US3819376A - Sensitometric modification by pre-exposure - Google Patents

Sensitometric modification by pre-exposure Download PDF

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Publication number
US3819376A
US3819376A US00300710A US30071072A US3819376A US 3819376 A US3819376 A US 3819376A US 00300710 A US00300710 A US 00300710A US 30071072 A US30071072 A US 30071072A US 3819376 A US3819376 A US 3819376A
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Prior art keywords
silver halide
image
layers
photosensitive element
halide emulsion
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US00300710A
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English (en)
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E Land
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Polaroid Corp
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Polaroid Corp
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Priority to US00300710A priority Critical patent/US3819376A/en
Priority to CA179,651A priority patent/CA1014399A/en
Priority to JP48111886A priority patent/JPS586938B2/ja
Priority to FR7337957A priority patent/FR2204819B1/fr
Priority to NLAANVRAGE7314685,A priority patent/NL175953C/xx
Priority to DE2353534A priority patent/DE2353534C3/de
Priority to GB4974073A priority patent/GB1451345A/en
Application granted granted Critical
Publication of US3819376A publication Critical patent/US3819376A/en
Priority to CA264,779A priority patent/CA1023592A/en
Anticipated expiration legal-status Critical
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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/26—Silver halide emulsions for subtractive colour processes
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/50—Peel-apart units, i.e. the image-forming section being separated from the image-receiving section
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • Y10T156/1007—Running or continuous length work
    • Y10T156/1008—Longitudinal bending
    • Y10T156/1011—Overedge bending or overedge folding

Definitions

  • SENSITOMETRIC MODIFICATION BY PRE-EXIPOSURE This invention is concerned with photography and, more particularly, with the formation of multicolor photographic images.
  • Multicolor photographic films have developed a number of procedures to minimize the efstored for a period of time after coating to allow the films to age, so that changes in sensitometry following coating have an opportunity to reach a plateau prior to sale. If the film is designed to be developed by a photofinisher or in a darkroom, processing of the exposed multicolor film is controlled within very narrow limits, typically within plus or minus a half degree of a prescribed temperature, in order to minimize sensitometric variations from film to film. Where the multicolor film is of the negative type, an opportunity to adjust the sensitometry occurs in printing the desired final positive image, during which operation the printing exposure may be appropriately color filtered.
  • a primary object of this invention is to provide a simple and economical method of modifying the sensitometry of a multicolor film subsequent to the manufacture thereof.
  • a further object of this invention is to provide multicolor films, particularly multicolor diffusion transfer films, wherein at least one of the blue-, greenand redsensitive silver halide emulsions contains a weak nonimagewise latent image.
  • Yet another object of this invention is to provide processes for manufacturing multicolor photographic films, wherein at least one of the blue-, greenand redsensitive silver halide emulsions is given a uniform,
  • the invention accordingly comprises the method involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the product possessing the features, properties and the relation of components which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • FIG. 1 is a somewhat schematic, perspective view illustrating a method of fabricating and assembling a succession of one type of photographic diffusion transfer multicolor film units, the sensitometry of which may be modified in accordance with this invention at some stage of the fabrication and assembly subsequent to coating the multicolor photosensitive element;
  • FIG. 2 is a graphic illustration of the blue, green and red D log E curves of a multicolor reflection print obtained by diffusion transfer processing a multicolor photosensitive element and which may be considered to, be a control for purposes of illustrating this invention.
  • FIGS. 3 and 4 are graphic illustrations of the blue, green and red D log E curves of two multicolor reflection prints obtained using the same components as used in obtaining the D log E curves shown in FIG. 2 except that the photosensitive elements were given a weak preexposure in accordance with this invention, the curves of FIGS. 3 and 4 thus illustrating the modification in sensitometry provided by this invention.
  • the present invention has special applicability to multicolor diffusion transfer films; for convenience, the invention will be illustrated by reference to multicolor diffusion transfer films designed to provide integral negative-positive reflection prints.
  • the photograph comprises the developed silver halide emulsions retained with the dye-image-- carrying layer as part of a permanent laminate.
  • the image-carrying layer is separated from the developed silver halide emulsions in said laminate by a lightreflecting layer, preferably a layer containing titanium dioxide,
  • a lightreflecting layer preferably a layer containing titanium dioxide
  • the color characteristics and qualities of multicolor images are conventionally expressed in terms of the H and D" or D log E curves of the blue, green and red exposure records contained in the multicolor image.
  • D log E" curves present the relationship of image density to the exposure resulting in the recorded image density, and the D log E curve is obtained by plotting the measured optical density against the logarithm of the exposure providing the measured density.
  • Such curves may be readily plotted for diffusion transfer multicolor positive images, the maximum transfer density being a measure of the minimum exposure received by the silver halide and the lowest transfer density being a measure of the maximum exposure received by the silver halide.
  • the portion of minimum densities (D,,.,-,,) of the D log E curve is referred to as the toe portion, and the portion of the curve reproducing maximum densities (D,,,,,,,,) is referred to as the shoulder portion.
  • the portion of the D log E curve over which the gradient or slope of the curve is substantially constant is a measure of the exposure range over which the density is proportional to log E and this portion of the curve may be considered an indication of the latitude of the film.
