|Publication number||US3888669 A|
|Publication date||Jun 10, 1975|
|Filing date||Sep 4, 1973|
|Priority date||Sep 4, 1973|
|Also published as||CA1036857A, CA1036857A1, DE2441751A1, DE2441751C2|
|Publication number||US 3888669 A, US 3888669A, US-A-3888669, US3888669 A, US3888669A|
|Inventors||Cardone Paul A|
|Original Assignee||Polaroid Corp|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (4), Referenced by (11), Classifications (7)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent Cardone 1 June 10, 1975 DIFFUSABLE DYES  Inventor: Paul A. Cardone, Framingham,
 Assignee: Polaroid Corporation, Cambridge,
 Filed: Sept. 4, 1973  Appl. No.: 393,799
Primary Examiner-Norman G. Torchin Assistant Examiner-Richard L. Schilling Attorney, Agent, or Firm-Robert M. Ford [5 7 ABSTRACT The present invention relates to photography, particularly, to photographic products specifically adapted for employment in specified photographic diffusion transfer color processes and, more particularly, to photographic products which comprise a fixed or permanent composite photosensitive structure including, as essential layers, in sequence, a first dimensionally stable layer transparent to actinic radiation; a polymeric layer dyeable by a diffusion transfer process dye image-forming material; a processing composition permeable opaque layer; a photosensitive silver halide layer having associated therewith a diffusion transfer process dye image-forming material; a processing composition permeable layer impermeable to a diffusion transfer process dye image-forming material; a second dimensionally stable layer transparent to actinic radiation; and means for providing a diffusion transfer process processing composition preferably retaining opacifying agent intermediate the dye imageforming material impermeable polymeric layer and the next adjacent second transparent dimensionally stable layer; and to specified photographic diffusion transfer color processes employing such products.
27 Claims, 9 Drawing Figures LAYER LAYER LAYER LAYER SENSlTlVE SILVER HALIM EMULSION LAYER YELLOW DYE EVELOPER iNSITIVE SILVER HAUDE EMUlSlW LAYER MMENTA DYE IVEUPER SENSITIVE SILVER HALIDE EMULSm LAYER CYAN (71E KVELIPER LAYER LAYER LAY ER SHEET PATENTED 10 PHOTOGRAPIIIC PRODUCTS AND PROCESSES WITH BARRIER LAYERS FOR DIFFUSABLE DYES BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is directed to providing new and improved diffusion transfer color process photographic film units adapted to provide, as a function of the point-to-point degree of photoexposure, by diffusion transfer processing dye transfer image formation.
2. Description of Prior Art As disclosed in U.S. Pat. No. 3,672,890 a composite photosensitive structure, particularly adapted for reflection type photographic diffusion transfer color process employment, which comprises a plurality of essential layers including, in sequence, a dimensionally stable layer preferably opaque to incident radiation; one or more silver halide emulsion layers having associated therewith a diffusion transfer process dye imageproviding material; a polymeric layer adapted to receive solubilized dye image-providing material diffusing thereto; and a dimensionally stable transparent layer, may be exposed to incident actinic radiation and processed by interposing, intermediate the silver halide emulsion layer and the reception layer, a processing composition and an opacifying agent, which may reflect incident radiation, in a quantity sufficient to mask dye image-providing material associated with the silver halide emulsion.
In a preferred embodiment, the composite photosensitive structure includes a rupturable container, retaining an alkaline processing composition and the opacifying agent, fixedly positioned extending transverse a leading edge of the composite structure in order to effect, upon application of compressive pressure to the container, discharge of the processing composition intermediate the opposed surfaces of the reception layer and the next adjacent silver halide emulsion.
The liquid processing composition, distributed inter mediate the reception layer and the silver halide emulsion, permeates the silver halide emulsion layers of the composite photosensitive structure to initiate development of the latent images contained therein resultant from photoexposure. As a consequence of the development of the latent images, dye image-providing material associated with each of the respective silver halide emulsion layers is individually mobilized as a function of the point-to-point degree of the respective silver halide emulsion layers photoexposure, resulting in imagewise distributions of mobile dye image-providing materials adapted to transfer, by diffusion, to the reception layer to provide the desired transfer dye image. Subsequent to substantial dye image formation in the reception layer, means associated with composite structure are adapted to convert the pH of the film unit from a first processing pH at which dye image'providing material is diffusible as a function of the film units photoexposure to a second pH at which the transfer dye image exhibits increased stability, preferably a sufficient portion of the ions of an alkaline processing composition transfers, by diffusion, to a polymeric neutralizing layer to effect reduction in the alkalinity of the composite film unit from a first alkaline processing pH to the second pH at which dye image-providing material is substantially nondiffusible, and further dye imageproviding material transfer is thereby substantially obviated.
The transfer dye image is viewed, as a reflection image, through the dimensionally stable transparent layer against the background provided by the opacifying agent, distributed as a component of the processing composition, intermediate the reception layer and next adjacent silver halide emulsion layer. The thus-formed opacifying stratum effectively masks residual dye image-providing material retained in association with the silver halide emulsion layer subsequent to processing.
