US3445227A - Electrophotographic imaging processes employing 2,4-diamino-triazines as the electrically photosensitive particles - Google Patents

Electrophotographic imaging processes employing 2,4-diamino-triazines as the electrically photosensitive particles Download PDF

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US3445227A
US3445227A US445179A US3445227DA US3445227A US 3445227 A US3445227 A US 3445227A US 445179 A US445179 A US 445179A US 3445227D A US3445227D A US 3445227DA US 3445227 A US3445227 A US 3445227A
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image
pigment
particles
suspension
color
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Lester Weinberger
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Xerox Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0698—Compounds of unspecified structure characterised by a substituent only
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G16/00—Electrographic processes using deformation of thermoplastic layers; Apparatus therefor
    • 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
    • G03G17/04—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 photoelectrophoresis
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/022—Layers for surface-deformation imaging, e.g. frost imaging
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0635—Heterocyclic compounds containing one hetero ring being six-membered
    • G03G5/064—Heterocyclic compounds containing one hetero ring being six-membered containing three hetero atoms

Definitions

  • This invention relates in general to imaging methods. More specifically, the invention concerns the use of electrically photosensitive pigments in electrophotographic imaging systems.
  • the photosensitive material must be an effective photoconductive insulator, i.e. must be capable of holding an electrostatic charge in the dark and dissipating the charge to a conductive substrate when exposed to light.
  • a base sheet of relatively low electrical resistance such as metal, paper, etc., hav ing a photoconductive insulating surface coated thereon, is electrically charged in the dark.
  • the charged coating is then exposed to a light image.
  • the charges leak off rapidly to the base sheet in proportion to the intensity of light to which any given area is exposed, the charge being substantially retained in non-exposed areas, forming a latent electrostatic image.
  • the coating is contacted with electrostatic marking particles in the dark.
  • a third class of electrophotographic imaging which utilizes electricallly photosensitive materials has recently been developed. This class consists of two systems of surface deformation imaging which are generally referred to as frost imaging and relief imaging. Frost imaging is described in detail in a publication entitled A Cyclic Xerographic Method Based on Frost Deformation by R. W. Gundlach and C. J. Claus, Journal of Photographic Science and Engineering, January-February edition, 1963. Relief imaging is described in detail in U.S. Patents 3,055,006; 3,163,872; and 3,113,179.
  • a plate may be made by overcoating a conductive substrate with a layer of a photoconductive insulating material, which is then overcoated with a thermoplastic material.
  • the photoconductive material may be dispersed in particulate form in the thermoplastic material and the mixture coated directly over the conductive substrate.
  • a uniform electrostatic charge is imposed on the plate surface, then the plate is exposed to a light-and-shadow image to be reproduced. The charge is dissipated in light struck areas but remains in unexposed areas.
  • the plate is heated or treated with a solvent vapor until the electrostatic attraction forces of the charge pattern exceed the surface tension forces of the film.
  • R represents an aryl or alkaryl group, substituted or unsubstituted; with tWo similar or different aryl-amino or alkaryl-amino compounds.
  • compositions produced by the above reaction have common characteristics of a brilliant yellow color; of
  • compositions within the general formula listed above those in which R and R represent substituted or unsubstituted amino-anthraquinones and R represents a polynuclear aromatic radical are preferred for use in electrophoretic imaging processes since they have especially pure color and are most highly photosensitive. They have been found to give the most desirable combination of color qualities and photosensitivity. Optimum results have been obtained with 2,4-di(1'-anthraquinonyl-amino)- 6-(1"-pyrenyl)-s-triazine. However, since the shade or tone of the compositions in the spectral and photosensitive responses vary silightly depending upon the substitutent used, intermediate values of these variables may be obtained by mixing several of the compositions of this invention.
  • compositions within the general formula listed above, and mixtures thereof, are especially useful as photosensitive pigment particles in electrophoretic imaging processes.
  • An exemplary electrophoretic imaging system is shown in the figure.
  • a transparent electrode generally designated 1 which, in this instance, is made up of a layer of optically transparent glass 2 overcoated with a thin optically transparent layer 3 of tin oxide, commercially available under the name NESA glass.
  • This electrode shall hereafter be referred to as the injecting electrode.
  • Coated on the surface of injecting electrode 1 is a thin layer 4 of [finely divided photosensitive particles dispersed in an insulating liquid carrier.
  • photosensitive for the purposes of this application, refers to the properties of a particle which, once attracted to the injecting electrode, will migrate away from it under the influence of an applied electric field when it is exposed to actinic electromagnetic radiation.
  • Liquid suspension 4 may also contain a sensitizer and/or a binder for the particles which is at least partially soluble in the suspen ing or carrier liquid,
  • a j ent to he liq id suspension 4 is a second electrode 5, hereinafter called the blocking electrode, which is connected to one side of the potential source 6 through a switch 7.