  • the blue, green and red D log E curves provides a means of expressing the relationship of these curves to each other, a relationship frequently referred to as color balance. If, for example, the skin tones appear greenish or bluish on visual inspection the extent of the apparent color imbalance may be quantitatively depicted by plotting the blue, green and red D log E curves on the same graph. If the slopes of the blue, green and red D log E curves match, i.e., they are the same or substantially the same, then the color film may be considered to be in sensitometric balance. It is not necessary that the several curves overlie one another. In practice, integral blue, green and red reflection densities are used; these densities are called integral because they measure the total density at a given wavelength independent of the dye or dyes responsible for that density.
  • D log E curves are considered to be a measure of the effect of variations in exposure upon the final image density, in reality they measure the amount of each dye controlled by the photographic system. Photoexposure is, of course, the major source of this control. Variations in manufacturing steps and storage prior to use also may have significant effects upon the amount of silver halide developable during processing,
  • imbalances in the color sensitometry of a given photographic system may be at least substantially, if not completely, reduced (corrected) by giving the photosensitive element a non-imagewise exposure to light of selected wavelength range(s) and intensity subsequent to coating of said photosensitive element.
  • This non-imagewise preexposure imparts a weak latent image of predetermined characteristics and thereby permits controlled modifications of the sensitometry of an already coated and aged photosensitive element. Desirable changes in color balance thus may be readily effected by changes in one, two or all three of the individual red, green and blue H and D curves. Reliance upon modifications of the processing composition to offset imbalances in the color sensitometry of the photosensitive element itself are greatly reduced, in many cases even to the point where a common processing composition may be used with all or almost all runs of the photosensitive element.
  • the preexposure contemplated by this invention adds the same absolute amount of exposure to each part of the D log E curve, the effect is to add a proportionately larger exposure to the shoulder portion of the positive curve.
  • the slope of the shoulder portion is changed and one may say that the shoulder portion is bent over.”
  • an individual curve also may be caused to slide over to more closely overlie one or both of the other curves, in whole or in part, if such a relationship is found desirable; this type of change in sensitometry may be used to change the film speed of one or more silver halide emulsions.
  • the preexposure may be to a specific wavelength range, e.g., to blue, green or red light, or it may be to a combination of several colors, or to both white light and a specific wavelength range or ranges. Indeed, it may be desirable in a given instance to preex pose to two different wavelength ranges in a ratio such that one silver halide emulsion receives more preexposure than does another. Such differential preexposures may provide useful interimage effects.
  • color filters are commercially available and may be used in the practice of this invention, including the well known Wratten filters.
  • the light transmission characteristics of many suitable filters are described in Kodak Filters For Scientific and Technical Uses, published by Eastman Kodak Co. as Kodak Publication No. 8-3. If necessary, filters of special light transmission characteristics may be readily prepared.
  • the preexposure contemplated by this invention is most advantageously applied after the photosensitive element has aged to maturity, i.e., the sensitometry of the photosensitive element as manufactured is no longer changing significantly with time. Indeed, the beneficial effects of preexposure may be offset, in whole or in part, by ageing changes if the preexposure is effected before the photosensitive element has completed ageing. In the same sense, the image-receiving system and the processing composition also should have reached their maturity prior to determining the desired preexposure.
  • Multicolor diffusion transfer images may be obtained using a variety of arrangements of the image-receiving layer and the silver halide emulsions.
  • these layers may be carried by a common support or by separate supports brought into superposition after photoexposure.
  • a particularly advantageous film" structure is shown in the aforementioned U.S. Pat. No. 3,415,644 wherein the requisite layers are in superposed relationship prior to and during photoexposure, and these layers are maintained in superposed relationship as a permanent laminate after processing and image formation.
  • Such film'units typically contain an outer transparent layer or support through which photoexposure is effected and the final multicolor image viewed, and another outer layer or support carrying at least the photosensitive layers, the latter support preferably being opaque. While these supports or sheet-like elements may simply be.
  • these elements are laminated together prior to photoexposure.
  • This prelamination provides a number of benefits, both during manufacture and in photoexposure.
  • the elements are delaminated by the distribution of a fluid processing composition which, upon solidification, bonds the elements together to form the desired permanent laminate. Procedures for forming such prelaminated film units wherein the two elements are temporarilylaminated together prior to exposure are described, for example, in U.S. Pat. No. 3,625,281 to Albert J. Bachelder and Frederick J. Binder and in U.S. Pat. No. 3,652,282 to Edwin H. Land,'both issued Mar. 28, 1972.
  • a prelaminated integral film unit is easier to handle and manipulate during assembly and during exposure'and processing within the camera; it is more compact and hence, permits smaller and less bulky film packs and. cameras; and it is less subject to buckling and distortion due to temperature and humidity changes and more likely to lie flat and remain planar during exposure. Since the elements are in contact throughout the entire extent of their facing surface, every portion of each element is exposed to substantially the same ambient conditions so that each portion has the same physical and chemical properties as every other portion and the elements produce uniform results, the photographically active 1973).
  • Film unit 10 comprises a first or photosensitive sheet 12, a second or image-receiving sheet 14, rupturable container 16 holding a quantity of a liquid processing composition, a mask or binding sheet 18, a trapping element 20 and a sealing strip 22.