In U.S. Pat. No. 3,415,644, the dimensionally stable layer of the film unit next adjacent the photosensitive layer or layers is disclosed to be opaque, the opacifying agent is initially disposed in an aqueous alkaline processing composition and the film units pH modulating means are disclosed to comprise a polymeric layer disposed intermediate the dimensionally stable transparent layer and the reception layer and adapted to reduce, subsequent to substantial dye transfer image formation, the pH of an aqueous alkaline processing composition from a first processing pH at which the dye-image-forming material or materials are soluble and diffusible in the composition as a function of the photoexposure of the photosensitive silver halide layer associated therewith to a second pH at which the dye imageforming material or materials are substantially nondiffusible and, as disclosed in U.S. Pat. No. 3,415,646, the dimensionally stable layer of the film unit next adjacent the photosensitive silver halide layer or layers is disclosed to be transparent to incident actinic radiation and, as further disclosed in U.S. Pat. No. 3,415,645, in such instance the opacifying agent may be initially disposed in the film unit intermediate the reception layer and next adjacent silver halide layer.
As disclosed in U.S. Pat. Nos. 3,615,421 and 3,661,585, the opacifying component of the film unit may optionally be initially disposed as a preformed processing composition permeable layer, intermediate the reception layer and next adjacent silver halide layer, in a concentration which prior to photoexposure is insufficient to prevent transmission therethrough of exposing actinic radiation and which, subsequent to processing, possesses an opacifying capacity effective to mask residual dye image-providing material retained associated with the film units silver halide emulsion layers, and in US. Pat. No. 3,647,435, the opacifying component of the film unit may optionally be initially formed in situ, intermediate the reception layer and next adjacent silver halide layer, during photographic processing of the film unit.
In US, Pat. No. 3,647,437, the opacifying component is disclosed to optionally comprise a lightabsorbing reagent such as a dye which is present as an absorbing species at the first pH and which may be converted to a substantially non-absorbing species at the second pH, and in U.S. Pat. Nos. 3,473,925; 3,573,042 and 3,576,626, opacifying and reflecting component, respectively, may be individually interposed intermediate the silver halide layer and reception layer by selective distribution from a composite or a plurality of rupturable containers.
In U.S. Pat. No. 3,573,043, the polymeric neutralizing layer is disclosed to be optionally disposed intermediate the dimensionally stable opaque layer and next adjacent essential layer, i.e., next adjacent silver halide/dye image-providing material component, to effect the designated modulation of film units environmental pl-l; U.S. Pat. No. 3,576,625 discloses the employment of particulate acid distributed within the film unit to effect the modulation of the environmental pH, and U.S. Pat. No. 3,573,044 discloses the employment of processing composition solvent vapor transmissive dimensionally stable layers to effect process modulation of dye transfer as a function of solvent concentration.
Where desired, the film unit may also be constructed in accordance with the disclosure of U.S. Pat. Nos. 3,594,164; 3,594,165; 3,689,262 and 3,701,656 to comprise a composite photosensitive structure including a transparent dimensionally stable layer carrying a reception layer, a processing composition permeable opaque layer and a photosensitive silver halide layer and the film unit may include a separate dimensionally stable sheet element adapted to be superposed on the surface of the photosensitive structure opposite the dimensionally stable layer and may further include means such as a rupturable container retaining processing composition for distribution of a processing composition intermediate the sheet and photosensitive structure to effect processing. As further disclosed in certain of the last-cited patents and applications, in structures wherein the receptor is positioned next adjacent the transparent layer or the processing composition and/or the sheet is to be separated from the remainder of the film unit subsequent to processing, the latter elements may optionally include opacifying component.
As disclosed in U.S. Pat. No. 3,620,724, the dimensionally stable layer referred to may be opaque and in which instance the photosensitive silver halide layer is positioned next adjacent the opaque support layer and the opacifying component of the film units processing composition permeable opaque layer will be disposed in the unit in a concentration insufficient to prevent transmission therethrough of exposing actinic radiation and which, subsequent to processing, possesses an opacifying capacity effective to mask residual dye image-providing material retained associated with the silver halide layer, and as disclosed in U.S. Pat. No. 3,647,434, the opacifying agent may be optionally formed in such film unit, in situ, during processing of the unit.
As disclosed in British Pat. No. 874,046, two or more separate diffusion transfer process images may be simultaneously provided by exposure and diffusion transfer processing of a film unit which includes a transfer process image-receiving layer located contiguous one major surface of a silver halide emulsion and an imagereceiving element superposed contiguous the opposite major surface of the emulsion during processing and, subsequent to processing, separating the imagereceiving element from its superposed relationship with the emulsion and, where required, the emulsion from its contiguous relationship with the image-receiving layer for viewing of the respective transfer images.
SUMMARY OF THE INVENTION The present invention is directed to novel photographic diffusion transfer color process film units and specifically to integral negative/positive, diffusion transfer process photographic film units adapted to provide, by diffusion transfer processing, photographic color image reproduction as a function of exposure of such film unit to incident actinic radiation.
