US3511655A - Laminations - Google Patents

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US3511655A
US3511655A US451894A US3511655DA US3511655A US 3511655 A US3511655 A US 3511655A US 451894 A US451894 A US 451894A US 3511655D A US3511655D A US 3511655DA US 3511655 A US3511655 A US 3511655A
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vinyl
layer
hydrolyzed
copolymer
image
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US451894A
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Howard C Haas
Harold O Buzzell
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Polaroid Corp
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Polaroid Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C11/00—Auxiliary processes in photography
    • G03C11/08—Varnishing, e.g. application of protective layers on finished photographic prints
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S283/00—Printed matter
    • Y10S283/904—Credit card

Definitions

  • Laminar structures comprising a color photograph bonded to a transparent embossable rigid or semi-rigid vinyl overlay through an intermediate layer of a vinyl lower alkyl ester-vinyl chloride copolymer, the surface of which is hydrolyzed, the image-bearing surface of the color photograph being bonded directly to the hydrolyzed surface of said intermediate layer or being bonded indirectly thereto through a layer consisting essentially of polyvinyl alcohol; and transparent ID cards having this structure.
  • This invention relates to a novel and improved card that serves to identify its holder.
  • a further object of the present invention is to provide an identification card, or the like, which bears a photographic likeness of its holder in color and which will automatically be defaced by, or will automatically reveal any attempt to change or alter said photographic likeness.
  • a further object of the present invention is to provide an identification card of the type described above which is durable and which will provide a long and useful service life.
  • a further object of the present invention is to provide novel laminations comprising photographic likenesses in color which cannot be separated without destroying or defacing said photographic likenesses.
  • a further object of the present invention is to provide an identification card of the type described above which is suitable for embossing and which is capable of permanently maintaining raised or embossed figures.
  • FIG. 1 is a cross-section, greatly magnified, of one stage in the preparation of a lamination made in accordance with this invention
  • FIG. 2 is a cross-section, greatly magnified, of a completed lamination made in accordance with this invention
  • FIG. 3 is a cross-section, greatly magnified of another embodiment of a lamination made in accordance with this invention.
  • FIG. 4 is ⁇ an illustration of one method of preparing the lamination of this invention.
  • FIG. 5 represents a plan view of one stage in the preparation of one embodiment of the laminations of this invention.
  • FIG. 6 represents a section taken along line 6-6 of FIG. 5;
  • FIG. 7 represents a section of the embodiment shown in FIGS. 5 and 6 when complete.
  • FIG. 8 represents a section of the embodiment shown in FIG. 2 when embossed.
  • a card or badge which comprises a photographic likeness of its holder in color together with any other desired identifying indica, which card or badge is laminated to a transparent rigid or semirigid film by way of a so-called security seal, that is, a seal which cannot be broken or tampered with without immediately clearly rendering obvious the intrusion by destroying or defacing the photographic likeness.
  • Such cards be embossable with certain information, such as with the holders name, address, or code number.
  • embossed cards may be placed in a small imprinter whereby the embossed indicia are applied to a receipt form or the like.
  • Such cards are generally termed self-writing since they eliminate the time that would be required to manually imprint the necessary indicia on the receipt form. It is necessary that such cards have an outer surface comprising a synthetic material capable of providing stable, sharp-edged raised letters or numerals as a result of a suitable embossing procedure, the techniques for which are well known to the art.
  • Synthetic films of the aforementioned nature are conventionally known as rigid vinyls or semi-rigid vinyls, and generally cornprise polyvinyl chloride/vinyl acetate resins which are blends of polyvinyl chloride and polyvinyl acetate or copolymers of vinyl chloride and vinyl acetate, having a relatively high chloride content.
  • a suitable plasticizer that is a plasticizer which is compatible ⁇ with the main polymeric materials and which does not significantly affect their embossability, may also be present.
  • the identification card contains a photographic likeness of its holder, it is desira-ble, in the interest of speed and efliciency, to provide a rapid means of obtaining such a likeness.
  • photographic images of the type which may be produced by color diffusion transfer processes. In such processes a sheet of photosensitive material is exposed to create therein a latent image. The latent image is developed and, concurrent with and under the control of this development, an imagewise distribution of colorproviding material is formed. At least a portion of these color-providing materials is transferred by means of an alkaline aqueous processing solution t0 a superposed image-receiving layer to form a color positive image thereon.
  • a latent image in a silver halide photosensitive element is developed in the presence of a dye developer and, as a result of this development, the dye developer in the exposed areas is oxidized and substantially immobilized. At least a portion of the immobilization is believed to be due, at least in part, to a change in the solubility characteristics of the dye developer upon oxidation and especially as regards its solubility in alkaline solutions.
  • the dye developer is unreacted and diffusible, and thus provides an imagewise distribution of unoxidized dye developer, dissolved in the liquid processing composition, as a function of the point-to-point degree of exposure of the silver halide emulsion.
  • At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer or element, said transfer excluding oxidized dye developer.
  • the image-receiving element receives a depthwise diffusion, from the developed emulsion, of unoxidized dye developer without appreciably disturbing the imagewlise distribution thereof to provide a reversed or positive color image of the developed image.
