US3853555A - Method of color imaging a layer of electrically photosensitive agglomerates - Google Patents

Method of color imaging a layer of electrically photosensitive agglomerates Download PDF

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Publication number
US3853555A
US3853555A US00310040A US31004072A US3853555A US 3853555 A US3853555 A US 3853555A US 00310040 A US00310040 A US 00310040A US 31004072 A US31004072 A US 31004072A US 3853555 A US3853555 A US 3853555A
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agglomerates
layer
imaging
field
mono
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US00310040A
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G Reinis
K Nelson
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Xerox Corp
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Xerox Corp
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Priority to NL7316301A priority patent/NL7316301A/xx
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G17/00—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process
    • G03G17/08—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process using an electrophoto-adhesive process, e.g. manifold imaging

Definitions

  • an electrically photosensitive imaging layer comprises a randomly mixed mono-layer of a plurality of at least two different electrically photosensitive agglomerates.
  • the imaging layer is placed between two members and subjected to a first electric field. Such field is then modified as by reducing, grounding or reversing the field. After such modification, the first field is substantially restored across the imaging layer prior to imagewise exposure of the imaging layer to electromagnetic radiation to which it is sensitive.
  • the imaging layer is then exposed to appropriate electromagnetic radiation and the members separated. Upon separation of the members exposed, agglomerates of the mono-layer of plurality of agglomerates are independently removed from the mono-layer in imagewise configuration thereby forming a multi-color copy of the original image on one of the sheets.
  • Another object of this invention is to provide a multicolor imaging method which allows the operator to determine the image contrast.
  • Another object of this invention is to provide a multicolor imaging method providing images of improved resolution.
  • images can be produced by the above described color imaging process having lower contrast, improved resolution and more density variation by means of oscillating the electric field across the imaging layer prior to exposing the imaging layer to actinic electromagnetic radiation.
  • the imaging layer of the process is subjected to a first electric field as in the usual case for exposure purposes and then modified as by reversing, grounding or reducing the field to an extent further defined below.
  • the field is then substantially restored and is maintained at a value considered suitable for exposure purposes as previously known in the art for such imaging layer. That is, while the restored field need not be of the same magnitude as the first field, it is one which provides imaging conditions and preferably is slightly higher in potential than the first field.
  • the restored field is sufficient to provide selective adhesion of the agglomerates in the imaging layer to the members between which they are sandwiched in accordance with the pattern of light and shadow to which they are exposed under saidfield.
  • the color imaging process is practiced in accordance with this invention by inserting field oscillation into the process at any point prior to exposure of the imaging layer to suitable electromagnetic radiation.
  • the field manipulation involves first raising the potential across the imaging layer to provide a first electrical field.
  • the field is then modified by reversing, grounding or reducing it.
  • the field is again altered or modified by raising the potential across the imaging layer typically to the extent of substantially restoring the original or first electric field across the imaging layer.
  • the actual values of field strength are dependent upon the nature of the imaging layer and the donor and receiver layers residing in the electrical field.
  • the strength of the electrical potential applied initially in the first electrical field across the imaging layer depends, as stated, on the structure of the sandwich or set and the materials employed therein. The potential strength required may, however, be easily determined. If too large a potential is applied, electrical breakdown of the sandwich will occur allowing arcing between the electrodes. If too little potential is applied, the imaging layer will not selectively adhere to the surface of the members in imagewise configuration should the imaging layer be exposed to suitable electromagnetic radiation at that time and the sandwich opened.
  • the preferred potential across the imaging layer is, however, in the range of from about 2,000 volts per mil. to about 7,000 volts per mi]. of insulating material in the field. Since relatively high potentials are utilized, it is desirable to insert a resistor in the circuit to limit the flow of current.