  • Sheets 12 and 14 are preferably rectangular, are substantially equal in width and arranged in superposed face-to-face contact with one another with the lateral edges of the sheets substantially in alignment.
  • the second sheet 14 is substantially longer than the photosensitive sheet 12 and includes a leading end section 24 extending beyond the leading edge of sheet 12 by a distance slightly in excess of the shorter dimension of container 16 and a trailing endsection 26 extending a relatively short distance beyond the trailing edge of photosensitive sheet 12.
  • the photosensitive and image-receiving sheets are laminated to one another throughout substantially the entire area of their facing surfaces except for a narrow region adjacent the leading edge of the photosensitive sheet.
  • Binding sheet 18 is preferably formed of a strong, light-opaque, white material such as, for example, a laminate including a layer of paper, a polymer and an opaque layer such as a metallic coating and/or pigment carried on or within a layer of sheet 18.
  • the mask or binding sheet is larger than the image-receiving sheet 14 and includes a leading end section 30, a trailing end section 32 and lateral marginal sections 34 adapted to be folded over the edges of the film unit.
  • Sheet 18 is adhered to the outer surface of sheet 14 substantially over the entire facing surfaces of the two sheets surrounding exposure opening 28. Lateral marginal sections 34 of sheet 18' are folded around the lateral edges of sheets 12 and 14 and secured to the margins of sheet 12. Trailing end section 32 of sheet 18 is folded around the trailing edge of sheet 14 and secured to the outer surface of photosensitive sheet 12 near the trailing edge thereof.
  • Container 16 is of the type shown in U.S. Pat. No. 2,543,181 and is formed by folding a rectangular blank of a fluid impervious sheet material medially and sealing the marginal sections of the blank to one another 1 to form a cavity for containing processing liquid. Coneffect their function. Moreover, processing, specifically, spreading of the processing liquid within the film unit, is facilitated since there is little or substantially no air between the sheets to interfere with liquid distributainer 16 is mounted on the leading edge section 24 of sheet 14 adjacent the leading edge of photosensitive sheet 12 in position to discharge its fluid contents between the photosensitive and image-receiving sheets.
  • Container 16 is retained in place by portion of lateral edge sections 34 secured to the ends of the container and leading end section 30 of binding sheet 18 which is folded aroung the leading edge of sheet 14 and secured to a longitudinal edge of the container.
  • Sealing strip 22 is secured to a longitudinal marginal section 36 of the container and the leading end margin of photosensitive sheet 12 and cooperates with the sheets to bridge the gap between the container and the photosensitive sheet and form a conduit for conducting the liquid from the container between the photosensitive and image-receiving sheets.
  • the film unit In the processing of the film unit shown, the film unit is advanced, container foremost, relative to and between a pair of pressure-applying members which initially apply compressive pressure to the container to eject its liquid contents between the photosensitive and image-receiving sheets and then distribute the mass of liquid between the sheets toward the trailing ends thereof to form a layer of substantially uniform, predetermined thickness at least coextensive with the area defined by exposure opening 28.
  • excess processing liquid may be provided in container 16 and the film unit includes trapping means for collecting and retaining excess processing liquid overrun.
  • these means comprise trapping element 24 shown as a narrow strip of a relatively thick sheet material formed with perforations and indentations 38 which occupy the major portion of trapping element 20.
  • the trapping element is secured between trailing end section 32 and the trailing end margins of sheets 12 and 14 with the perforations and indentations 38 cooperating with sheets 12, 14 and 18 to provide spaces for collecting and retaining excess processing liquid overrun.
  • component transport is achieved by utilizing a common component of the film units themselves as the means for transporting the components throughout the major portion of the fabrication and assembly operations.
  • This common component is the mask or binding sheet 18 which is initially provided in the form of an elongated web or strip designated 40 in FIG. 1, the locations at which strip 40 is folded and cut to provide mask 18 being indicated by dot-dash lines.
  • Strip 40 has a width substantially equal to the length of binding sheet 18 and remains intact as a continuous strip throughout all but the last two assembly operations.
  • the components of the individual film units are mounted on and attached to strip 40 as the latter is moved intermittently or continuously through the various fabrication, assembly and inspection stations at which the components of the succession of film units are assembled to form film units each having its longitudinal dimension extending in a direction transverse to the length of strip 40.
  • Strip 40 which forms a succession of binding sheets 18 is of substantial length, i.e., hundreds of feet, and has a width equal to the overall length of each binding sheet. It may be in coiled form and provision may be made for splicing the trailing end of a strip to the leading end of the next succeeding coil of strip 40 without interrupting the fabrication and assembly operation.
  • the first operation performed on strip 40 as part of the fabrication and assembly process illustrated in FIG. 1, is a cutting operation in which the rectangular exposure opening 28 is formed and notches 42 and 44 are formed in the opposite lateral margins of strip 40 to prevent overlap and excessive thickness in the regions in which the mask sheet is folded around the edges of the image-recording sheet during subsequent assembly operation.
  • the cutting operation may be performed by conventional means such as a punch and die.
  • the photosensitive and second sheets 12 and 14 may be brought into the assembly operation as separate, elongated strips, in the preferred embodiment illustrated, the photosensitive and second sheets (strips) are also supplied in the form of coils having widths equal to the lengths of the respective sheets and are laminated to one another prior to being brought into association with strip 40.
