 1.00 parts filaments. The preferred developer mixture including filaments as illustrated in Fig. 2 comprises 49% carrier 17, 49 % filament 20 and 2% toner 18.
It is to be realized that the filament material being discussed may vary in length and diameter and that the amount of filament material mixed with a developer mix is dependent to some extent on these variables. For example, if filament 20 comprises a long length such as /1 inch then a tendency exists for filaments 26 to cluster and there follows a flowing of the filaments 20 across image bearing surface 12 as a clustered group. When this occurs a raking of the image is observed. This clustering and raking problem can be overcome to some extent by using large diameter filaments when employing long lengths in the filament material. A further technique of avoiding the clustering effect is to employ a low percentage of filament 20 to developer mix somewhere, for example, in the range of 2% to 3%. If shorter lengths as, for example inch are used larger percentage ratios of filament to developer may be employed.
The mechanism of operation now believed to effect large, solid area coverage as well as to avoid the halo effect is believed somewhat apparent when considering Fig. 2. For example, filament 20 also designated 21, it is to be observed, extends across a charged area as well as an uncharged area of image bearing surface 12. Since filament 21 is conductive, it, like any other conductor, has a supply of free electrons and while over both a charged and an uncharged area there is a flow within filament 21 controlled by the surrounding electric fields. There thus results polarization of charge within this filament so that negative charge appears over the positively charged areas of plate 11 and positive charge appears over the uncharged areas of plate 11. This member although polarized remains an equipotential member and thus presents a close- 1y spaced equipotential surface to the image bearing surface 12. Since the negative charged area of filament 21 is positioned over the positive charged area of image bearing surface 12 strong electrostatic lines of force exist between the positive charges and filament 21 and thus lines of force extend directly outward from the surface of plate 11. There follows particle deposition in accordance with linesof force as disclosed previously and there results particle deposition in accordance with the charge pattern. It is noted that areas of filament 21 over uncharged areas of image bearing surface 12 are positive with respect to the image bearing surface and thus there follows a tendency to avoid particle deposition on the image bearing surface in these areas. Acc0rdingly, filament 21 when positioned as illustrated in Fig. 2 acts first to cause particle deposition in accordance with the charge on the surface being developed as well as to prevent deposition in areas of background thus producing background-free high quality copy. Considering now filament 20, also designated 22, it is seen that this filament is positioned over an uncharged area. Being over an uncharged area it is in a neutral condition and will tend to have no real effect on whether particles deposit or do not deposit on the surface of image bearing layer 12. In fact it will act as any carrier particle. Looking now to filament 20, also designated 23, it is seen that this particle is in physical contact with filament 20, also designated 25, which is in contact with filament 20, also designated 26, which is in contact with filment 20, also designated 27, which is in contact with filament 20, also designated 21. Since these filaments are conductive and are in contact, filament 23 will assume a slightly positive relationship in respect in respect to the uncharged area of photoconductive insulating layer 12 over which it is now positioned. This will aid also in preventing background deposition.
It is to be realized that Fig. 2 illustrates a brief moment in the flow of the cascading developer 16 across plate 11 and that a moment later this contact relationship between various filament particles is likely to be broken and a moment later it may be made anew with other particles, etc. Accordingly, there is a continuing change of filament reltaionship to the surface being developed, but as this change takes place and as the developer mixer moves across the surface of the plate, developrnent electrode effects through the flowing filaments are extended to all areas of the plate to a substantially average level and result in a uniform high quality image developed in accordance with the charge pattern. It is also to be noted that control of the developed image may be exercised through control of the developer mixture. Thus, and for example, if it is desired to develop large charged areas it is generally preferred to use longer filaments whereas with the average mixture of broad areas of charge and narrow areas of charge it is generally preferred to use an intermediate length in the filament material and with relatively small broad areas of charge it. is generally preferred to use the shorter length filaments. It is noted that the length of filament chosen is selected because of its bridging capabilities. Thus, with the larger areas of charge it is preferred to have a long filament in order that probability of bridging from the broad area of charge to the uncharged area is greater thereby effecting particle deposition in the central zone more readily than if shorter filaments are employed. This may also be accomplished, however, if a larger percentage of the smaller particles are incorporated into the developer mix.