  • the image-receiving element used in processes of the aforementioned type generally comprises an opaque or transparent support coated with an image-receiving layer of a dyeable material which is permeable to the alkaline aqueous processing solution.
  • the dyeable material 'prefera-bly comprise polyvinyl alcohol together with a polyvinyl pyridine polymer such as a poly-4-viny1 pyridine polymer.
  • a polyvinyl pyridine polymer such as a poly-4-viny1 pyridine polymer.
  • Diffusion transfer photographic processes of the type described above are particularly adapted for use in a Polaroid Land Camera made by Polaroid Corporation, Cambridge, Mass. 02139, or a smaller camera structure such, for example, as the camera forming the subject matter of US. Pat. No. 2,435,717 issued to Edwin H. Land on Feb. 10, 1948.
  • the image-receiving element which comprises the diffusion transfer color photograph may be pressed directly onto the surface of the hydroxylated polymer layer without additional wetting. lf the latter method is employed, i.e., no additional wetting of the image-receiving element prior to lamination, the lamination procedure should take place as soon as possible after the image-receiving element is stripped from the photosensitive element, preferably within 10 seconds thereof. If a longer time is permitted to elapse, while the image-receiving element may still be damp, the moisture remaining on its surface may be insufficient to provide a good security seal.
  • the embossible films which are laminated to diffusion transfer color photographs in accordance with this invention comprise high chloride content polyvinyl chloride/ vinyl acetate rigid vinyls, such as Vynex NVH-860, a polyvinyl chloride/vinyl acetate resinous film having an average acetate content of 15% and including minor amounts of appropriate stabilizers, ultraviolet absorbers, lubricants, and the like, commercially available from Nixon-Baldwin Chemicals Inc., Nixon, NJ.; Oriex 7-300-18, a biaxially oriented rigid vinyl similar in composition to Vynex, also available from Nixon-Baldwin Chemicals, Inc.; and VCA-3615 semirigid vinyl, a high chloride content polyvinyl chloride/ vinyl acetate resin similar in composition to the foregoing materials except that it includes a minor amount of an appropriate plasticizer, commercially available from Bakelite C0., a Division of Union Carbide and Carbon Corp., New York, N.Y.
  • an appropriate plasticizer
  • the precise ratio of vinyl chloride to vinyl acetate in the rigid or semi-rigid vinyl overlay is not critical in the preparation of laminations characterized by security seals in accordance with this invention, other than that the vinyl comprise a major amount of vinyl chloride and a minor amount of vinyl acetate.
  • the vinyl overlay must be both substantially transparent and capable of maintaining embossed figures having permanent sharp edges.
  • a bonding layer to the vinyl comprising a surface-hydrolyzed vinyl lower alkyl ester-vinyl chloride copolymer having a vinyl chloride content on a molar basis of no more than -about 50% and preferably no less than about 30%. It has been found that if the copolymer contains more vinyl chloride than about 50%, even after surface hydrolysis, the overlay exhibits a tendency to separate from the photograph.
  • Copolymers containing less than about 30% vinyl chloride may also be employed; however, while such materials generally provide satisfactory security seals with semi-rigid, or plasticized, vinyls, they do not always adhere uniformly to the unplasticized rigid vinyls described above.
  • the vinyl lower alkyl ester is vinyl acetate.
  • the copolymer may be prepared, for example, by combining the vinyl lower alkyl ester and vinyl chloride in the desired ratio in a suitable pressurized vessel under an inert atmosphere, along with appropriate quantities of a polymerization catalyst, such as ammonium, sodium, or potassium persulfate, benzoyl peroxide, etc., a wetting agent such as sodium lauryl sulfate, and water, and optionally, an emulsion stabilizer such as acetic acid and a redox reaction initiator to decompose the catalyst, such as sodium bisulte.
  • a polymerization catalyst such as ammonium, sodium, or potassium persulfate, benzoyl peroxide, etc.
  • a wetting agent such as sodium lauryl sulfate
  • an emulsion stabilizer such as acetic acid and a redox reaction initiator to decompose the catalyst, such as sodium bisulte.
  • the last-mentioned material enables the copolymerization reaction to he run at relatively low ternperatures, thereby avoiding undesirable pressure buildup.
  • the mixture is warmed, stirred, or tumbled, and allowed to react for a suitable length of time, after which the resulting latex is acid-coagulated, filtered, washed and dried.
  • copolymers for the bonding layer in laminations prepared in accordance with the teachings of this invention may be prepared by any one of the many techniques known to the art of synthetic resins.
  • copolymers so prepared are dissolved in any organic solvent in which they are soluble, preferably a lowboiling ketone such as acetone forVquick-drying properties.
  • a lowboiling ketone such as acetone forVquick-drying properties.
  • the resulting solution is then applied to one side of a rigid or semi-rigid vinyl film as described above and dried.
  • the surface of the copolymer layer so applied is then hydrolyzed, preferably by the following procedure:
  • the entire film is immersed at a temperature of about 30- 50 C. for a short period of time in a hydrolyzing solution comprising a mixture of a material capable of hydrolyzing the vinyl acetate groups at the surface of the copolymer layer to vinyl alcohol groups, e.g., an alkali metal hydroxide, and a material capable of softening the copolymer layer, such as a water-alcohol blend and preferably, a water-lower alcohol mixture having a water-toalcohol ratio of about 1:1 by volume.
  • a hydrolyzing solution comprising a mixture of a material capable of hydrolyzing the vinyl acetate groups at the surface of the copolymer layer to vinyl alcohol groups, e.g., an alkali metal hydroxide, and a material capable of softening the copolymer layer, such as a water-alcohol blend and preferably, a water-low
  • the preferred reaction time is about seconds at about 40 C. Reaction times of less than about 13 seconds at this temperature, tend to result in insufficient hydrolysis of the acetate groups for a good security seal; longer reaction times effect deeper hydrolysis of the copolymer layer which, while not being detrimental to the security seal, does nothing to enhance it. It will be appreciated that by routine experimentation, the reaction time and temperature required for an effective degree of hydrolysis where other vinyl lower alkyl esters are employed can be readily determined.