  • the opposite side of potential source 6 is connected to the injecting electrode .1 so that when switch 7 is closed, an electric field is applied across the liquid suspension 4 between electrodes 1 and 5.
  • Electrode 5 is made in the form of a roller having a conductive central core 11 connected to the potential source 6.
  • the core is covered with a layer of a blocking electrode material 12, which may be Baryta paper.
  • the particle suspension is exposed to the image to be reproduced while potential is applied across the blocking and injecting electrodes by closing switch 7.
  • Roller 5 is caused to roll across the top surface of injecting electrode 1 with switch 7 closed during the period of image exposure.
  • This light exposure causes exposed particles originally attracted to electrode 1 to migrate through the liquid and adhere to the surface of the blocking electrode, leaving behind an image on the injecting electrode surface which is a duplicate of the original transparency 9'.
  • the relatively volatile carrier liquid evaporates off, leaving behind the particulate image.
  • This image may then be fixed in place as, for example, by placing a lamination over its top surface or a dissolved binder material in the carrier liquid such as parafiin wax or other suitable binder that comes out of solution as the carrier liquid evaporates. About 3% to 6% by weight of paraflin binder in the carrier has been found to produce good results.
  • the carrier liquid itself may be paraffin wax or other suitable binder.
  • the pigment image remaining on the injecting electrode may be transferred to another surface and fixed thereon.
  • This system can produce either monochromatic or polychromatic images depending upon the type and number of different colored particles suspended in the carrier liquid and the color of light to which this suspension is exposed in the process.
  • any suitable insulating liquid may be used as the carrier for the particles in the system.
  • Typical carrier materials are decane, dodecane, N-tetradecane, paraffin, beeswax, or other thermoplastic materials, Sohio Odorless Solvent (a kerosene fraction available from Standard Oil Company of Ohio), and Isopar-G (a long chain satuarted aliphatic hydrocarbon available from Humble Oil Company of New Jersey). Good quality images have been produced with voltages ranging from 300 to 5,000 volts, in the apparatus of the figure.
  • particles of a single color are dispersed in the carrier liquid and exposed to a black-and-white image.
  • a single color image results, corresponding to a conventional black-and-white photography.
  • the particles are selected so that those of different colors respond to different wavelengths in the visible spectrum coresponding to their principal absorption bands.
  • the particles should be selected so that their spectral response curves do not have substantial overlap, thus allowing for good color separation and subtractive multicolor image formation.
  • the particle dispersion should include cyan colored particles sensitive mainly to red light, magenta colored particles sensitive mainly to green light, and yellow colored particles sensitive mainly to blue light.
  • Any suitable cyan and magenta colored photosensitive particles having the desired spectral responses may be used with the yellow particles of this invention to form a particle suspension in a carrier liquid for color imaging. From about 2 to about percent particles by weight have been found to produce good results. The addition of small amounts (generally ranging from 0.5 to 5 mole percent) of electron donors or acceptors to the suspensions may impart significant increases in system photosensitivity.
  • kerosene fraction available from Standard Oil of Ohio and the magnitude of the applied potential is 2,500 volts.
  • All pigments which have a relatively large particle size as received commercially or as made are ground in a ball mill for 48 hours to reduce their size to provide a more stable dispersion which improves the resolution of the final images.
  • the exposure is made with a 3200 K. lamp through a conventional positive black-and-white transparency.
  • Example I The suspension comprises about 7 parts 2,4 di-(1'- anthraquinonyl-amino)-6-(1"-pyrenyl)-s-triazine in about 100 parts Sohio Odorless Solvent 3440. This suspension, when exposed to a black-and-white image, produces a monochromatic image in yellow-and-White corresponding to the original.
  • Example II The suspension comprises about 7 parts of 2,4-di-(1'- anthraquinonyl-amino)-6-(1" naphthyl)-s-triazine. This suspension, when exposed to a black-and-white image, produces an excellent image corresponding to the original.
  • a suspension including equal amounts of three different colored pigments is made up by dispersing the pigments in finely divided form in Sohio Odorless Solvent 3440 so that the pigments constitute about 8 percent of the mixture.
  • This mixture may be referred to as a tri-mix.
  • the mixtures are individually tested by coating them on a NESA glass substrate and exposing them as in Example I above, except that a multicolor Kodachrome transparency is interposed between the light source and the plate instead of the black-andwhite transparency.
  • a multicolored image is projected on the plate as the roller moves across the surface of the coated NESA glass substrate.
  • a Baryta paper blocking electrode is employed and the roller is held at negative potential of about 2,500 volts with respect to the substrate.
  • the roller is passed over the substrate six times, being cleaned after each pass. Potential application and exposure are both continued during the six passes by the roller. Then the quality of the image left on the substrate is evaluated as to density and color separation.