  • Resistors on the order of from about 1 megohm to about 20,000 megohms are conveniently employed. While the potential across the imaging layer is not varied during the exposure step of the imaging process, alternating current can be employed prior to such exposure step. Thus, direct current or alternating current can be employed prior to the imagewise exposure step of the process. Direct current is preferred clue to the relatively high potential employed and appropriate circuitry for alternating current would be necessary if the operator of the process desired to employ this type of electrical power source.
  • Another embodiment of this invention includes both types of electrical fields. That is, one may oscillate the field across the imaging layer by subjecting the layer to a field of alternating current. After such treatment, the
  • imaging layer is then subjected to direct current of imaging intensity and the process completed as described below.
  • direct current of imaging intensity For example, high voltage 60 cycle AC current of about 3,000 volts, per mil. of insulating material in the field is applied across the imaging layer for about one second. The field is discontinued and a DC field of about the same strength is applied while the imaging layer is exposed to actinic radiation and the sandwich subsequently separated.
  • a transformer is preferably employed with the AC field to provide an output to the electrodes of high voltage and low current.
  • V the original potential across the imaging layer
  • V the dielectric constant of the receiving member
  • K that of the donor member
  • K that of the imaging layer
  • K and the thickness of the donor member d the receiver member (d and the imaging layer
  • V The maximum reduced potential (V can be calculated for any particular manifold set by the formula:
  • the altered or modified field is then again modified so as to restore the electrostatic charges initially induced into the imaging layer by the first electrical field.
  • This easliy accomplished by subjecting the imaging layer to a second electric field of the same polarity and typically of substantially the same potential as first employed. As mentioned above, potentials slightly higher than that first employed are preferred in most instances.
  • the imaging layer is exposed to electromagnetic radiation to which it is sensitive.
  • the usual procedures and materials employed in the color imaging process described in copending application Ser. No. 222,619 are practiced in concert with the field alteration step employed in accordance with this invention.
  • FIG. I shows schematically a side view of a first embodiment photosensitive imaging member for use in the invention
  • FIG. 2 shows one method of releasing the agglomerates in another embodiment of the invention
  • FIG. 3 shows exposure of the imaging member to light of different colors
  • FIG. 4 shows separation of the imaging member to produce the final full-color image
  • FIG. 5 shows schematically a side sectional view of an alternative embodiment photosensitive imaging member for use in the invention.
  • FIG. I shows a color imaging member generally designated 1 which is made up of several components.
  • Donor member 2 has coated on one surface thereof a layer of imaging material comprising a randomly mixed mono-layer of a plurality of at least two different electrically photosensitive agglomerates. Utilizing subtractive polychromatic image formation, these agglomerates are colored Magenta, Yellow and Cyan. The different colors for the particle agglomerates in FIG. I are indicated by M for Magenta, Y for Yellow and C for Cyan.
  • Each agglomerate with layer 3 of FIG. 1 contains a single color, for example, an agglomeration of many pigment particles of a single color, or a combination of pigment or dye with encapsulating binder.
  • the photosensitive particles may be transparent and provided with color suitable for use in the subtractive color system.
  • Color separation in the imaging member I of FIG. 1 is obtained by the stabilization of the differently colored electrically photosensitive particles in the imaging layer and the configuration of the layer such that the stabilized particles may freely respond to the combined effect of electromagnetic radiation and an applied potential by selectively adhering to either of the donor or receiver members, 2 and 5, respectively, of FIG. I, depending upon the polarity of the applied potential.
  • Such stabilization is achieved by either impaction whereby the individual electrically photosensitive particles are impactly agglomerated into agglomerates of the desired size, or by encapsulating the individual electrically photosensitive particles in a binder.
  • the impaction technique is satisfactorily carried out in a Svedgari Attritor Impactor, manufactured by the Union Process, Incoporated of Akron, Ohio; and the encapsulation technique is achieved through a novel agglomeration process disclosed herein.