As is apparent in the illustration in Fig. 2, toner particles 18 also adhere in a releasable fashion to filament 20. This is because of the triboelectric relationship between the toner particle 18 and the filament 20, and adherence between toner particle 18 and filament 20 in no way detracts from the quality of the image developed.
In fact, developer mixtures excluding carrier 17 have been tried and have been very successful in developing images. It is noted in this respect that filament 20 is after all of the same triboelectric relationship to the toner as the carrier material and accordingly can act as the carrier material. A problem, however, which has been present to date employing filament 20 as both filament 20 and carrier 17 is the tendency for the developer mixture to rake the surface being developed. Thus, the developed image occasionally includes a streaked pattern as if raked whenthe carrier is omitted; whereas, with a developer mixture employing a carrier material 17 this pattern is avoided. It is presently believed that the carrier material is beneficial in providing the wheels to cause the entire developer mixture 16 to roll across the surface being developed without dragging or raking as it apparently occasionally does without carrier 17. Accordingly, it is generally preferred that developer mixtures according to this invention also include carrier 17, and carrier 17 may be composed of the same material as filament 20. When carrier material 17 is not present in the developer mixture, then the developer mixture may comprise 1 part toner 18, to 20-200 parts filament and preferably 1 part toner to 50-120 parts filament.
In summary, filaments 20 added to xerographic cascade developers in accordance with this invention should comprise a good electrical conductor having a substantially neutral triboelectric relationship to the carrier and the same triboelectric relationship to the toner as the carrier has to the toner and. should be in strip, chopped wire or filament-like form whereby conductive bridging of an area over the surface being developed can readily take place.
What is claimed is:
1. A xerographic developer for electrostatic latent images comprising, in mixture, a first component comprising granular carrier particles having a size range of from 20 to 200 mesh, a second component comprising filamentary electrically conductive particles having a length in the range of from about ,6 inch to about /1 inch and having diameters in the range of about from 1 to 20 mils, and a third component comprising pigmented toner powder particles no larger than about 20 microns, each of said first and said second components being triboelectrically different from said third component and each having a triboelectric relationship of like polarity with respect to said third component and said second component having a substantially neutral triboelectric relationship with respect to said first component, a developer mixture comprising one part of said third componeat to 20 to 200 parts of said first component and the first and third component mixture comprising about parts to about 5 to 150 parts of said second component.
2. A xerographic developer for electrostatic latent images comprising, in mixture, a first component comprising granular carrier particles in' the size range of about from 30 to 100 mesh, a second component comprising filamentary electrically conductive particles having lengths in the range of from about A; to /zinch and having diameters in the range of from about 3 to 10 mils, and a third component comprising: pigmented toner powder particles in the range of about. 5 to 10 microns in size, each of said first and said second components being triboelectrically different from said third component and each having a triboelectric relationship of like polarity with respect to said third component and said second component having a substantially neutral triboelectric relationship with respect to said first component, one part of said third component being mixed with 50 to parts of said first component and 100 parts of the mixture of said first component and said third component being mixed with 20 to 100 parts of said second component.
3. A developer in accordance with claim 2 in which the carrier comprise about 49% by weight of the mixture, the filamentary particles comprise about 49% by weight of the mixture, and the toner material comprises about 2% by weight of the mixture.
4. The developer of claim 2 in which said second component comprises filamentary electrically conductive particles having a length of about A inch.
-5. The developer of claim 2 in which said second component comprises Nichrome.
6. The developer of claim 2 in which said second component comprises nickel-coated copper.
7. The developer of claim 2 in which said second component comprises copper strands which have been exposed to sulphur fumes at a high temperature.