  • Example III The pigment mix consists of, as a magenta pigment, Watchung Red B, a barium salt of 1-(4-methyl-5'-chloro- 2'-sulfonic acid) azobenzene-Z-hydroxy-3-naphthoic acid, C.I. number 15865 available from Du Pont, as a cyan pig- :ment, Monolite Fast Blue GS, the alpha form of metalfree phthalocyanine, C.I. No. 74100, available from the Arnold Hoffman Company, and as a yellow pigment 2,4-di- 1-anthraquinonyl-amino)-6- 1"-pyrenyl) -s-triazine.
  • This tri-mix when exposed to a multi-colored image, produces a full color image with good density and color separation.
  • the pigment mixture consists of, as a magenta pigment, Locarno Red X-1686, C.I. No. 15865, 1-(4'-methyl- 5-chloro-2-sulfonic acid) azabenzene-Z-hydroxy-3-naphthoic acid, available from American Cyanamid, as a cyan pigment, Cyan Blue GTNF, the beta form of copper phthalocyanine, 01. No. 74160, available from Collway Colors, and as a yellow pigment 2,4-di-(1-naphthylamino)-6-( 1"-perylenyl)-s-triazine. This tri-mix is exposed to a multi-colored image and produces a full color image corresponding to the original.
  • Locarno Red X-1686 C.I. No. 15865
  • 1-(4'-methyl- 5-chloro-2-sulfonic acid) azabenzene-Z-hydroxy-3-naphthoic acid available from American
  • the pigment mixture consists of a magenta pigment, Naphtho Red B, 1-(2-methoxy5nitrophenylazo)-2-hydroxy-3"-nitro-3-naphthanilide, C.I. No. 12355, available from Collway Colors; a cyan pigment, a polychloro substituted copper phthalocyanine, C.I. No. 74260, available from Imperial Color and Chemical Company, and a yellow pigment 2,4(3'-cyano-anthraquinonyl-1'-amino)-6- (2"-cyano-1"-pyrenyl)-s-triazine. This tri-mix is exposed to a multi-color image and produces a full color image of good density and color separation.
  • a magenta pigment Naphtho Red B, 1-(2-methoxy5nitrophenylazo)-2-hydroxy-3"-nitro-3-naphthanilide, C.I. No. 12355, available from Collway Colors
  • Example VI The pigment mixture consinsts of a magenta pigment, Vulcan Fast Red BBE Toner 35-2201, 3,3'-dimethoxy- 4,4 biphenyl-bis(l-phenyl-3"methyl-4-azo- -perylene-5"-one), C.I. No. 21200, available from Collway Colors; a cyan pigment, Cyan Blue, 3,3'-methoxy-4,4'-diphenyl-bis(1"-azo-2"-hydroxy-3"-naphthanilide), C.I. No.
  • Example VII The pigment suspension consists of a magenta pigment, Indofast Brilliant Scarlet Toner, 3,4,9,10-bis(N,N'-pmethoxyphenyl-imido)perylene, C.I. No. 71140, available from Harmon Colors; a cyan pigment, Monolite Fast Blue GS, the alpha form of metal-free phthalocyanine,
  • the pigment suspension consists of a magenta pigment Calcium Litho Red, the calcium lake of an azo dye, 1- (2'-azo-naphthalene-1-sulfonic acid)-2-hydroxy-naphtho, OJ. No. 15630, available from Collway Colors; a cyan pigment, Cyan Blue XR, the alpha form of copper phthalocyanine, available from Collway Colors, and a yellow pigment, 2,4-di-(3,8 dimethoxy-anthraquinonyl-l-ami no)-6-(l"-chrysenyl)-s-triazine. This tri-mix is exposed to a multi-colored image and produces a full color image of good density and color separation.
  • a magenta pigment Calcium Litho Red the calcium lake of an azo dye, 1- (2'-azo-naphthalene-1-sulfonic acid)-2-hydroxy-naphtho, OJ. No. 15630, available from Collway Colors
  • xerographic plates may be produced by coating a relatively conductive substrate, e.g. aluminum or paper, with a dispersion of particles of the photosensitive pigment of the above general formula in a resin binder.
  • the pigment-resin layer may also be cast as a self-supporting film.
  • the plate formed may be both with or without an overcoating on the photoconductive layer.
  • the photosensitive pigment-resin photoconductive layer may be used in the formation of multilayer sandwich configurations adjacent a dielectric layer, similar to that shown by Golovin et al., in the publication entitled, A New Electrophotographic Process, Effected by Means at Combined Electret Layers, Dodklady Akad. Nauk SSSR, vol. 129, No. 5, pp. 1 088 1011, November-December, 1959.
  • Suitable materials for this purpose may include aluminum, steel, brass, metalized or tin oxide coated glass, semiconductive plastics and resins, paper and any other convenient material. Any suitable dielectric material may be used to overcoat the photoconductive layer.
  • a typical overcoating is bichromated shellac.
  • any suitable organic binder or resin may be used in combination with the pigment to prepare the photoconductive layer of this invention.