  • the laminating process essentially comprises guiding the photosensitive and image-receiving sheet along converging paths into superposed relation, distributing a laminating liquid between the sheets and pressing them into face-to-face contact.
  • a pair of laminating rollers 46 and 48 may be employed for advancing the sheets thereb'etween into face-to-face contact and pressing the sheets together with a nozzle 50 for introducing the laminating liquid between the sheet at the nip of rollers 46 and 48.
  • a particularly useful laminating liquid comprises an aqueous solution of a water-soluble polyethylene glycol, as described and claimed in the copending application of Edwin H. Land, Ser. No. 247,023 filed Apr. 24, 1972.
  • the assembly process begins with the bringing together of a laminate comprising the photosensitive and image-receiving sheets, and carrier strip 40 and adhering the laminate to the carrier strip which thereafter functions to transport sections of the sheets (laminate) as well as the other components of the film units through subsequent fabrication, assembly and inspection operations.
  • the carrier strip 40 is moved upwardly over a guide 52 and then along a generally horizontal path through a succession of machine stations in which the assembly and inspection operations are performed.
  • the laminate comprising photosensitive and second sheets 12 and 14 is advanced by suitable means such as a pair of rollers 54 and 56 into superposition with strip 40 at guide 52.
  • the laminate is advanced from between rollers 54 and 56 between a knife 58 and anvil 60 operative to cut the laminate transversely to form a leading end edge normal to the lateral edges of the laminate.
  • Both carrier strip 40 and the laminate are advanced into superposition such that the leading edge designated 62 of the laminate is located approximately one quarter of the distance from an edge of an exposure opening 28 in strip 40 and the adjacent edge of the preceding exposure opening.
  • strip 40 may be moved either continuously or intermittently, the latter method being illustrated in FIG. 1, and motion of strip 40 and the section of the laminate are arrested with the leading edge margin of the laminate, located with respect to strip 40 as previously indicated, disposed between the jaws, one of which is shown and designated 64, of a heat sealing device adapted to apply heat and compressive pressure to strip 40 and the laminate to bond the leading edge portion of image-receiving sheet 14 to strip 40.
  • a heat sealing device adapted to apply heat and compressive pressure to strip 40 and the laminate to bond the leading edge portion of image-receiving sheet 14 to strip 40.
  • the upper surface of strip 40 is coated with a conventional heat activated adhesive formed, for example, of a thermoplastic polymer.
  • Carrier strip 40 is then advanced to a second heat sealing station including a pair of juxtaposed jaws one of which is shown and designated as 66, for sealing the imagereceiving sheet to carrier strip 40 in the region completely surrounding the exposure opening 28 in the carrier strip.
  • a second heat sealing station including a pair of juxtaposed jaws one of which is shown and designated as 66, for sealing the imagereceiving sheet to carrier strip 40 in the region completely surrounding the exposure opening 28 in the carrier strip.
  • knife 58 is actuated to sever the laminate to the desired length and the strip is caused to advance a greater distance than the laminate to provide spacing between the trailing edge of the section of the laminate severed from the remainder of the laminate and the new leading edge of the laminate formed by actuation of knife 58.
  • the process is basically one of heat sealing the laminate to the carrier strip, advancing the carrier strip so as to move the laminate heat sealed thereto toward the leading edge, severing the laminate to length and then advancing the'next succeeding leading end portion of the laminate into position with respect to strip 40 to be heat sealed.
  • the photosensitive and image-receiving sheets are not prelaminated by distribution of a laminating liquid, they may at least be temporarily attached to one another by heat sealing jaws located adjacent knife 58, preferably ahead of the knife and adapted to soften and bond to one another portions of the facing polymeric layers of the two sheets in regions which are located near the margins of the sheets in the completed film unit.
  • a container 16 is attached to an end lateral marginal portion of strip 40 which comprises leading end section 30 of mask sheet 18 and a trapping element 20 is mounted on a marginal section of strip 40 which comprises a trailing end section 32 of mask sheet 18.
  • the container 16 is attached by heat sealing the longitudinal margin of the container located opposite marginal sections 16, by gripping the leading end section and the margin of the container between a pair of heat sealing jaws.
  • Trailing element 20 is similarly mounted at the opposite edge of strip by compressing the element and trailing end section between a pair of heat sealing jaws.
  • the trapping element may take the form of an elongated strip or web severed from the remainder thereof immediately prior to or subsequent to adherence by heat sealing to carrier strip 40.
  • Each container 16 may be formed as one of a succession of containers produced by a continuous process and severed from a strip of containers by a knife and anvil 68 and'70 immediately prior to or subsequent to heat sealing of the container to carrier strip 40.
  • sealing strip 22 is heat sealed to a longitudinal marginal section 36 of container 16 prior to severance of the container from the remainder of a strip of containers.
  • Sealing strip 22 may also take the form of an elongated, coiled strip and heat sealing thereof to the strip of containers may be either a continuous or an intermittent operation performed by compressing the containers and strip 22 between a pair of heat sealing members one of which is shown as jaw 72 in FIG. 1. In this manner both sealing strip 22 and a container 16 are severed simultaneously and to the same length. As is previously noted, this may be accomplished either subsequent to or prior to adherence of the container to a margin of strip 40.