  • security sealed laminations comprising diffusion transfer color photographic prints may be prepared by placing the wet surface of the print against the surface hydrolyzed vinyl acetate-vinyl chloride copolymeric layer as described above and pressing the surfaces together. High pressures are not necessary to achieve the security bond, but may aid in the exclusion or expulsion of any air which may be trapped between the layers, and may reduce the time necessary for the bond to setf If the color print is damp immediately prior to lamination, water alone may be used to wet the photographic print surface or the hydrolyzed copolymer surface in order to form a security seal.
  • the water used to wet the surfaces includes dissolved polyvinyl alcohol which provides a doping material. Solutions containing up to 10% polyvinyl alcohol, preferably completely hydrolyzed, have been found to be particularly efficacious in this respect. Higher concentrations of polyvinyl alcohol may be employed but such solutions give no added advantage in the preparation of the lamination and may prove undesirably viscous for mechanical consideration. Moreover, the higher the polyvinyl alcohol concentration in the wetting solution, the longer it takes for the seal to set and dry.
  • the wet diffusion transfer photographic image may be simply placed in face-to-face relationship with the hydrolyzed polymeric surface and pressure applied directly.
  • the print to be laminated may be fed, together with the transparent overlay material, between two rolls ordinarily known as V-ing rolls. If the surfaces have not been wet previously, they can be readily wetted during the latter lamination procedure by spreading a droplet of water along one edge of the surface of the print or the hydrolyzed copolymer surface immediately prior to its being fed into the V-ing rolls. The droplet of water then forms at the nip between the surfaces being laminated and passes over the surfaces, thus effectively providing the necessary moisture.
  • the hydrolysis techniques described above may not always result in a uniformly hydrolyzed surface. While diffusion transfer color photographs can be satisfactorily bonded to such surfaces in a security seal, it has been found that the uniformity of the seal can be improved by providing a thin layer of polyvinyl alcohol on the hydrolyzed copolymer surface prior to its lamination to the print surface.
  • the simplest procedure for achieving such a layer is coating the hydrolyzed copolymer surface with an aqueous solution of hydrolyzed polyvinyl alcohol, drying the coating, and laminating the polyvinyl alcohol surface to the diffusion transfer color photograph by the same methods described above, in which there was no separate polyvinyl alcohol layer.
  • concentration of polyvinyl alcohol in the coating solution is not critical, but is preferably less than about 10%, so that the layer can dry in a relatively short time.
  • a thin sheet of poly-vinyl alcohol can be laminated to the hydrolyzed copolymer surface with water, or preferably, water containing up to 10% by weight polyvinyl alcohol, by any of the various methods well known to the laminating art.
  • the outer surface ofthe polyvinyl alcohol sheet is then laminated to the image-bearing surface of the diffusion transfer color photograph by the same techniques described previously.
  • the polyvinyl alcohol sheet may, if desired, comprise a light-polarizer.
  • a second security feature is added to the final laminated photographic image, in addition to that provided by the security bond. Any attempt to tamper with or otherwise alter the surface of the laminate, e.g., by cutting into the material or heating it, affects the light-polarizing properties of the surface to the extent that the attemped alteration or intrusion can be readily detected with a suitable light-polarizing analyzer.
  • transparent lightpolarizing sheets as a security feature for laminates is described and claimed in the copending U.S. patent application of Robert L. Malster, Ser. No. 451,895, filed concurrently herewith, now U.S. Pat. No. 3,313,052.
  • FIG. 1 represents the layers as previously described immediately prior to lamination, comprising a diffusion transfer color photograph 9, a rigid or semi-rigid vinyl overlay 10 on which a layer 11 of vinyl lower alkyl ester-vinyl chloride copolymer has been coated and the surface 12 hydrolyzed.
  • a drop of wetting solution 13 has been placed between the diffusion transfer photograph 9 and surface-hydrolyzed layer 11 which, when spread between the layers, effects their bonding together in a security seal. It will be appreciated that, as described above, if the diffusion transfer color photograph is still wet from photographic processing, wetting solution 13 may be unnecessary.
  • FIG. 2 represents the structure shown in FIG. 1, in which the wetting liquid has been spread, and the respective layers pressed together to form security bond 14, thus completing the lamination.
  • FIG. 3 is a cross section, greatly magnified, of another embodiment of the laminations of this invention, wherein a layer of polyvinyl alcohol is interposed between the image-bearing surface of a diffusion transfer color photograph and the copolymer-coated vinyl overlay.
  • the lamination comprises a rigid or semi-rigid vinyl sheet 10 having bonded thereto a surface-hydrolyzed (12) layer 11 of vinyl lower alkyl ester-vinyl chloride, to the hydrolyzed surface 12 of which is bonded a layer 15 of polyvinyl alcohol.
  • the image-bearing surface of a diffusion transfer color photograph 9 is in turn bonded to the polyvinyl alcohol layer 15.
  • FIG. 4 is a cross section, greatly magnified, of a laminated diffusion transfer color photograph being prepared by one of the methods described previously.
  • the sheet materials comprising the diffusion transfer color photograph 9 and rigid or semi-rigid vinyl sheet 10 with its surface-hydrolyzed (12) layer 11 of vinyl lower alkyl ester-vinyl chloride copolymer, are fed between two V-ing rolls 22 and 16 rotatably mounted and suitably driven in directions indicated by the arrows on the rolls.
  • Rolls 22 and 16 are adjustable with respect to the distances between centers so that a suitable pressure may be brought to bear upon the contacting surface of the sheets.