  • the resin used in the present invention must be more resistive than about 10 and preferably more than 10 ohm/cm. under the conditions of xerographic use.
  • Typical resins include thermoplastics such as polyvinylchloride, polyvinylacetates, polyvinylidenechloride, polystyrene, polybutadiene, polymethacrylates, polyacrylics, polyacrylonitrile, silicone resins, chlorinated rubber, and mixtures and copolymers thereof where applicable; and thermosetting resins such as epoxy resins including halogenated epoxy and phenoxy resins, phenolics, epoxy-phenolic copolymers, epoxy ureaformaldehyde copolymers, epoxy melamine formaldehyde copolymers and mixtures thereof where applicable.
  • Other typical resins are epoxy esters, vinyl epoxy resins, tall-oil modified epoxies, and mixtures thereof where applicable.
  • any other suitable resin may be used, if desired.
  • other binders such as parafiin and mineral Waxes may be used, if desired.
  • the pigments may be incorporated in the dissolved or melted binder resin by any suitable means such as strong sheet agitation, preferably with simultaneous grinding. These include ball milling, roller milling, sand milling, ultrasonic agitation high-speed blending and any desirable combination of these methods. Any suitable range of pigment-resin ratios may be used.
  • the pigment-resin-solvent slurry (or the pigment-resin rnelt) may be applied to the conductive substrate by any of the well-known painting or coating methods, including spraying, flow coating, knife coating, C1CtrO'COalilI1g,
  • Mayer bar drawdown, dip coating, reverse roll coating, etc. Spraying in an electric field may be preferred for the smoothest finish and dip coating for convenience in the laboratory.
  • the setting, drying and/or curing steps for these plates are generally similar to those recommended for films of the particular binder used for other painting applications.
  • pigment-epoxy plates may be cured by adding a cross-linking agent and stoving according to approximately the same schedule as other baking enamels made with the same resins and similar pigments for paint applications.
  • a very desirable aspect of these pigments is that they are stable against chemical decomposition at the temperatures normally used for a wide variety of bake-on enamels and, therefore, may be incorporated in very hard glossy photoconductive coatings, similar to automotive or kitchen appliance resin finishes.
  • the thickness of the photoconductive films may be varied from about 1 to about 100 microns, depending on the required individual purpose.
  • Self-supporting films for example, cannot usually be manufactured in thicknesses thinner than about 10 microns, and they are easiest to handle and use in the 15 to micron range.
  • Coatings on the other hand, are preferably formed in the 5 to 30 micron range. For certain compositions and purposes, it is desirable to provide an overcoating; this should usually not exceed the thickness of the photoconductive coating, and preferably not about one-quarter of the latter. Any suitable overcoating material may be used such as bichromated shellac.
  • Xerographic plates for use as in the following examples are prepared as follows.
  • Mixtures using specific pigments and resin binders are prepared by ball milling the pigment in a solution of a resinous binder and one or more solvents until the pigment is Well dispersed. This is done by adding the desired parts of the pigment to the desired parts of resin solution in a suitable mixing vessel. A quantity of one-eighth inch steel balls are added and the vessel is rotated for approximately one-half hour in order to obtain a homogeneous dispersion.
  • the cooling slurry is applied onto an aluminum substrate with a wire drawdown rod and force dried in an oven for about 3 minutes at about 100 C. The coated sheets are dark rested for about one hour and then tested.
  • the xerographic plate is initially prepared by mixing about 10 parts Lucite 2042, an ethyl methacrylate polymer available from Du Pont, about parts benzene and about 2 parts 2,4-di-(1'-anthraquinonyl-amino)-6-(1"- pyrenyl)-s-triazine. The mixture is coated onto an aluminum substrate to a thickness of about 8 microns and cured. The plate is charged negative in the dark by means of a corona discharge to a potential of about 400 volts. The charged plate is exposed to a film positive for about 30 seconds by means of a high intensity, long wave, ultra-violet lamp (1680 microwatts/cm. of 3660 a.u.
  • the latent electrostatic image is developed by cascading Xerox 1824 toner over the plate.
  • the powder image on the plate is electrostatically transferred to a receiving sheet and heat fused.
  • the image on the receiving sheet is of excellent quality and corresponds to the original.
  • the plate is wiped clean of any residual toner and reused as in the above manner.
  • Example X A xerographic plate is prepared by initially mixing about 10 parts Lucite 2042, about 90 parts benzene and about 9 2 parts 2,4-di-(1'-anthraquinonyl-amino) 6 (1"perylenyl)-s-triazine. The mixture is coated onto an aluminum substrate to a thickness of about 8 microns and cured. The plate is charged, exposed and developed as in Example VIII above. The image produced is observed to be of good quality.