  • Such layer configuration is a random mixture of the differently colored electrically photosensitive particle agglomerates so that good color balance is achieved; and more importantly, the thickness of the imaging layer is about that of the diameter of the agglomerates but no greater than twice the diameters.
  • the tops and bottoms of the agglomerates are not necessarily co-planar, one with the other, nor are the agglomerates necessarily touching or spaced a preselected distance apart.
  • the imaging layer is, therefore, a mono-layer of agglomerates and will be referred to throughout as such; but it is understood, of course, that such terminology means any configuration of agglomerates less than two complete and superimposed layers of agglomerates and one which will allow color separation of the agglomerates in the imaging method employed.
  • mono-layer 3 comprises differently colored particles: for example, a Magenta pigment, a Yellow pigment, and a Cyan pigment are agglomerated in separate batches (uni-mixes), by either impaction or the novel process disclosed below, and then all three uni-mixes are mixed and uniformly dispersed by sonification. Satisfactory dispersing by sonification is provided by any of the standard dispersion equipment models available from the Branson Sonic Power Company of Danbury, Conn. The uniformly dispersed agglomerates are then coated onto the donor member 2 at a thickness equal to about the diameter of the agglomerates by any suitable coating method well-known to those skilled in the art.
  • the imaging layer comprises a randomly mixed mono-layer of a plurality of different electrically photosensitive agglomerates.
  • electrically photosensitive agglomerates or agglomerates shall include both electrically photosensitive particle agglomerates or particles agglomerates and electrically photosensitive particle-binder agglomerates or particle-binder agglomerates; the former terms referring to agglomerates containing only electrically photosensitive particles, and the latter terms referring to the combination of such particles and binder.
  • donor member 2 has a conductive backing l which is optional where donor member 2 is insulating and which may be eliminated.
  • Receiver member 5 is in contact with the upper surface of the imaging mono-layer 3 and when receiver member 5 is insulating, you can optionally have, as shown in FIG. ]l, a conductive backing layer a.
  • a preferred method is to provide an imaging member of FIG. ll wherein a suitable binder or cement for the agglomerates is included in the imaging layer.
  • the cement is dissolved as, for example, by means illustrated in FIG. 2 wherein a suitable solvent 8 is applied to the imaging layer from container 7.
  • a suitable solvent 8 is applied to the imaging layer from container 7.
  • the imaging set is then placed in an electric field as is shown in FIG. 3 using the conductive coating 4 and 6 as the electrodes which are connected to power supply 16 through resistor I6 and double through switch 19.
  • a first electrical field is applied to the electrodes and prior to exposure of the imaging layer to actinic electromagnetic radiation, the field is modified by changing switch 19 from position A to position B. Modifications may also be achieved by lowering the voltage or grounding the'circuit as described above. subse quent to such modification, the first or original electric field is restored by changing switch 19 from position 8 7 back to position A.
  • the final applied field need not be exactly the same potential as the first field as preferably slightly greater.
  • FIG. 3 schematically shows this exposure of the set to different areas of light being projected through donor substrate 2.
  • Area 9 represents that projection of white light, area 10, the projection of no light; area ill, the projection or red light, area 112, the projection of blue light; area 13, the projection of green light; and area M, the projection of yellow light.
  • the imaging member l is separated as shown in FIG. 4, producing a visible multi-colored image. With subtractive color formation, as shown in FIG. 4, the positive image conforming to the orginal is ordinarily formed on the donor member 2. The applied potential of the restored or third field condition is maintained across the imaging material during the separating step.
  • white light projection in area 9 results in the transfer of the Magenta, Yellow and Cyan b colored individual agglomerates exposed to such projection to the receiver member 5, leaving a white or transparent area on donor member 2.
  • all of the individual agglomerates remain on the donor substrate, combining to form a black-appearing area on donor substrate 2 via light scattering.
  • red light is projected, as in area llll, any Cyan material exposed will transfer to receiving sheet 5 upon stripout, leaving be hind the Magenta and Yellow areas which by light scattering effect combine to appear red to the eye.
  • FIGS. ll, 3 and 4 may have incoporated many various materials for each of the components to the imaging set.
  • At least one of donor member 2 or receiver member 5 should be at least partially transparent so that an image may be projected onto the imaging layer therethrough.