  • Numeral 13 designates a bead of wetting liquid maintained at the nip between the two sheets of material undergoing lamination adjacent the point of contact. As the bead 13 is forced by the rotation of rolls 22 and 16 over the surfaces of the layers being laminated, it wets the surfaces sufficiently to provide for the formation of security bond 14.
  • FIGS. through 7 represent a special embodiment of this invention, which may be characterized as an envelope or pouch comprising a diffusion transfer color photograph laminated to one of its inner surfaces in a security bond.
  • FIG. 5 is a plan view of an envelope or pouch which has been prepared for providing the aforementioned embodiment, prior to lamination.
  • the envelope or pouch comprises Wall 17, which is made up of a transparent rigid or semi-rigid vinyl overlay coated with a surface-hydrolyzed vinyl lower alkyl ester-vinyl chloride copolymer as previously described.
  • Wall 17 is heat, solvent, or adhesive-sealed around a portion of its periphery 1'8 to a non-adhesive backing 19, which is preferably flexible, leaving the remainder of the periphery open for the insertion of the diffusion transfer color photograph.
  • FIG. 6 is a section taken along lines 6 6 of FIG. 5, and shows the relationship of rigid or semi-rigid vinyl layer with its surface-hydrolyzed (12.) layer 11 of vinyl lower alkyl ester-vinyl chloride copolymer, both of which when taken together comprise the front wall 17 of the envelope, sealed at its periphery 18 to backing 19. It is noted that in the absence of water, the hydrolyzed sur- 8 face 12 will exhibit no tendency to adhere to non-adhesive backing 19.
  • Envelopes or pouches so prepared provide ready structures for lamination to diffusion transfer color photographs.
  • the photograph is either taken While still fresh and wet from photographic processing, or is mechanically wetted, and is inserted into the pouch or envelope by Way of its open end, in such a way that the image-bearing surface of the photograph is immediately adjacent to the hydrolyzed surface.
  • the entire envelope is subjected to pressure, such as by passing it between V- ing rolls as described above, to provide the security bond. (The use of V-ing rolls to provide the necessary pressure gives the additional advantage that any excess wetting solution can be forced out of the envelope by way of its open end.)
  • the envelope is then sealed along its remaining open end.
  • FIG. 7 is a section similar to that of FIG. 6, showing the relationship of all of the elements when a completed laminate is prepared as just described.
  • the final structure is an envelope or pouch comprising a transparent front wall 17, made up of a vinyl overlay 10 of a rigid or semi-rigid vinyl film having a layer 11 on its inner surface of a surface-hydrolyzed vinyl lower alkyl estervinyl chloride copolymer, to the hydrolyzed surface 12 of which is bonded the image-bearing surface of a diffusion transfer color photograph 9 in a security bond 14.
  • Front wall 17 is sealed about its entire periphery 18 and 20 to non-adhesive backing 19 to provide a sealed, tamperproof lamination.
  • FIG. 8 represents an embodiment substantially identical to that given in FIG. 2, showing the relationship of the various elements when the lamination has been embossed with raised characters 21.
  • the bottle was sealed under an atmosphere of nitrogen and tum-bled at about 45 C. for about 21/2 hours.
  • the resulting latex was coagulated with a small amount of concentrated hydrochloric acid.
  • the coagulated polymer was filtered, Iwashed well with water to remove all traces of the Nornol-C, dissolved in acetone-methanol, precipitated into Water, and dried.
  • the resulting copolymer had a vinyl acetate to vinyl chloride molar ratio of 7:3.
  • Example II A copolymer was prepared by the procedure of Example I, except that the bottle was tumbled for a period of about 18 hours; a substantially identical product was recovered.
  • Example III A copolymer was prepared by the procedure of Example I, except that the glacial acetic acid was omitted from the reaction mixture. A substantially identical product was recovered.
  • Example IV A copolymer prepared by the procedure of Example I having a vinyl acetate to vinyl chloride molar ratio of 7:3 was dissolved in acetone to provide a solution having a concentration of about 1%. The solution was coated onto one side of an extruded high chloride content polyvinyl chloride/vinyl acetate resinous film having an average acetate content of about (commercially available from Nixon-Baldwin Chemicals Inc., Nixon, NJ under the trade name Vynex NVH-860), and the coating thus applied was allowed to dry.
  • the entire film so treated was immersed for about 15 seconds at about 40 C. in a solution prepared by dissolving 50() g. of sodium hydroxide in a mixture of 500 cc. of water and 500 cc. of methanol. Thereafter, the film was removed from the solution, washed with water until the surface was neutral as determined with pHydrion paper, and dried.
  • Example V The procedure of Example IV was followed, except the film coated with the copolymer was a plasticized high chloride content vinyl chloride/vinyl acetate semi-rigid vinyl, commercially available from Bakelite Co., a Division of Union Carbide and Carbon Corp., New York, N.Y., designated as VCA-3615 resin.
  • Example VI The procedure of Example IV was followed except that the film coated with the copolymer was a biaxially oriented polyvinyl chloride-acetate resin having an average acetate content of 15%, commercially available from Nixon-Baldwin Chemicals Inc., under the trade name Oriex 7-300-18.
  • Example VII The procedure of Example IV was followed except that the copolymer used to coat the rigid vinyl film had a vinyl acetate to vinyl chloride molar ratio of 1:1.
  • Example VIII A plasticized semi-rigid vinyl film substantially identical to that used in Example V was coated with a 1% solution of polyvinyl acetate in acetone. The coating was allowed to dry, and the film was surface-hydrolyzed by the procedure given in Example IV.
  • Example X A lamination was prepared as in Example IX, except that following stripping from its photosensitive element, the surface of the image carrying layer was allowed to dry completely, and was subsequently wet with a solution of 2% completely hydrolyzed polyvinyl alcohol in water. The resulting lamination exhibited a security bond substantially identical to that of the lamination prepared in Example IX, but there was less tendency for air bubbles to be trapped between the layers.