  • Example XI A xerographic plate is prepared by initially mixing about 10 parts Lucite 2042, about 90 parts benzene and about 2 parts 2,4,-di-(1'-anthraquinonyl-amino)-6-(1"-4" ethylphenyl)-s-triazine. The mixture is coated onto an aluminum substrate to a thickness of about 8 microns and cured. The plate is charged negative in the dark by means of a corona discharge to a potential of about 400 volts. The charge plate is exposed for about 45 seconds to a light-and-shadow image using a Simmons Omega D3 Enlarger equipped with a tungsten light source operating at 2950 K. color temperature.
  • Illumination level incident on the plate is 2.8 foot candles as measured with a Weston Illumination Meter Model No. 756.
  • the latent electrostatic image is then developed by cascading Xerox 1824 toner over the plate.
  • the powder image on the plate is electrostatically transferred to a receiving sheet and heat fused.
  • the image on the receiving sheet is of good quality and corresponds to the original.
  • the plate is wiped clean of any residual toner and reused as in the above-described manner.
  • the third electrophotographic imaging process in which the above-listed novel photosensitive pigments are useful is that referred to as surface deformation imaging. As discussed above, this includes both frost and relief deformation of the surface of a deformable layer in image configuration.
  • Any suitable imaging method may be used in the surface deformation imaging processes of the present invention.
  • the following methods are typical:
  • the photoconductive thermoplastic layer is first substantially uniformly charged and exposed to a light and shadow image to be reproduced.
  • the material is then heated until it deforms to form a frost pattern corresponding to the light and shadow image.
  • the frost image thus formed is subsequently fixed or set by permitting the heat deformable layer to cool below its softening point.
  • the image may be erased by reheating the layer in charge free condition to its softening point.
  • thermoplastic layer is uniformly charged and exposed to a light and shadow image.
  • the material is then exposed to a solvent vapor, which softens the surface so that it deforms to form a frost pattern corresponding to the light and shadow image.
  • solvent is removed by evaporation to fix or set the image. This image may be layer erased by resoftening the layer surface, by heat or additional solvent vapor.
  • a relief image may be formed by scanning the thermoplastic layer with an electron beam, either while the layer is softened, or just prior to heat or solvent softening. This image may be set by returning the layer to its pre-softened condition.
  • any of the methods described in detail in copending applications 193,277, 232,494, and 388,322 filed May 8, 1962, Oct. 23, 1962 and Aug. 7, 1964, respectively, may be used in the process of this invention.
  • the methods of forming the frost or relief image may vary depending upon the intended use of the resulting product.
  • the heat deformable layer may be pretreated before uniformly charging the surface thereof.
  • various suitable methods may be used to selectively fix and/or erase the material in imagewise configuration.
  • any suitable material may be used as the surface deformable coating over the photoconductive layer or as the binder for the photosensitive pigments in a selfdeformable layer.
  • Typical surface deformable thermoplastic polymers are low molecular weight polymers or oligomers. Any suitable polymer may be used in the surface deformation process of this invention; typical polymers are aromatic polymers such as polystyrene, alpha methylstyrene; copolymers made from styrene and other materials such as vinyl toluene, methyl-styrene, polyalphamethyl styrene, chlorinated styrene, and polymers and copolymers made from petroleum cuts and indene polymers; phenolics such as phenol aldehyde resins, phenol formaldehyde resins and mixtures thereof; vinyl polymers such as polyvinylacetate, polyvinylalcohol, polyvinylbutyral, butylmethyl-acrylate-styrene polymers, but
  • the heat deformable image either relief or frost may be formed either (1) by direct deformation of the thermoplastic binder containing the photosensitive pigment or (2) by overcoating the pigment-binder layer with a thermoplastic layer which is itself deforrnable.
  • Example XII A plate is prepared by initially mixing about 10 parts Lucite 2042, an ethyl methacrylate polymer available from Du Pont, about parts benzene and about 2 parts 2,4 di(1' anthraquinonyl-amino) 6 (1"-[2-cyano]- pyrenyl)-s-triazine. This mixture is coated onto an aluminum substrate to a thickness of about 8 microns and cured. The plate is then overcoated with about a 10 micron layer of Piccofiex -A (a polyvinylchloride resin obtained from Pennsylvania Industrial Chemicals Company). The composite plate is then charged to a negative potential of about 1,000 volts in the dark by means of a corona discharge.
  • Piccofiex -A a polyvinylchloride resin obtained from Pennsylvania Industrial Chemicals Company
  • the charged plate is exposed through a film positive for about 30 seconds to a high intensity, long wave, ultra-violet lamp (1680 microwatts/cm. of 3660 an. radiation at a distance of 18 inches).
  • the latent electrostatic image is then developed by placing the plate on a heated platen maintained at about 70 C. As the plate is heated to the softening point of the overcoating, a series of very small wrinkles or folds spontaneously forms in unexposed areas, giving the image a frosted appearance.