8. A developer for electrostatic latent images comprising, in mixture, a first component comprising filamentary electrically conductive particles having a length in the range of from about ,6 to inch and having diameters in the range of from about 1 to 20 mils, and a second component comprising pigmented toner powder particles no larger than about 20 microns, said first and said secnd components being admixed one part of said second component to about 20 to 200 parts of said first component, said first and said second components being triboelectrically diiferent from each other to cause said second component to electrostatically adhere to said first component when said first and said second components are admixed and said triboelectric relationship being of an intensity to allow said second component to be released to an electrostatic charge pattern when said mixture of said first and said second component are cascaded across an electrostatic image bearing surface.
9. The developer of claim 8 in which said first component comprises Nichrome.
10. The developer of claim 8 in which said first component comprises yellow brass.
11. The developer of claim 8 in which said first component comprises nickel-coated copper.
12. The developer of claim 8 "n which said first component comprises copper strands which have been exposed to sulphur fumes at a high temperature.
13. A developer for electrostatic latent images comprising, in mixture, a first component comprising filamentary electrically conductive particles having an average length of about A inch and having diameters in the range of from about 3 to 10 mils, and a second component comprising pigmented toner powder particles in the size range of from about 5 to microns, said first and said second components being admixed one part of said second component to 50 to 120 parts of said first component, said first and said second components being triboelectrically different from each other to cause said second component to adhere to said first component when said first and said second components are admixed and said triboelectric relationship being of an intensity to allow said second component to be released to an electrostatic charge pattern when said mixture of said first and said second component are cascaded across an electrostatic image bearing surface.
14. A xerographic developer for electrostatic images comprising, in mixture, a first component comprising granular carrier particles having a size range of from about 30 to about 100 mesh, a second component comprising filamentary electrically conductive particles having a length of about inch to about /2 inch and having a diameter in the range of from about 3 to about 10 mils, and a third component comprising pigmented toner particles in the range between about 5 to about 10 microns, said components being admixed one part of said third component to 50 to parts of said first component and the third and first component mixture being admixed with said second component in a ratio of 100 parts of the mixture of the third and first components to 20 to 100 parts of said second component.
15. The developer of claim 14 in which said second component comprises filamentary electrically conductive particles having a length of about inch.
16. A developer for electrostatic latent images comprising, in mixture, a first component comprising granular carrier particles having a size range of from 20 to 200 mesh, a second component comprising filamentary particles of yellow brass having a length in the range of about inch to about inch and having a diameter in the range of about 1 to 20 mils, and a third component comprising pigmented toner particles no larger than about 20 microns, each of said first and said second components being triboelectrically different from said third component and each having a triboelectric relation of like polarity with respect to said third component and said second component having a substantially neutral triboelectric relationship with respect to said first component, said developer comprising a toner carrier mixture in mixture with yellow brass, said toner carrier mixture comprising one part toner to 20 to 200 parts carrier, and said developer comprising about 100 parts of said toner carrier mixture in mixture with about 5 to parts filamentary particles of yellow brass.
17. A xerographic developer for electrostatic latent images comprising, in mixture, a first component comprising granular carrier particles having a size range of from 20 to 200 mesh, a second component comprising filamentary electrically conductive particles having a length of from about inch to about inch and having a diameter in the range from about 1 to 20 mils, and a third component comprising pigmented toner powder particles no larger than about 20 microns, said mixture comprising one part toner to 20 to 200 parts carrier and the toner carrier mixture comprising about 100 parts to about 5 to 150 parts filamentary particles.