  • Example XI A lamination was prepared exactly as in the foregoing example, except that the solution of 2% completely hydrolyzed polyvinyl alcohol in water was swabbed onto the hydrolyzed copolymer surface on the rigid vinyl overlay instead of the image-bearing surface of the photographic print. An identical lamination resulted.
  • Example XII A diffusion transfer color photograph was prepared as in Example IX and was allowed to dry. The surface of the photograph was wetted with a 2% polyvinyl alcohol solution in water and was pressed firmly against the surface-hydrolyzed 7:3 vinyl acetate-vinyl chloride copolymer layer on a semi-rigid vinyl film substantially identical to that prepared in Example V. The resulting lamination was substantially identical to the one prepared in Example X, except that it exhibited a higher degree of flexibility.
  • Example XIII A lamination was prepared as in Example XI except that the overlay was a biaxially oriented rigid vinyl film having a layer of surface-hydrolyzed 7:3 vinyl acetatevinyl chloride copolymer, substantially identical to that prepared in Example VI. The resulting lamination was substantially identical to that prepared in Example X.
  • Example XIV A lamination was prepared as in Example XI except that the overlay was an extruded rigid vinyl film having a layer of surface-hydrolyzed 1:1 vinyl acetate-vinyl chloride copolymer, substantially identical to that prepared in Example VII. The resulting lamination was substantially identical to that prepared in Example X.
  • Example XV A 1% solution of vinyl acetate in acetone was coated onto a semi-rigid vinyl film substantially identical to that described in Example V. The coating was allowed to dry, after which it was surface-hydrolyzed following the procedure of Example IV. A diffusion transfer color photograph, prepared as in the foregoing examples, was allowed to dry, and was subsequently wet with a 2% solution of polyvinyl alcohol and pressed firmly onto the hydrolyzed vinyl acetate surface. The resulting lamination was substantially identical to that prepared in Example XI.
  • Example XVI A one-inch wide strip of a linear dichroic polyvinylenepolyvinyl alcohol light-polarizing sheet having a cellulose acetate butyrate backing, commerci-ally available from Polaroid Corporation, Cambridge, Mass. 02139, and designated as type KN-42, was swabbed with a doping solution consisting of 10% by weight polyvinyl alcohol in water, and was pressed firmly against the surface-hydrolyzed 7:3 vinyl acetate-vinyl chloride layer on a rigid vinyl film prepared as described in Example IV.
  • the image-bearing surface of a diffusion transfer color photograph prepared as in the foregoing examples and dried, was wetted with the same doping solution, and was then pressed onto the vinyl film in such a way that the polarizer strip was sandwiched between the image-bearing surface and the vinyl film, and covered a portion but not all of the photographic image.
  • the resulting lamination exhibited a security seal similar to those described in the above examples.
  • the laminate includes a strip of light-polarizing material, an ⁇ additional security feature is added to the final laminated photographic-image as described previously.
  • Example XVII A rigid vinyl film was coated with a layer of vinyl acetate-vinyl chloride copolymer and hydrolyzed as in Example IV. An yaqueous solution containing 4% by Weight completely hydrolyzed polyvinyl alcohol was doctored onto the hydrolyzed copolymeric surface and dried. The dry, image-bearing surface of a diffusion transfer color photograph prepared as in the foregoing examples was wet with a solution of 2% completely hydrolyzed polyvinyl alcohol in water, and was then pressed firmly against the polyvinyl alcohol surface on the rigid vinyl. The resulting lamination exhibited a security seal of excellent uniformity, and similar in strength to the seals provided in the foregoing examples.
  • test (2) in which the laminates were packed in Dry Ice, the laminates readily shattered; the image could still not be separated from the rest of the laminate, even in a fragmented condition.
  • diffusion transfer image-receptive elements of the type described above generally comprise at least in part polyvinyl alcohol.
  • the bond which forms between the surface of such an element and the surface-hydrolyzed vinyl acetate-vinyl chloride copolymerie layer is considerably stronger than bonds generally formed when simple polyvinyl alcohol surfaces are water-laminated to other polyvinyl alcohol surfaces.
  • image-receiving elements of the aforementioned type comprise not only polyvinyl alcohol but also, in addition to the vinyl pyridine polymers mentioned above, they contain dyes, and the residuum of developing reagents, and additionally may contain mordants, hardening agents, and the like, which materials, especially the polyvinyl pyridine, may have some effect on the security bond formation.
  • image as used in the foregoing discussion is intended to include not only photographic likenesses of given individuals, but also, especially when applied to identification cards and the like, includes photographically recorded indicia which may form a part of the final picture.
  • An additional security feature may be provided for the laminations of this invention by printing a so-called security symbol in the photographic image by suitable means at the time of photographic exposure and prior to lamination.
  • the security symbol may comprise a suitable design or pattern which is placed in the optical path during photoexposure in such a way as to form part of the photographic image, overlying a small portion of the edge of the photographic likeness and extending into a portion of the graphic area.
  • This expresl2 sion is intended to include the use of a plurality of colors to obtain black.
  • a laminar structure comprising a first layer comprising a transparent, embossable polyvinyl chloride/ vinyl acetate resinous films having a major portion of vinyl chloride and a minor portion of vinyl acetate; a second transparent layer adjacent and bonded to said first layer consisting essentially of a vinyl lower alkyl ester-vinyl chloride copolymer having a chloride to alkyl ester molar ratio of no more than about 1:1, the surface of said layer away from said first layer having been treated with a hydrolyzing solution of alkali metal hydroxide dissolved in a liquid that is a softening ⁇ agent for Isaid copolymer to hydrolyze vinyl lower alkyl ester groups of said copolymer to vinyl alcohol groups; and a third layer adjacent to said second layer comprising a diffusion transfer color photograph, the image-bearing surface of which is bonded to said treated surface of said second layer.