  • the next operations in the fabrication and assembly process are folding operations in which the leading end section 30 to which a container is attached and the trailing end section 32 to which a trapping element 20 is attached, are folded through so that the container is brought into face-to-face relation with the leading end section 24 of the image-receiving sheet and the trapping element 20 is brought into face-to-face relation with the trailing end sections of the photosensitive and image-receiving sheets and is confined between the trailing end sections and trailing end section 32 of sheet 18.
  • the folding operations may be accomplished by conventional means such as plows and/or movable fingers such as are well-known in the art.
  • the next assembly operations involve the heat sealing of stip 22 to the leading margin of photosensitive sheet 12 and the heat sealing of trailing end section 18 to the photosensitive sheet near the trailing edge thereof.
  • These heating sealing operations are accomplished by conventional means in the same manner as the previously described heat sealing operations, namely by compressing the sheets to be sealed to one another between a pair of heated jaws.
  • Heat sealing of strip 22 and trailing end section 32 to the outer surface of the photosensitive sheet complete the assembly operations in which a succession of film units, in various stages of assembly and fabrication are coupled to one another and transported by carrier strip 40.
  • the fabrication and assembly apparatus will'also include a number of inspection stations which serve to insure that each successive fabrication and assembly operation has been performed correctly.
  • These inspection means will include means adapted to determine, for example, whether or not the laminated and photosensitive and image-receiving sheets are properly aligned with strip 40; that the leading edge of each section of the laminate is properly located with respect to an exposure aperture; that trapping element 20 is attached to the carrier strip and is properly located thereon; that a container and heat sealing strip 22 are attached to the carrier strip and properly located thereon; and that the various folding and sealing devices have performed as required.
  • Such inspection means are well-known in the art and include mechanical, optical and pneumatic devices for sensing the presence and/or location of the various components.
  • the purpose of providing continuous monitoring of the fabrication and assembly process is to-promptly identify improperly fabricated or assembled film units immediately following the particular fabrication or assembly step being monitored so that action can be taken to correct the operation which is resulting in the defect and to promptly identify the defective film unit so that subsequent assembly operations are not performed thereon and components wasted, and the film unit will be rejected or set aside for salvage of components and- /or further remedial work at a subsequent stage in the manufacturing process.
  • the sucstations Following heat sealing of the leading and trailing end sections 30 and 32 to the photosensitive sheet, the sucstations.
  • lateral marginal sections 34 are folded and in the second station, sections 34 are heat sealed to the lateral margins of photosensitive sheet 12.
  • the film units are preferably advanced in a direction transverse to their previous direction so that folding may be accomplished by conventional means such as plows and/or fingers and the heat sealing steps may be performed either continuously as by advancing the margins of each film unit between pairs of heat sealing rollers, or intermittently by clamping the margins between heat sealing jaws two of which are shown in FIG. 1 and designated 78.
  • each film unit Upon completion of this last operation, the assembly of each film unit is complete and following a final inspection the film unit is ready to be loaded separately or together with other film units into a suitable lighttight container or cassette in which it is exposed within a camera.
  • the present invention provides for modification of the sensitometry of a multicolor film by effecting a controlled, non-imagewise (uniform) exposure of the coated photosensitive element.
  • This preexposure may be effected at any convenient stage of the fabrication and assembly operation.
  • a preexposure station is provided just before the laminate 12 is cut into film unit-size segments and joined to the carrier strip 40.
  • the preexposure station comprises a light source 84 positioned to expose a predetermined portion of the photosensitive sheet 12 through image-receiving sheet 14, a color filter 86.
  • a plurality of preexposure stations may be provided, each adapted to provide a non-imagewise exposure of a predetermined nature.
  • a single preexposure station may include several different color filters, each having the requisite light transmission properties required to effect exposure to the desired wavelength range or ranges. If it becomes necessary to reduce the intensity of the light transmitted by the color filter, a suitable neutral density filter may be included in the light path. Suitable shielding means, not shown, are provided to prevent light transmitted by the filter(s) from striking unintended portions of the photosensitive element.
  • the light source may be one which is pulsed, such as a strobe, in synchronization with the intermittent assembly operation shown in FIG. 1; appropriate indexing means may be provided to insure registration of the preexposed area with the image area defined by the mask 18. Because the preexposure step utilizes extremely low light intensities, the light source 84 will require replacement only infrequently, and its light emission characteristics will remain substantially constant for long periods of use.
  • the preexposure station is positioned just before the laminate 14 is severed into film unit segments mounted on the carrier web 40.
  • the preexposure station may be positioned just before the knife 74 severs the carrier web 40 or at any other convenient stage of the fabrication and assembly operation, including effecting the desired preexposure before the photosensitive sheet 12 is laminated to the image receiving sheet 14.
  • a continuous light source may be more efficient than an intermittent light source.
  • the preexposure step also may be preformed on the completely assembled individual film units 10, this altemative is less preferred because of the reduced ease of handling the individual film units as compared with the embodiments wherein preexposure is effected while the photosensitive element is carried by a carrier sheet, as in FIG. 1.
  • a photosensitive element is exposed to a suitable multicolor step-wedge and diffusion transfer processed with a given processing composition and image-receiving element.