  • Example XIII A plate is prepared by initially mixing about 10 parts of Staybelite Ester No. 10, available from the Hercules Powder Co., about 90 parts benzene and about 2 parts 2,4 di ('1' anthl'aquinonyl-amino)-6-(1"-pyrenyl)-striazine. The mixture is coated onto an aluminum substrate to a thickness of about 10 microns and cured. The plate is charged negative in the dark by means of a corona discharge to a potential of about 1,000 volts. The charged plate is contact exposed to a film positive for about 30 seconds using a high intensity, long wave, ultraviolet lamp (1680 microwatts/cm. of 3660 an. radiation at a distance of 18 inches). The frost image is developed by placing the plate on a heated platen maintained at about 70 C. As the plate is heated to the softening point of the resin, frost again appears in image configuration.
  • Example XIV A xerographic plate is prepared by initially mixing about parts Lucite 2042, about 90 parts benzene and about 2 parts 2,4-di-(3',8-dimethoxy-anthraquinonyl-1'- amino)6-(1"-chrysenyl)-s-triazine. The mixture is coated onto an aluminum substrate to a thickness of about 8 microns and cured. The plate is then overcoated with about a 10 micron layer of Staybelite Ester No. 10. The composite plate is given an electrostatic charge, exposed, and heated to the softening point of the overcoating, as in Example XIII above. When this threshold point is reached, an excellent frost image appears.
  • pigment compositions and/ or the pigment-resin compositions of this invention may be dye sensitized, if desired, or may be mixed or other wise combined with other photoconductors, both organic and inorganic.
  • the method of electrophoretic imaging comprising subjecting a layer of a suspension to an applied electric field between at least two electrodes, at least one of which is partially transparent, and simultaneously exposing said suspension to an image through said transparent electrode with activating electromagnetic radiation whereby a pigment image is formed on at least one of said electrodes; said suspension comprising a plurality of finely divided particles of at least one color, said particles of one color comprising a photosensitive pigment having the general formula:
  • R R and R are each selected from the group consisting of aryl, substituted aryl, alkaryl and substituted alkaryl.
  • the method of electrophoretic imaging comprising subjecting a layer of a suspension to an applied electric field between at least two electrodes, at least one of which is partially transparent, and simultaneously exposing said suspension to an image through said transparent electrode with activating electromagnetic radiation whereby a pigment image is formed on at least one of said electrodes; said suspension comprising a plurality of finely divided particles of at least one color, said particles of one color comprising a photosensitive pigment having the general formula:
  • R is a polynuclear aromatic radical
  • R and R are anthraquinone radicals.
  • the method of electrophoretic imaging comprising subjecting a layer of a suspension to an applied electric field between at least two electrodes, at least one of which is partially transparent and simultaneously exposing said suspension to an image through said transparent electrode with activating electromagnetic radiation whereby a pigment image is formed on at least one of said electrodes; said suspension comprising a plurality of finely divided particles of at least one color, said particles of one color comprising as a photosensitive pigment 2,4-di- 1'-anthraquinonyl-amino)-6-(1"-pyrenyl) -s-triazine having the structure:
  • the method of electrophoretic imaging comprising subjecting a layer of a suspension to an applied electric field between at least two electrodes, at least one of which is a blocking electrode, and simultaneously exposing said suspension to an image with activating electromagnetic radiation whereby a pigment image is formed on at least one of said electrodes; said suspension com prising a plurality of finely divided particles of at least one color, said particles of one color comprising a photosensitive pigment having the general formula:
  • R R and R are each selected from the group consisting of aryl, substituted aryl, alkaryl and substituted alkaryl.
  • the method of electrophoretic imaging comprising subjecting a layer of a suspension to an applied electric field between at least two electrodes, at least one of which is a blocking electrode, and simultaneously exposing said suspension to an image with activating electromagnetic radiation whereby a pigment image is formed on at least one of said electrodes; said suspension comprising a plurality of finely divided particles of at least one color, said particles of one color comprising a photosensitive pigment having the general formula:
  • the method of electrophoretic imaging comprising subjecting a layer of a suspension to an applied electric field between two electrodes, at least one of which is at least partly transparent, said suspension comprising a plurality of finely divided particles of at least two diflFerent colors in an insulating carrier liquid, the particles of each color comprising a photosensitive pigment whose principal light absorption band substantially coincides with its principal photosensitive response, simultaneously exposing said suspension to a light image through said partially transparent electrode and then separating said electrodes whereby a pigment image is formed on the surface of at least one of said electrodes, the particles of one color comprising compositions having the general formula:
  • R R and R are each selected from the group consisting of aryl, substituted aryl, alkaryl and substituted alkaryl.
  • the method of electrophoretic imaging comprising subjecting a layer of a suspension to an applied electric field between two electrodes, at least one of which is at least partly transparent, said suspension comprising a plurality of finely divided particles of at least two ditferent colors in an insulating carrier liquid, the particles of each color comprising a photosensitive pigment whose principal' light absorption band substantially coincides with its principal photosensitive response, simultaneously exposing said suspension to a light image through said partially transparent electrode and then separating said electrodes whereby a pigment image is formed on the surface of at least one of said electrodes, the particles of one color comprising compositions having the general formula:
  • R is a polynuclear aromatic radical; and, R and R are anthraquinone radicals.