  • a laminar structure las defined in claim 1 wherein said image-bearing surface of said diffusion transfer color photograph comprises polyvinyl alcohol and poly-4-vinyl pyridine.
  • a tamper-proof identification card comprising a laminar structure as defined in claim 1.
  • a laminar structure comprising a first layer comprising a transparent, embossable polyvinyl chloride! vinyl acetate resinous fil-m having a major portion of vinyl chloride and a minor portion of vinyl acetate; a second transparent layer adjacent and bonded to said first layer consisting essentially of la vinyl lower alkyl ester-vinyl chloride copolymer having a chloride to alkyl ester molar ratio of no more than about 1:1, the surface of said second layer away from said first layer having been treated with a hydrolyzing solution of alkali metal hydroxide dissolved in a liquid that is a softening agent for said copolymer to hydrolyze vinyl lower alkyl ester groups of said copolymer to vinyl alcohol groups; a third layer adjacent to said second layer and bonded to said treated surface thereof, consisting essentially of polyvinyl alcohol; and a fourth layer adjacent to said second layer comprising a diffusion transfer color photograph, the image-bearing surface of which is bonded to said third layer.
  • the process for preparing a laminar structure which comprises coating a transparent, embossable polyvinyl chloride/vinyl acetate resinous film having a major portion of vinyl chloride and a minor portion of vinyl acetate with a solution consisting essentially of a vinyl acetate/ vinyl chloride copolymer having a chloride to acetate molar ratio of no more than about 1:1 dissolved in an organic solvent therefor; drying the coating formed thereby; applying to the surface of said coating a hydrolyzing solution comprising an alkali metal hydroxide dissolved in a liquid medium which is a softening agent for said coating at a temperature of about 30 to 50 C. to hydrolyze vinyl acetate groups to vinyl alcohol groups; washing and neutralizing the surface th'us hydrolyzed; and pressing onto said hydrolyzed surface the surface of a diffusion transfer color photograph, at least one of said surfaces being wet when pressed.
  • An envelope structure comprising a first transparent wall, which first wall comprises a first outer layer comprising a transparent, embosable polyvinyl chloride/ vinyl acetate resinous film and a second inner layer ⁇ bonded to said first layer consisting essentially of a vinyl lower alkyl ester-vinyl chloride copolymer having a chloride to alkyl ester molar ration of no more than about 1:1, the surface of said second layer away from said first layer having been treated with a hydrolyzing solution of alkali metal hydroxide dissolved in a liquid that is a softening agent for said copolymer to hydrolyze vinyl lower alkyl ester groups of said copolymer to vinyl alcohol groups; and a second wall, which second wall comprises a backing for said first wall, and which backing is sealed along a portion of its periphery to said first wall.
  • a tamper-proof, embossable laminar structure comprising a first wall, which first wall comprises a first outer layer comprising a transparent, embossable polyvinyl chloride/ vinyl acetate resinous film, a second inner layer bonded to said first layer consisting essentially of a vinyl lower alkyl ester-vinyl chloride copolymer having a chloride to alkyl ester molar ratio of no more than about 1:1, the surface of said second layer away from said first layer having been treated with a hydrolyzing solution of alkali metal hydroxide dissolved in a liquid that is a softening agent for said copolymer to hydrolyze vinyl lower alkyl ester groups of said copolymer to vinyl alcohol groups; and a third layer comprising a diffusion transfer color photographic print, the image-bearing surface of which is bonded to said treated surface of said second layer; and a second wall, which wall comprises a backing for said first wall, and which backing is sealed about its periphery to said
  • a transparent, embossable film structure comprising a first layer comprising a transparent, embossable polyvinyl chloride/vinyl acetate resinous film having a major portion of vinyl chloride and a minor portion of vinyl acetate, and a second layer adjacent and bonded to said first layer consisting essentially of a vinyl lower alkyl ester-vinyl chloride copolymer having an alkyl ester to about 1:1, the surface of said second layer away from said first layer having been treated with a hydrolyzing solution of alkali metal hydroxide dissolved in a liquid that is a softening agent for said copolymer to hydrolyze vinyl lower alkyl ester groups of said copolymer to vinyl alcohol groups.
  • a process for preparing a transparent, embossable film structure which comprises coating one surface of a transparent, embossable polyvinyl chloride/vinyl acetate resinous film having a major portion of vinyl chloride and a minor portion of vinyl acetate, with a solution consisting essentially of a vinyl acetate-vinyl chloride copolymer having an acetate to chloride molar ratio of from about 7:3 to about 1:1 dissolved in an organic solvent therefor; drying the coating formed thereby; treating the surface of said coating with a hydrolyzing solution comprising an alkali metal hydroxide dissolved in a liquid medium which is a softening agent for said coating for at least about 15 seconds at a temperature of between about 30 C. and 50 C. to hydrolyze vinyl acetate groups to vinyl alcohol groups; and washing the surface thus hydrolyzed with water until it is neutral.
  • a hydrolyzing solution comprising an alkali metal hydroxide dissolved in a liquid medium which is a softening agent for
  • a first layer comprising a transparent, ⁇ embossablepolyvinyl chloride/vinyl acetate resinous iilrn having a major portion of vinyl chloride and a minor portion of vinyl acetate; a second layer adjacent and bonded to said first layer consisting essentially of a Vinyl lower alkyl ester-vinyl chloride copolymer having an alkyl ester to chloride molar ratio of from about 7:3 to 1:1, the surface of said second layer away from said first layer having been treated with a hydrolyzing solution of alkali metal hydroxide dissolved in a liquid that is a softening agent for said copolymer to hydrolyze vinyl lower alkyl ester groups of said copolymer to vinyl alcohol groups; and a third layer consisting essentially of polyvinyl alcohol bonded to the hydrolyzed surface of said second layer.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Credit Cards Or The Like (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US451894A 1965-04-29 1965-04-29 Laminations Expired - Lifetime US3511655A (en)