  • the blue, green and red D log E curves of the resulting multicolor transfer image (control image) are prepared. Examination of these D log E curves will indicate to one skilled in color photographic sensitiometry the manner and extent to which the individual D log E curves depart from the desired curve shape. From this examination, one may determine by routine analysis and experimentation how much additional exposure would be required of what wavelength range or ranges to bring the individual D log E curve(s) closer to their desired shape(s).
  • the photosensitive element of another film unit having the identical photosensitive element, image-receiving element and processing composition as used in obtaining the control image, is then given a uniform exposure to light of the wavelength range(s) and intensity estimated to be necessary to provide the desired changes in the D log E curves of the control image.
  • the blue, green and red D log E curves of the resulting test multicolor tranfer image are then prepared and compared with the control. While more than one test may be required to determine the preexposure effective to give the desired D log E curve shape changes, such tests may be performed rapidly and easily, and the number of tests required to determine the most suitable preexposure very rapidly decreases with experience.
  • FIGS. 2, 3 and 4 Blue, green and red D log E curves are reproduced in FIG. 2 for a control integral negative positive reflection print.
  • FIGS. 3 and 4 illustrate the changes effected in the D log E curves as a result ofgiving another section of the same photosensitive element different preexposures followed by processing unsing the same image-receiving system and processing composition as used in forming the control integral negative-positive reflection print.
  • all components of the film unit were kept constant and the differences in curve shapes result directly from the specific preexposures.
  • preexposure was effected using an E, G and G Mark 6 Sensitometer set at 10' seconds exposure using a Xenon strobe exposure source, with the photosensitive element approximately 6 inches from the light source.
  • the D log and E curves reproduced in FIG. 3 were obtained following preexposure in the described manner through a 2.60 neutral density filter and a Wratten 21 color filter, while the curves reproduced in FIG. 4 were obtained as a result of preexposure through a 2.60 neutral density filter and a Wratten 23 filter.
  • a Wratten 21 transmits visible light above about 540 nm and appears orange in color; it passes less green than red light and no blue light.
  • a Wratten 23 filter transmits visible light above about 560 nm and appears light red in color; it transmits a wavelength range similar to that of the Wratten 21 filter but effects less green exposure relative to the red exposure obtained with the Wratten 2l filter.
  • a comparison of the D log E curves clearly shows highly desirable curve shape changes, providing increased" dynamic range and changesin slope bringing the individual curves into a more parallel relationship to give improved color balance and increased red speed.
  • the preexposures described above were effected through the image-receiving element 14 subsequent to the lamination thereof to the photosensitive element 12. indeed, it has been found that the beneficial effects of preexposure for sensitometric modification are retained over a longerperiod if the photosensitive layers are part of a laminate between polymeric supports. While the reasons for this stabilizing effect of the laminate upon the preexposure beneficial effects are not known, it is believed that the insulation to changes in ambient conditions provided by the laminate is particularly significant.
  • the polymeric supports provide protection against atmospheric components which might cause or facilitate fading of the latent image imparted by preexposure.
  • the polymeric supports may comprise any of the conventional film base materials, and preferably are substantially impermeable to oxygen transmission. Polyesters, such as polyethylene terephthalate, are particularly useful'supports.
  • the preexposure intensity is such as to provide a weak latent image, although the preexposure may be so low as to merely bring the resulting latent image to just below the threshold of developability.
  • the preexposure level is such that any reduction in D contributed by the silver halide emulsion(s) preexposed as compared with the corresponding control is preferably no more than about 0.l to 0.2; higher preexposure levels may be used if found necessary.
  • the intensity of the preexposure is very low, e.'g., about l/2,500 to 1/400 the exposure required to provide fully exposed areas, i.e., the exposure corresponding to the D of the positive image.
  • this invention provides a method for maintaining the photographic consistency of a total diffusion transfer system, notwithstanding normal variations in manufacture and ageing of the components.
  • the herein disclosed use of preexposure to modify andadjust the sensitometry of a multicolor system has found to be a very effective method of modifying the color balanace of a multicolor diffusion transfer film.
  • This method reduces the need for modification of the processing composition for use with manufacturing variants of the multicolor photosensitive element.
  • the rebalancing method is one which permits maximum flexibility in the manufacturing and coating operations so that only a minimum of photosensitive material need be deemed unusable as out of specification" with respect to color balance.
  • the rebalancing method is brought into operation at a relatively late stage of the film manufacturing operation, providing the ability to adjust after the photographic system has aged to equilibrium values.
  • the photosensitive element may be of the multilayer type, as in the illustrative disscussion,'or of the screen type such as described in US. Pat. No. 2,968,554.
  • a multicolor photosensitive element for use in forming diffusion transfer images comprising a support carrying a blue-sensitive silver halide emulsion, a
  • each of said silver halide emulsions having associated therewith, respectively, a yellow image dye-providing material, a magenta image dye-providing material, and a cyan image dye-providing material, at least one of said silver halide emulsions containing a weak uniform latent image formed by uniform exposure of said photosensitive element, after coating of said silver halide emulsions, to light of a predetermined wavelength range, said preexposure being of an intensity and wavelength range adapted to bring the slopes of the D log E curves of the positive transfer images obtained from said silver halide emulsions following image-wise exposure into a more nearly parallel relationship with each other.
  • each said image dye-providing material is.a dye developer.