References Cited in the file of this patent s. 112...), r' a

Claims (1)

1. A XEROGRAPHIC DEVELOPER FOR ELECTROSTATIC LATENT IMAGES COMPRISING, IN MIXTURE, A FIRST COMPONENT COMPRISING GRANULAR CARRIER PARTICLES HAVING A SIZE RANGE OF FROM 20 TO 200 MESH, A SECOND COMPONENT COMPRISING FILAMENTARY ELECTRICALLY CONDUCTIVE PARTICLES HAVING A LENGTH IN THE RANGE OF FROM ABOUT 1/16 INCH TO ABOUT 3/4 INCH AND HAVING DIAMETERS IN THE RANGE OF ABOUT FROM 1 TO 20 MILS, AND A THIRD COMPONENT COMPRISING PIGMENTED TONER POWDER PARTICLES NO LARGER THAN ABOUT 20 MICRONS, EACH OF EACH AND SAID SECOND COMPONENTS BEING TRIBOELECTRICALLY DIFFERENT FROM SAID THIRD COMPONENT AND EACH HAVING A TRIBOELECTRIC RELATIONSHIP OF LIKE POLARITY WITH RESPECT TO SAID THIRD COMPONENT AND SAID SECOND COMPONENT HAVING A SUBSTANTIALLY MENTRAL TRIBOELECTRIC RELATIONSHIP WITH RESPECT TO SAID FIRST COMPONENT, A DEVELOPER MIXTURE COMPRISING ONE PART OF SAID THIRD COMPONENT TO 20 TO 200 PARTS OF SAID FIRST COMPONENT AND THE FIRST AND THIRD COMPONENT MIXTURE COMPRISING ABOUT 100 PARTS TO ABOUT 5 TO 150 PARTS OF SAID SECOND COMPONENT.
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Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3212888A (en) * 1961-06-12 1965-10-19 Xerox Corp Method for developing latent electrostatic charge halftone images
US3215527A (en) * 1960-09-02 1965-11-02 Rca Corp Method for preparing cured polymeric etch resists using a xerographic developer containing a curable polymer
US3231374A (en) * 1960-09-02 1966-01-25 Rca Corp Methods for preparing etch resists using an electrostatic image developer composition
US3234017A (en) * 1959-11-05 1966-02-08 Agfa Ag Process for the production of developed electrophotographic images including application of a breakdown potential to discrete small areas of a photoconductor
US3236639A (en) * 1959-09-04 1966-02-22 Azoplate Corp Two component partially removable electrophotographic developer powder and process for utilizing same
US3241998A (en) * 1960-07-12 1966-03-22 Australia Res Lab Method of fixing xerographic images
US3349676A (en) * 1965-04-02 1967-10-31 Xerox Corp Xerographic development electrode apparatus
US3369917A (en) * 1963-09-10 1968-02-20 Daniel B. Granzow Magnetic brush development of electrostatic images utilizing a high voltage corona
US3607342A (en) * 1966-11-29 1971-09-21 Fuji Photo Film Co Ltd Method of development of electrostatic images
DE2227285A1 (en) * 1971-06-10 1973-01-04 Xerox Corp DEVELOPER MIX
US3767578A (en) * 1971-06-10 1973-10-23 Xerox Corp Carrier material for electrostatographic developer
US3770482A (en) * 1971-01-18 1973-11-06 Beatrice Foods Co Electrostatic coating method of applying multilayer coating
US3824924A (en) * 1966-12-07 1974-07-23 Continental Can Co Electrostatic screen printing and cleaning
US3828670A (en) * 1968-10-31 1974-08-13 Continental Can Co Method and apparatus for electrostatic printing using triboelectric inking developers
US3833364A (en) * 1968-11-18 1974-09-03 Xerox Corp Method of developing electrostatic image charge
US3859913A (en) * 1970-08-28 1975-01-14 Heller William C Jun Apparatus and process for printing
US3865611A (en) * 1972-11-09 1975-02-11 Xerox Corp Method for electrostatic image development employing toner and carrier supported by a conductive liquid electrode surface
US3977871A (en) * 1975-08-15 1976-08-31 International Business Machines Corporation Electrophotographic developer with fibers of polytetrafluoroethylene
US4018601A (en) * 1969-06-19 1977-04-19 Xerox Corporation Electrostatographic magnetic brush imaging process employing carrier beads comprising high purity nickel