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US45170565A 1965-04-29 1965-04-29
US45189465A 1965-04-29 1965-04-29
US84390769A 1969-07-03 1969-07-03

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JP (2) JPS5249362B1 (enrdf_load_html_response)
BE (1) BE680225A (enrdf_load_html_response)
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Cited By (11)

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US3647442A (en) * 1965-04-29 1972-03-07 Polaroid Corp Laminations
US3655494A (en) * 1969-05-12 1972-04-11 Polaroid Corp I. d. card laminar structures and processes for making same
US3683806A (en) * 1970-05-20 1972-08-15 Murray Rudolph Theft-proof credit card assembly
US3725184A (en) * 1971-02-04 1973-04-03 Addressograph Multigraph Coated vinyl film
US3896726A (en) * 1972-06-19 1975-07-29 Gen Binding Corp Embossed monolithic identification credit card
US4300887A (en) * 1980-03-31 1981-11-17 Replogle Globes, Inc. Method of manufacture of raised relief illuminated globe
US4322461A (en) * 1980-01-07 1982-03-30 Polaroid Corporation ID Card laminar structures and a method for preparation thereof using a transfered adhesive
US4414731A (en) * 1980-03-31 1983-11-15 Replogle Globes, Inc. Method of manufacture of raised relief illuminated globe
US20050233120A1 (en) * 2004-04-15 2005-10-20 Campbell Printing Company Image laminate apparatus and method
US20140219710A1 (en) * 2013-02-07 2014-08-07 GM Global Technology Operations LLC Heat stake joining of adhesively bonded thermoplastic components
US20150170551A1 (en) * 2013-12-18 2015-06-18 Infosight Corporation Identification Method and Tag for Painted Substrates