  • a photographic film unit adapted to be exposed and processed to produce a diffusion transfer image in color and comprising, in combination:
  • a laminate including two dimensionally stable layers and a plurality of layers intermediate said dimensionally stable layers, at least one of said dimensionally stable layers being transparent, said plurality of layers including an image-receiving layer and a blue-sensitive silver halide emulsion, a greensensitive silver halide emulsion and a red-sensitive silver halide emulsion, each of said silver halide emulsions having associated therewith, respectively, a yellow image dye-providing material, a magenta image dye-providing material, and a cyan image dye-providing material, at least one of said silver halide emulsions containing a weak uniform latent image formed by uniform exposure of said photosensitive element, after coating of said silver halide emulsions, to light of a predetermined wavelength range, said preexposure being of an intensity and wavelength range adapted to bring the slopes of the D log E characteristic curves of the positive transfer images obtained from said silver halide emulsions following imagewise exposure
  • a rupturable container releasably retaining a fluid processing composition, said rupturable container being coupled to said laminate in position to discharge its liquid contents for spreading between a predetermined pair of said layers of said laminate to thereby cause delamination of said laminate between said predetermined layers thereof.
  • each of said dimensionally stable layers comprise polyethylene terephthalate.
  • each said image dye-providing material is a dye developer.
  • the method of improving the sensitometry of a multicolor photosensitive element comprising a blue-sensitive silver halide emulsion, a greensensitive silver halide emulsion and a red-sensitive silver halide emulsion, each of said silver halide emulsions having associated therewith, respectively, a yellow image dye-providing material, a magenta image dye-providing material and a cyan image dye-providing material, said method comprising imparting a weak uniform latent image to at least one of said silver halide emulsions prior to photoexposing said silver halide emulsions imagewise, said weak uniform latent image being formed by a uniform low intensity exposure to light of a predetermined wavelength range.
  • each said image dye-providing material is a dye developer.
  • a method of manufacturing a multicolor photosensitive element for use in a multicolor diffusion transfer process comprising the steps of (a) coating a multicolor photosensitive element comprising a support carrying a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion and a redsensitive silver halide emulsion, each of said silver halide emulsions having associated therewith, respectively, a yellow image dye-providing material, a magenta image dye-providing material, and a cyan image dye-providing material; (b) exposing a sample section of said multicolor photosensitive element to a color sensitometry target; (0) diffusion transfer processing said exposed multicolor photosensitive element and analyzing the resulting multicolor transfer image to determine the blue, green and red D log E characteristic curves of said transfer image as obtained from said blue-, green-, and red-sensitive silver halide emulsions thus processed and the deviation of each from a desired aim characteristic curve; and (d) uniformly
  • a photographic product which comprises a first polymeric support substantially impermeable to oxygen, a red-sensitive silver halide emulsion; a greensensitive silver halide emulsion; and a blue-sensitive silver halide emulsion; said silver halide emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer; an image-receiving layer for receiving image dyes transferred thereto as a function of exposure and development of said silver halide emulsion layers; a second polymeric support which is transparent and through which said image-receiving layer may be viewed; a rupturable container releasably holding a processing composition adapted, upon distribution between predetermined layers of said product to develop said silver halide emulsions and to effect the formation of a transfer image in dye in said image-receiving layer, said processing composition also being adapted to provide a permanent laminate including said developed silver halide emulsions and said image-
  • Apparatus for assembling a diffusion transfer film unit comprising, in combination:
  • c. means for supplying a rupturable container for each film unit, said rupturable container releasably holding a processing composition
  • Apparatus as defined in claim 24 further including means for temporarily laminating said first and second elements together with said photosensitive layers between the outer layers forming said laminate, said photosensitive layers being exposable through one of said outer layers.
  • Apparatus as defined in claim 24 wherein said means for uniformly exposing said photosensitive element comprise a stroboscopic light source and means for positioning at least one light filter between said light source and said photosensitive element.
  • a multicolor photosensitive element for use in forming diffusion transfer images comprising a support carrying a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion and a redsensitive silver halide emulsion, each of said silver halide emulsions having associated therewith, respectively, a yellow image dye-providing material, a magenta image dye-providing mateiral, and a cyan image dye-providing material, at least one of said silver halide emulsions containing a weak uniform latent image formed by uniform exposure of said photosensitive element, after coating of said silver halide emulsions, to light of a predetermined wavelength range, said preexposure being of an intensity and wavelength range adapted to modify the D log E curves of the positive transfer images obtained from said silver halide emulsions following imagewise exposure to more closely correspond with predetermined D log E curves.

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US00300710A 1972-10-25 1972-10-25 Sensitometric modification by pre-exposure Expired - Lifetime US3819376A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US00300710A US3819376A (en) 1972-10-25 1972-10-25 Sensitometric modification by pre-exposure
CA179,651A CA1014399A (en) 1972-10-25 1973-08-27 Photographic product and method of manufacture
JP48111886A JPS586938B2 (ja) 1972-10-25 1973-10-04 カクサンテンシヨゾウケイセイヨウ タシヨクカンコウヨウソ
FR7337957A FR2204819B1 (de) 1972-10-25 1973-10-24
NLAANVRAGE7314685,A NL175953C (nl) 1972-10-25 1973-10-25 Werkwijze voor het verbeteren van de sensitometrie.