US4148640A (en) * 1974-03-11 1979-04-10 Eastman Kodak Company Developer compositions having electrically conducting filaments in carrier particle matrix
US4341854A (en) * 1980-09-22 1982-07-27 Eastman Kodak Company Method for flash fusing toner images
US4373131A (en) * 1980-09-22 1983-02-08 Eastman Kodak Company Apparatus for flash fusing tuner images
US4404269A (en) * 1980-11-17 1983-09-13 Mita Industrial Co., Ltd. Developer containing magnetic and non-magnetic toner
US4414321A (en) * 1980-11-27 1983-11-08 Mita Industrial Co. Ltd. Dry composite blended magnetic developer of resin encapsulated fine magnetite and resin encapsulated coarse magnetite
US4416964A (en) * 1980-09-02 1983-11-22 Mita Industrial Co., Ltd. Dry magnetic developer containing a non-pulverizing agglumerate of cubic magnetite particles
US4472490A (en) * 1980-09-03 1984-09-18 Matsushita Electric Industrial Co., Ltd. Image forming particles
US4504562A (en) * 1980-11-27 1985-03-12 Mita Industrial Co., Ltd. One-component type magnetic developer comprises particles of cubic magnetite
US4672018A (en) * 1985-12-16 1987-06-09 Xerox Corporation Flash fusing process with prespheroidized toner
US4683187A (en) * 1984-11-26 1987-07-28 Amnon Goldstein Dry process electrostatic developer comprising a generally round magnetic carrier and a flake-type carrier
US4794651A (en) * 1984-12-10 1988-12-27 Savin Corporation Toner for use in compositions for developing latent electrostatic images, method of making the same, and liquid composition using the improved toner
US5158852A (en) * 1989-11-22 1992-10-27 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Electrophotographic development process
US5328795A (en) * 1989-03-29 1994-07-12 Bando Chemical Industries, Ltd. Toners for use in electrophotography and production thereof
US5407771A (en) * 1984-12-10 1995-04-18 Indigo N.V. Toner and liquid composition using same
US5547795A (en) * 1994-06-22 1996-08-20 Hitachi Metals, Ltd. Magnetic carrier for developer
US5851717A (en) * 1995-04-24 1998-12-22 Ricoh Company, Ltd. Developer for use in electrophotography, and image formation method using the same

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US2638416A (en) * 1948-05-01 1953-05-12 Battelle Development Corp Developer composition for developing an electrostatic latent image
US2573881A (en) * 1948-11-02 1951-11-06 Battelle Development Corp Method and apparatus for developing electrostatic images with electroscopic powder
US2705199A (en) * 1951-09-12 1955-03-29 Harold E Clark Method of developing an electrostatic latent image
US2786439A (en) * 1953-06-30 1957-03-26 Rca Corp Electrophotographic developing apparatus
US2758524A (en) * 1953-12-30 1956-08-14 Rca Corp Electrostatic photographic printing
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Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236639A (en) * 1959-09-04 1966-02-22 Azoplate Corp Two component partially removable electrophotographic developer powder and process for utilizing same
US3234017A (en) * 1959-11-05 1966-02-08 Agfa Ag Process for the production of developed electrophotographic images including application of a breakdown potential to discrete small areas of a photoconductor
US3241998A (en) * 1960-07-12 1966-03-22 Australia Res Lab Method of fixing xerographic images
US3215527A (en) * 1960-09-02 1965-11-02 Rca Corp Method for preparing cured polymeric etch resists using a xerographic developer containing a curable polymer
US3231374A (en) * 1960-09-02 1966-01-25 Rca Corp Methods for preparing etch resists using an electrostatic image developer composition
US3212888A (en) * 1961-06-12 1965-10-19 Xerox Corp Method for developing latent electrostatic charge halftone images