  • complete transparency is had as, for example, by use of Mylar polyester film manufactured by the Dupont Co. of Wilmington, Del.
  • Insulating materials suitable for use in members 2 and 5 are polyethylene, polyethylene terephthalate (Mylar polyester film), cellulose acetate, and the like, optionally backed by conductive electrode material, such as evaporated tin oxide.
  • Opaque material, such as paper may also be used for one of these members. Either of members 2 and 5 may also singularly provide the dual characteristics of transparency and conductivity.
  • Typical conductive transparent materials include cellophane, conductively coated glass, such as tin or indium oxide coated glass, aluminum coated glass or similar coatings on plastic substrates.
  • NESA a tin oxide coated glass available from Pittsburgh Plate Glass Co., is often used because it is a good conductor and is highly transparent and is readily available.
  • the imaging mono-layer 3 of individual agglomerates may comprise any suitable electrically photosensitive material within or on the surface of the particle agglomerates which has suitable color and spectral response.
  • the agglomerates may be: either particle agglomerates or particle-binder agglomerates; that is, they may consist entirely of the electrically photosensitive material or may comprise a photosensitive material dispered in a binder.
  • the size of the agglomerates ranges from about 0.1 to 25 microns in diameter; optimum, from about 3 to 15; and preferred, from about 5 to 10.
  • Typical highly colored photosensitive materials include: Algol Yellow GC, 1, 2, 5, 6- di(C.C-diphenyl) thiazole-anthraquinone, C.
  • a suitable binder for the particle-binder agglomerates will preferably comprise insulating waxes or polymers as formerly employed.
  • Typical waxes and polymers include low melt waxes, such as octadencane, nonadecane, eicosane and mixtures thereof; microcrystalline waxes; paraffin waxes; waxes made from hydrogenated oils; polyethylenes; modified styrenes; vinylacetate-ethylene copolymers; vinyl chloride-vinyl acetate copolymers; styrene-vinyl toluene copolymers; polypropylenes; and mixtures thereof.
  • the electrical potential is shown in FIGS. 3 and 4 as being applied from a potential source 115 having a conductive pathway between conductive backing 6 and conductive backing 4; that is, imaging member 1 is placed between electrodes (conductive backings 4 and 6) having different electrical potential.
  • an electrical charge can be imposed upon one or both of the donor-member and receiving member before or after forming the sandwich by any one of the several known methods for inducing a static electrical charge into a material. Static charges can be imposed by contacting the sheet or substrate with an electrically charged electrode. Additionally, one or both sheets may be charged using corona discharge devices, such as those described in U.S. Pat. No. 2,588,699 to Carlson, U.S. Pat. No.
  • Imaging occurs when charges are imposed.
  • the maximum limit of applied potential is the breakdown of imaging member 1, such that conductivity of the member 11 is sufficient to prevent imaging. This will vary depending upon the materials utilized.
  • imaging member 11 of FIGS. 11, 3 and 4. it'is preferable to prefabricate imaging member 11 of FIGS. 11, 3 and 4. This is especially true from the viewpoint of a mere user of imaging member 11.
  • the manufacturer may wish not only to stabilize the photosensitive particles for imaging but to further stabilize imaging mono-layer 3 and to render the entire imaging member 11 sufficiently rigid to withstand handling, transportation and storage operations.
  • This can be accomplished by cementing the agglomerates within imaging layer 3 together with a soluble interagglomerate cement.
  • the cement is preferably insulating.
  • the agglomerates withstand the cementing and solvent addition without losing their identity as agglomerates.
  • cleaner background is produced when the agglomerates are preferably particle-binder agglomerates which areinsoluble in the solvent used to dissolve, the cement.
  • Suitable cements include Piccotex 75, Piccotex and Piccotex available from the Pennsylvania Industrial Chemical Co. the AROCLOR series of polychlorinated polyphenyls available from Monsanto and other solid or semi-solid resins and polymers soluble in hydrocarbon solvents.
  • Typical materials which are solvents include kerosene, carbon tetrachloride, petroleum v ether, silicone oils, such as dimethylpolysiloxanes, long chain aliphatic hydrocarbon oils, such as those ordinarily used as transformer oils, trichloroethylene, chlorobenzene, benzene, toluene, xylene, hexane, acetone, vegetable oils and mixtures thereof; member of the FREON series of chlorinated, fluorinated hydrocarbons available from E: I. du Pont de Nemours; and, of preference, is Sohio Odorless Solvent 3440, a kerosene fraction available from Standard Oil of Ohio.
  • FIG. 5 there is shown therein an alternative embodiment of my invention.