  • the method of electrophoretic imaging comprising subjecting a layer of a suspension to an applied electric field between two electrodes, at least one of which is at least partly transparent, said suspension comprising a plurality of finely divided particles of at least two different colors in an insulating carrier liquid, the particles of each color comprising a photosensitive pigment whose principal light absorption band substantially coincides with its principal photosensitive response, simultaneously exposing said suspension to a light image through said partially transparent electrode and then separating said electrodes whereby a pigment image is formed on the surface of at least one of said electrodes, the particles of one color comprising 2,4-di(l'-anthraquinonyl-amino) 6 (l-pyrenyl)-s-triazine having the structure:
  • the method of electrophoretic imaging comprising subjecting a layer of a suspension to an applied electric field between two electrodes, at least one of which is a blocking electrode, said suspension comprising a plurality of finely divided particles of at least two different colors in an insulating carrier liquid, the particles of each color comprising a photosensitive pigment whose principal light absorption band substantially coincides with its principal photosensitive response, simultaneously exposing said suspension to a light image and then separating said electrodes whereby a pigment image is formed on the surface of at least one of said electrodes, the particles of one color comprising compositions having the general formula:
  • R R and R are each selected from the group consisting of aryl, substituted aryl, alkaryl and substituted alkaryl.
  • the method of electrophoretic imaging comprising subjecting a layer of a suspension to an applied electric field between two electrodes, at least one of which is a blocking electrode, said suspension comprising a plurality of finely divided particles of at least two difierent colors in an insulating carrier liquid, the particles of each color comprising a photosensitive pigment whose principal light absorption band substantially coincides with its principal photosensitive response, simultaneously exposing said suspension to a light image and then separating said electrodes whereby a pigment image is formed on the surface of at least one of said electrodes, the particles of one wherein:
  • R is a polynuclear aromatic radical
  • R and R are anthraquinone radicals.
  • the method of electrophoretic imaging comprising subjecting a layer of a suspension to an applied electric field between two electrodes, at least one of which is a blocking electrode, said suspension comprising a plurality of finely divided particles of at least two different colors in an insulating carrier liquid, the particles of each color comprising a photosensitive pigment whose principal light absorption band substantially coincides with its principal photosensitive response, simultaneously exposing said suspension to a light image and then separating said electrodes whereby a pigment image is formed on the surface of at least one of said electrodes, the particles of one color comprising 2,4 di (1-anthraquinonyl-amino)-6- -pyrenyl)-s-triazine having the structure:
  • R R R R are each selected from the group consisting of aryl, substituted aryl, alkaryl and substituted alkaryl.
  • a xerographic plate comprising a photoconductive layer comprising a binder material and a composition having the general formula:
  • R is a polynuclear aromatic radical; and, R and R are anthraquinone radicals.
  • a Xerographic plate comprising a photoconductive 16 layer comprising a binder material and 2,4-di-(l'-anthraquinonylamino) 6 (1" pyrenyl) s triazine having the structure:
  • a process for forming a latent xerographie image on a photoconductive layer comprising a photoconductive pigment and an organic binder, which comprises electrostatically charging said layer and exposing said layer to a pattern of activating electromagnetic radiation; said photoconductive pigment comprising the composition having the general formula:
  • R R and R are each selected from the group consisting of aryl, substituted aryl, alkaryl and substituted alkaryl.
  • a process for forming a latent xerographic image on a photoconductive layer comprising a photoconductive pigment and an organic binder, which comprises electrostatically charging said layer and exposing said layer to a pattern of activating electromagnetic radiation; said photoconductive pigment comprising the composition having the general formula:
  • R is a polynuclear aromatic radical
  • R and R are anthraquinone radicals.
  • a process for forming a latent xerographic image on a photoconductive layer comprising a photoconductive pigment and an organic binder, which comprises electrostatically charging said layer and exposing said layer to a pattern of activating electromagnetic radiation; said photoconductive pigment comprising 2,4-di-(1'-anthraquinonyl-amino) 6 (1" pyrenyl)-striazine having the structure:
  • a method for forming an image on a surface deformable recording medium which comprises electrostatically charging a recording medium, exposing said medium to a pattern of light-and-shadow and maintaining the surface of said medium in a sufliciently viscous condition to thereby deform at least a portion of said surface in a configuration corresponding to said pattern of lightand-shadow
  • said recording medium comprises photoconductive pigment particles in a thermoplastic binder, said photoconductive pigment comprising the composition having the general formula R1 N tilt Rr-NH( C-NEE-Rs wherein:
  • R R and R are each selected from the group con- 18 sisting of aryl, substituted aryl, alkaryl, and substituted alkaryl.