DE2353534A DE2353534C3 (de) 1972-10-25 1973-10-25 Verfahren zur Beeinflußung der farbsensitometrischen Eigenschaften von farbphotographischem Sofortbildaufzeichnungsmaterial für das Diffusions-Übertragungsverfahren
GB4974073A GB1451345A (en) 1972-10-25 1973-10-25 Photographic colour diffusion transfer product and method of manufacture
CA264,779A CA1023592A (en) 1972-10-25 1976-11-03 Sensitometric modification by pre-exposure

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CA (1) CA1014399A (de)
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FR (1) FR2204819B1 (de)
GB (1) GB1451345A (de)
NL (1) NL175953C (de)

Cited By (8)

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Publication number Priority date Publication date Assignee Title
US3990898A (en) * 1974-06-26 1976-11-09 Polaroid Corporation In-process color balance adjustment of photographic film using filter dyes
US4172640A (en) * 1977-12-30 1979-10-30 Polaroid Corporation Movie camera having supplemental exposure
US4329411A (en) * 1974-12-30 1982-05-11 Polaroid Corporation Multicolor diffusion transfer products
US4634244A (en) * 1985-12-16 1987-01-06 Daniel Jobin Flashing device for motion picture camera
US5328787A (en) * 1993-05-24 1994-07-12 Eastman Kodak Company Method for assessing and controlling the sensitometric characteristics of photographic products
US6334209B1 (en) * 1998-09-03 2001-12-25 Kabushiki Kaisha Toshiba Method for exposure-mask inspection and recording medium on which a program for searching for portions to be measured is recorded
US20040202463A1 (en) * 1999-07-02 2004-10-14 Fuji Photo Film Co., Ltd. Method of and apparatus for manufacturing instant photography film unit
US20050248813A1 (en) * 2004-05-06 2005-11-10 Eastman Kodak Company Two-stage exposure device for watermarking film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53144330A (en) * 1977-05-23 1978-12-15 Fuji Photo Film Co Ltd Correcting device for color temperature of camera

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Publication number Priority date Publication date Assignee Title
US3241961A (en) * 1961-11-16 1966-03-22 Du Pont Process for forming images
US3352672A (en) * 1964-04-09 1967-11-14 Eastman Kodak Co Photographic direct positive color process and element
US3647437A (en) * 1970-12-18 1972-03-07 Polaroid Corp Photographic products, processes and compositions
US3752723A (en) * 1971-04-20 1973-08-14 Polaroid Corp Method of manufacturing self developing photographic film units

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1266438A (fr) * 1960-09-03 1961-07-07 Agfa Ag Procédé pour influencer la gradation d'un matériel de copie photographique en couleurs
AU450148B2 (en) * 1970-12-18 1974-06-27 Polaroid Corp. Color diffusion transfer film unit containing a temporary barrier for developing restrainers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3241961A (en) * 1961-11-16 1966-03-22 Du Pont Process for forming images
US3352672A (en) * 1964-04-09 1967-11-14 Eastman Kodak Co Photographic direct positive color process and element
US3647437A (en) * 1970-12-18 1972-03-07 Polaroid Corp Photographic products, processes and compositions
US3752723A (en) * 1971-04-20 1973-08-14 Polaroid Corp Method of manufacturing self developing photographic film units

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3990898A (en) * 1974-06-26 1976-11-09 Polaroid Corporation In-process color balance adjustment of photographic film using filter dyes
US4329411A (en) * 1974-12-30 1982-05-11 Polaroid Corporation Multicolor diffusion transfer products
US4172640A (en) * 1977-12-30 1979-10-30 Polaroid Corporation Movie camera having supplemental exposure
US4634244A (en) * 1985-12-16 1987-01-06 Daniel Jobin Flashing device for motion picture camera
US5328787A (en) * 1993-05-24 1994-07-12 Eastman Kodak Company Method for assessing and controlling the sensitometric characteristics of photographic products
US6334209B1 (en) * 1998-09-03 2001-12-25 Kabushiki Kaisha Toshiba Method for exposure-mask inspection and recording medium on which a program for searching for portions to be measured is recorded
US20040202463A1 (en) * 1999-07-02 2004-10-14 Fuji Photo Film Co., Ltd. Method of and apparatus for manufacturing instant photography film unit
US6922979B2 (en) 1999-07-02 2005-08-02 Fuji Photo Film Co., Ltd. Method of and apparatus for manufacturing instant photography film unit
US20050248813A1 (en) * 2004-05-06 2005-11-10 Eastman Kodak Company Two-stage exposure device for watermarking film
US7777859B2 (en) 2004-05-06 2010-08-17 Eastman Kodak Company Two-stage exposure device for watermarking film

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DE2353534A1 (de) 1974-05-09
NL7314685A (de) 1974-04-29
NL175953C (nl) 1985-01-16
FR2204819B1 (de) 1982-06-11
CA1014399A (en) 1977-07-26
DE2353534C3 (de) 1982-09-02
FR2204819A1 (de) 1974-05-24
JPS4975329A (de) 1974-07-20
NL175953B (nl) 1984-08-16
JPS586938B2 (ja) 1983-02-07
GB1451345A (en) 1976-09-29
DE2353534B2 (de) 1981-02-19

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