  • This alternate embodiment is in all other respects identical to that in FIGS. 1, 3 and 4 and like-numbered components in FIG. 5 are identical to like-numbered components in those figures.
  • the one aspect in which these embodiments of the invention differ is the use of two adhesive layers, 17 and 18, in FIG. 5, to balance the adhesion between the mono-layer 3 and receiver member 5 with the adhesion between mono-layer 3 and donorsubstrate 2.
  • This embodiment of the invention dampens out any natural tendencies that the various suitable electrically photosensitive materials (incorporated within the individual particle agglomerates of monolayer 3) may have to possess greater adhesion for donor member 2 over receiver member 6.
  • Adhesive layers 117 and 18 preferably comprise the same material so as to insure adhesive balance. However, layers 17 and 118 may each comprise a different material provided the adhesion is substantially balanced.
  • layers 17 and 18 may each comprise a different material provided the adhesion is substantially balanced.
  • the materials that may be suitably incorporated within the layers 117 and 18 comprise solids and semisolids and thereby facilitate commercial manufacture, assembly, storage, maintenance and handling of the fabricated imaging member and provide a neater imaging member with which the consumer may work.
  • the user of the imaging member fabricated in accordance with the second embodiment of the invention need not remove receiver sheet 5 prior to image production.
  • the FIG. 5 embodiment of the invention is practiced in all other respects in a manner identical to the practice to the first embodiment of the invention with the added requirement that the layers 117 and 118 must be in a liquid state at the time of stripout. That is to say, at some point of the practice of the FIG. 5 embodiment of the invention, the imaging member is subjected to a temperature whichwill liquify the thermally liquifiable layers 17 and 18. Such liquefaction can occur either before, during or after the exposure step. For some materials, normal ambient temperatures will be adequate, however, when higher melting point layers are employed, heat is applied to the manifold set.
  • EXAMPLE I A yellow colored dispersion of micron agglomerates is made by ball milling for two hours 3 gm. of yellow pigment described in U.S. Pat. No. 3,447,922 (N- 2 "-pyridyl-8, l3-dioxodinaphtho (2. l-b,2'3 d)dfuran-6-carboxamide) in 60 ml. of DC naptha which has been purified through a clay column. After milling, 5 gm. of a modified polystyrene, available from the Pennsylvania industrial Chemical Company under the tradename Piccotex 75, and ml.
  • Sohio Odorless Solvent 3440 are added thereto and the solids dissolved by heating the dispersion to 65C under moderate stirring. The dispersion is ball milled for an additional 2 hours. Then 60 ml. of isopropyl alcohol is added under rapid stirring thereby precipitating the solids about the yellow pigment particles. The dispersion and precipitate are vacuum filtered and flushed with 200 ml. of isopropyl alcohol. The resulting moist filter cake is dispersed in 80 ml. of isopropyl alcohol by sonification. A
  • cyan colored dispersion of 5 micron agglomerates is prepared by ball milling 3 gm. of purified metalfree alpha phthalocyanine pigment with 0.2 gm. of lndanthrone Blue (C. l. Vat Blue 6) available from Du Pont de Nemours in 80 cc of petroleum ether (90-120C) for 2 hours, 3 gm.
  • C. l. Vat Blue 6 lndanthrone Blue
  • the imaging member is then exposed through the receiver member to I00 ft.-candles of light for 1 second through a standard photographic color test target comprising a neutral step density wedge and cyan and yellow filters; the receiver and donor members are separated thereby yielding a positive cyan and yellow image on the Mylar receiver member in areas corresponding to the filters in the test target.
  • the images exhibit two intermediate 0.3 density steps.
  • Example II PRIOR ART The procedure of Example I is repeated with the exception that the field oscillation step is omitted. Upon separating the members, there is provided an image having 0 intermediate 0.3 density steps.
  • a method of imaging comprising:
  • agglomerates are particle agglomerates' 3.
  • said agglomerates are particle-binder agglomerates.

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US00310040A 1972-11-28 1972-11-28 Method of color imaging a layer of electrically photosensitive agglomerates Expired - Lifetime US3853555A (en)

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Cited By (2)

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US4113482A (en) * 1976-01-22 1978-09-12 Xerox Corporation Migration imaging method involving color change
US4172721A (en) * 1974-10-04 1979-10-30 Xerox Corporation Dye-amplified imaging process

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172721A (en) * 1974-10-04 1979-10-30 Xerox Corporation Dye-amplified imaging process
US4113482A (en) * 1976-01-22 1978-09-12 Xerox Corporation Migration imaging method involving color change

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