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Publication number Priority date Publication date Assignee Title
FR1499022A (fr) * 1966-11-14 1967-10-20 Fotochem Werke Berlin Veb Procédé de fabrication de couches auxiliaires pour matières photographiques à base de polymères synthétiques
GB1509175A (en) * 1974-04-11 1978-04-26 Agfa Gevaert Production of adhesive transfers using photographic diffusion transfer
US4115618A (en) * 1976-02-02 1978-09-19 Polaroid Corporation Novel protective plastomeric sheet for identification card
US4378392A (en) * 1980-12-30 1983-03-29 Segel Joseph M Laminate to extend the life of photographs
US4407932A (en) * 1981-03-12 1983-10-04 Minnesota Mining & Manufacturing Co. Fade-resistant and abrasion resistant photographic reproduction, method of preparing, and photographic product therefor
ATE17211T1 (de) * 1981-07-20 1986-01-15 Interlock Sicherheitssyst Verfahren zur herstellung eines kartenfoermigen informationstraegers.
DE3130032A1 (de) * 1981-07-30 1983-02-17 Agfa-Gevaert Ag, 5090 Leverkusen Faelschungssicheres dokument
US4865938A (en) * 1986-12-19 1989-09-12 Brother Kogyo Kabushiki Kaisha Photo and pressure sensitive recording media comprising an adhesive agent
DE3852924T2 (de) * 1987-10-23 1995-05-24 Fuji Photo Film Co Ltd Büchlein mit Lichtbild.
DE3850342T2 (de) * 1987-10-28 1994-10-13 Fuji Photo Film Co Ltd Büchlein mit Lichtbild.
US5066047A (en) * 1990-09-05 1991-11-19 Polaroid Corporation Process for incorporating hologram into laminar structure with photograph
US6020436A (en) * 1993-03-09 2000-02-01 The Chromaline Corporation Photosensitive resin composition
US5362106A (en) * 1993-03-25 1994-11-08 Moore Business Forms, Inc. Self-sealing card assembly on carrier and methods of manufacture
US5466324A (en) * 1993-11-29 1995-11-14 Polaroid Corporation Apparatus and process for separation of laminae
US5666223A (en) * 1995-12-01 1997-09-09 Polaroid Corporation High-efficiency K-sheet polarizer

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US2397272A (en) * 1942-12-04 1946-03-26 Polaroid Corp Identification badge
US2458639A (en) * 1944-10-13 1949-01-11 Carbide & Carbon Chem Corp Vinyl copolymer and process for its production
US2647049A (en) * 1947-02-25 1953-07-28 Polaroid Corp Photographic element for color photography and a process of producing multicolor pictures
US2774669A (en) * 1953-04-13 1956-12-18 Dick Co Ab Diazotype reproduction process
US2882631A (en) * 1952-09-05 1959-04-21 Boone Philip Display materials, devices and systems
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color
US3148061A (en) * 1960-08-22 1964-09-08 Polaroid Corp Photographic diffusion transfer processes employing image receiving layers containing poly-4-vinylpyridine

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US3152901A (en) * 1962-03-07 1964-10-13 Security Cards Res Inc Credit card or the like
US3511655A (en) * 1965-04-29 1970-05-12 Polaroid Corp Laminations
US3498788A (en) * 1966-07-05 1970-03-03 Polaroid Corp Novel laminations for identification cards

Patent Citations (7)

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Publication number Priority date Publication date Assignee Title
US2397272A (en) * 1942-12-04 1946-03-26 Polaroid Corp Identification badge
US2458639A (en) * 1944-10-13 1949-01-11 Carbide & Carbon Chem Corp Vinyl copolymer and process for its production
US2647049A (en) * 1947-02-25 1953-07-28 Polaroid Corp Photographic element for color photography and a process of producing multicolor pictures
US2882631A (en) * 1952-09-05 1959-04-21 Boone Philip Display materials, devices and systems
US2774669A (en) * 1953-04-13 1956-12-18 Dick Co Ab Diazotype reproduction process
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color
US3148061A (en) * 1960-08-22 1964-09-08 Polaroid Corp Photographic diffusion transfer processes employing image receiving layers containing poly-4-vinylpyridine

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647442A (en) * 1965-04-29 1972-03-07 Polaroid Corp Laminations
US3655494A (en) * 1969-05-12 1972-04-11 Polaroid Corp I. d. card laminar structures and processes for making same
US3683806A (en) * 1970-05-20 1972-08-15 Murray Rudolph Theft-proof credit card assembly
US3725184A (en) * 1971-02-04 1973-04-03 Addressograph Multigraph Coated vinyl film
US3896726A (en) * 1972-06-19 1975-07-29 Gen Binding Corp Embossed monolithic identification credit card
US4322461A (en) * 1980-01-07 1982-03-30 Polaroid Corporation ID Card laminar structures and a method for preparation thereof using a transfered adhesive
US4300887A (en) * 1980-03-31 1981-11-17 Replogle Globes, Inc. Method of manufacture of raised relief illuminated globe
US4414731A (en) * 1980-03-31 1983-11-15 Replogle Globes, Inc. Method of manufacture of raised relief illuminated globe
US20050233120A1 (en) * 2004-04-15 2005-10-20 Campbell Printing Company Image laminate apparatus and method
US20140219710A1 (en) * 2013-02-07 2014-08-07 GM Global Technology Operations LLC Heat stake joining of adhesively bonded thermoplastic components
US9403318B2 (en) * 2013-02-07 2016-08-02 GM Global Technology Operations LLC Heat stake joining of adhesively bonded thermoplastic components
US20150170551A1 (en) * 2013-12-18 2015-06-18 Infosight Corporation Identification Method and Tag for Painted Substrates

Also Published As

Publication number Publication date
JPS5427280B1 (enrdf_load_html_response) 1979-09-08
DE1547994C3 (de) 1979-09-27
US3647442A (en) 1972-03-07
DE1547994A1 (de) 1970-01-02
DE1547994B2 (de) 1979-01-25
JPS5249362B1 (enrdf_load_html_response) 1977-12-16
BE680225A (enrdf_load_html_response) 1966-10-28
GB1151771A (en) 1969-05-14

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