  • a method for forming an image on a surface deformable recording medium which comprises electrostatically charging a recording medium, exposing said medium to a pattern of light-and-shadow and maintaining the surface of said medium in a sufficiently viscous condition to thereby deform at least a portion of said surface in a configuration corresponding to said pattern of lightand-shadow, said recording medium comprising a coating of photoconductive pigment particles in an organic binder on a supporting substrate and an overcoat of thermoplastic material on said coating; said photoconductive pigment comprising the composition having the general formula:
  • R R and R are each selected from the group consisting of aryl, substituted aryl, alkaryl, and substituted alkaryl.

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US445179A 1965-04-02 1965-04-02 Electrophotographic imaging processes employing 2,4-diamino-triazines as the electrically photosensitive particles Expired - Lifetime US3445227A (en)

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US20030074741A1 (en) * 2001-10-18 2003-04-24 The Procter & Gamble Company Process for the manufacture of polycarboxylic acids using phosphorous containing reducing agents
US20030088923A1 (en) * 2001-10-18 2003-05-15 The Procter & Gamble Company Textile finishing composition and methods for using same
US20030111633A1 (en) * 2001-10-18 2003-06-19 Gardner Robb Richard Durable press treatment of fabric
US20030110573A1 (en) * 2001-10-18 2003-06-19 The Procter & Gamble Company Textile finishing compositon and methods for using same
US20040104148A1 (en) * 1999-08-20 2004-06-03 Lomas David A. Controllable space velocity reactor and process
US6989035B2 (en) 2001-10-18 2006-01-24 The Procter & Gamble Company Textile finishing composition and methods for using same
US7018422B2 (en) 2001-10-18 2006-03-28 Robb Richard Gardner Shrink resistant and wrinkle free textiles

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US3244516A (en) * 1959-04-09 1966-04-05 Azoplate Corp Electrophotographic mateiral and process
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US2650920A (en) * 1951-09-27 1953-09-01 American Cyanamid Co Triazine vat dyes
US2832779A (en) * 1955-03-30 1958-04-29 Basf Ag Production of 4-aryl-2.6-dihydroxy-1.3.5-triazines
US3130046A (en) * 1959-01-07 1964-04-21 Azoplate Corp Electrophotographic reproduction material
US3244516A (en) * 1959-04-09 1966-04-05 Azoplate Corp Electrophotographic mateiral and process
US3238041A (en) * 1962-05-08 1966-03-01 Xerox Co Relief imaging of photoresponsive member and product
US3258336A (en) * 1962-05-08 1966-06-28 Xerox Corp Strippable layer frost printing

Cited By (15)

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Publication number Priority date Publication date Assignee Title
US20040104148A1 (en) * 1999-08-20 2004-06-03 Lomas David A. Controllable space velocity reactor and process
US6989035B2 (en) 2001-10-18 2006-01-24 The Procter & Gamble Company Textile finishing composition and methods for using same
US7018422B2 (en) 2001-10-18 2006-03-28 Robb Richard Gardner Shrink resistant and wrinkle free textiles
US20030110573A1 (en) * 2001-10-18 2003-06-19 The Procter & Gamble Company Textile finishing compositon and methods for using same
US20030088923A1 (en) * 2001-10-18 2003-05-15 The Procter & Gamble Company Textile finishing composition and methods for using same
US6841198B2 (en) 2001-10-18 2005-01-11 Strike Investments, Llc Durable press treatment of fabric
US20030074741A1 (en) * 2001-10-18 2003-04-24 The Procter & Gamble Company Process for the manufacture of polycarboxylic acids using phosphorous containing reducing agents
US7008457B2 (en) 2001-10-18 2006-03-07 Mark Robert Sivik Textile finishing composition and methods for using same
US20030111633A1 (en) * 2001-10-18 2003-06-19 Gardner Robb Richard Durable press treatment of fabric
US20060085920A1 (en) * 2001-10-18 2006-04-27 Scheper William M Textile finishing composition and methods for using same
US20060090266A1 (en) * 2001-10-18 2006-05-04 Gardner Robb R Shrink resistant and wrinkle free textiles
US20060090267A1 (en) * 2001-10-18 2006-05-04 Sivik Mark R Textile finishing composition and methods for using same
US7144431B2 (en) 2001-10-18 2006-12-05 The Procter & Gamble Company Textile finishing composition and methods for using same
US7169742B2 (en) 2001-10-18 2007-01-30 The Procter & Gamble Company Process for the manufacture of polycarboxylic acids using phosphorous containing reducing agents
US7247172B2 (en) 2001-10-18 2007-07-24 The Procter & Gamble Company Shrink resistant and wrinkle free textiles

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BE743891A (enrdf_load_stackoverflow) 1970-06-30
DE1522686B2 (de) 1975-10-30
GB1146019A (en) 1969-03-19

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