US3369917A (en) * 1963-09-10 1968-02-20 Daniel B. Granzow Magnetic brush development of electrostatic images utilizing a high voltage corona
US3349676A (en) * 1965-04-02 1967-10-31 Xerox Corp Xerographic development electrode apparatus
US3607342A (en) * 1966-11-29 1971-09-21 Fuji Photo Film Co Ltd Method of development of electrostatic images
US3824924A (en) * 1966-12-07 1974-07-23 Continental Can Co Electrostatic screen printing and cleaning
US3828670A (en) * 1968-10-31 1974-08-13 Continental Can Co Method and apparatus for electrostatic printing using triboelectric inking developers
US3833364A (en) * 1968-11-18 1974-09-03 Xerox Corp Method of developing electrostatic image charge
US4018601A (en) * 1969-06-19 1977-04-19 Xerox Corporation Electrostatographic magnetic brush imaging process employing carrier beads comprising high purity nickel
US3859913A (en) * 1970-08-28 1975-01-14 Heller William C Jun Apparatus and process for printing
US3770482A (en) * 1971-01-18 1973-11-06 Beatrice Foods Co Electrostatic coating method of applying multilayer coating
DE2227285A1 (en) * 1971-06-10 1973-01-04 Xerox Corp DEVELOPER MIX
US3767578A (en) * 1971-06-10 1973-10-23 Xerox Corp Carrier material for electrostatographic developer
US3865611A (en) * 1972-11-09 1975-02-11 Xerox Corp Method for electrostatic image development employing toner and carrier supported by a conductive liquid electrode surface
US4148640A (en) * 1974-03-11 1979-04-10 Eastman Kodak Company Developer compositions having electrically conducting filaments in carrier particle matrix
US3977871A (en) * 1975-08-15 1976-08-31 International Business Machines Corporation Electrophotographic developer with fibers of polytetrafluoroethylene
US4416964A (en) * 1980-09-02 1983-11-22 Mita Industrial Co., Ltd. Dry magnetic developer containing a non-pulverizing agglumerate of cubic magnetite particles
US4472490A (en) * 1980-09-03 1984-09-18 Matsushita Electric Industrial Co., Ltd. Image forming particles
US4341854A (en) * 1980-09-22 1982-07-27 Eastman Kodak Company Method for flash fusing toner images
US4373131A (en) * 1980-09-22 1983-02-08 Eastman Kodak Company Apparatus for flash fusing tuner images
US4404269A (en) * 1980-11-17 1983-09-13 Mita Industrial Co., Ltd. Developer containing magnetic and non-magnetic toner
US4504562A (en) * 1980-11-27 1985-03-12 Mita Industrial Co., Ltd. One-component type magnetic developer comprises particles of cubic magnetite
US4414321A (en) * 1980-11-27 1983-11-08 Mita Industrial Co. Ltd. Dry composite blended magnetic developer of resin encapsulated fine magnetite and resin encapsulated coarse magnetite
US4683187A (en) * 1984-11-26 1987-07-28 Amnon Goldstein Dry process electrostatic developer comprising a generally round magnetic carrier and a flake-type carrier
US4794651A (en) * 1984-12-10 1988-12-27 Savin Corporation Toner for use in compositions for developing latent electrostatic images, method of making the same, and liquid composition using the improved toner
US5407771A (en) * 1984-12-10 1995-04-18 Indigo N.V. Toner and liquid composition using same
US4672018A (en) * 1985-12-16 1987-06-09 Xerox Corporation Flash fusing process with prespheroidized toner
US5328795A (en) * 1989-03-29 1994-07-12 Bando Chemical Industries, Ltd. Toners for use in electrophotography and production thereof
US5158852A (en) * 1989-11-22 1992-10-27 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Electrophotographic development process
US5547795A (en) * 1994-06-22 1996-08-20 Hitachi Metals, Ltd. Magnetic carrier for developer
US5851717A (en) * 1995-04-24 1998-12-22 Ricoh Company, Ltd. Developer for use in electrophotography, and image formation method using the same

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