In accordance with the present invention, the film units will comprise a plurality of layers including, in relative order, afirst dimensionally stable layer transparent to incident actinic radiation; a diffusion transfer process dye image-forming material impermeable layer permeable to processing composition; one or more photosensitive silver halide layers having associated therewith one or more diffusion transfer process dye image-forming materials; an opaque layer; a second transparent layer adapted to receive dye image-forming material diffusing thereto and a second dimensionally stable layer transparent to incident actinic radiation; means for providing, intermediate the first dimensionally stable layer and next adjacent dye image-forming material impermeable layer, opacifying agent; and means for providing a processing composition in contact with the photosensitive layers, and, in a particularly preferred embodiment, a processing composition possessing a first pH at which the diffusion transfer process dye image-forming material is diffusible during processing and means for modulating the pH of the film unit from the first pH to a second pH at which dye image-forming material is substantially nondiffusible subsequent to substantial dye transfer image formation.
In accordance with a specifically preferred embodiment of the present invention, a film unit assemblage of the aforementioned general structural parameters will be adapted to be processed, subsequent to photoexposure, in the presence of actinic radiation and may be fabricated to employ, as opacifying agent interposed intermediate the first dimensionally stable layer and next adjacent dye image-forming material impermeable layer subsequent to photoexposure, an inorganic lightreflecting pigment dispersion and the means for interposing the opacifying agent and the processing composition will comprise a rupturable container, retaining the opacifying agent disposed in the processing composition selected, fixedly positioned extending transverse a leading edge of the film unit and adapted, upon application of compressive pressure, to distribute its contents intermediate the first dimensionally stable layer and next adjacent dye image-forming material impermeable layer.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a fragmentary perspective view of one embodiment of a photographic film unit in accordance with the invention;
FIGS. 2, 4 and 6 are diagrammatic enlarged crosssectional views of the film unit of FIG. 1, along section line 2-2, illustrating the association of elements during the three illustrated stages of the performance of a diffusion transfer process, for the production of a multicolor transfer image according to the invention, the thickness of the various materials being exaggerated, and wherein FIG. 2 represents an exposure stage, FIG. 4 represents a processing stage and FIG. 6 represents a product of the process; and
FIGS. 3, 5 and 7 are diagrammatic, further enlarged cross-sectional views of the film unit of FIGS. 2, 4 and 6, along section lines 33, 5-5 and 77, respectively, further illustrating, in detail, the arrangement of layers comprising the photosensitive laminate during the three illustrated stages of the transfer process;
FIG. 8 is a perspective view of a film pack comprising an assemblage of the film units; and
FIG. 9 is a longitudinal sectional view taken substantially midway between the sides of the film pack of FIG. 8.
DETAILED DESCRIPTION OF THE INVENTION As previously characterized, diffusion transfer photographic processing in accordance with the present invention may be employed to provide a positive reflection dye image, as a direct function of actinic radiation incident on a film unit assemblage which unit is preferably constructed to comprise a plurality of sequential layers including a first dimensionally stable layer transparent to incident radiation; a first transparent layer permeable to processing composition and impermeable to diffusion transfer process dye image-forming material diffusing thereto; one or more photosensitive silver halide layers having associated therewith one or more diffusion transfer process dye image-forming materials; an opaque layer; a layer adapted to receive dye imageforming material diffusing thereto, a second dimensionally stable layer transparent to incident radiation; means for interposing intermediate the first dimensionally stable layer and the next adjacent dye imageforming material impermeable layer opacifying agent, preferably an inorganic reflecting pigment dispersion, in a concentration effective to provide, subsequent to selective photoexposure of the silver halide layer, protection of the silver halide layer from further exposure to actinic radiation incident on the dimensionally stable layer; and means for converting the pH of the film unit from the first processing pH to a second pH at which the dye image-forming material is substantially nondiffusible subsequent to substantial dye image-forming material diffusion to the reception layer.
In view of the fact that the preferred dye imageforming materials comprise dyes which are silver halide developing agents, as stated above, for purposes of simplicity and clarity, the present invention will be further described hereinafter in terms of such dyes, without limitation of the invention to the illustrative dyes denoted, and, in addition the photographic film unit structure will be detailed hereinafter employing the last-mentioned preferred structural embodiment, without limitation of the invention to the preferred structure denoted.
The dye developers are compounds which contain, in the same molecule, both the chromophoric system of a dye and also a silver halide developing function. By a silver halide developing function is meant a grouping adapted to develop exposed silver halide. A preferred silver halide developing function is a hydroquinonyl group. Other suitable developing functions include ortho-dihydroxy-phenyl and orthoand para-amino substituted hydroxyphenyl groups. In genera], the developing function includes a benzenoid developing function, that is, an aromatic developing group which forms quinonoid or quinone substances when oxidized.
The dye developers are preferably selected for their ability to provide colors that are useful in carrying out subtractive color photography, that is, the previously mentioned cyan, magenta and yellow. The dye developers employed may be incorporated in the respective silver halide emulsion, in a preferred embodiment, or in a separate layer contiguous the respective silver halide stratum. Specifically, the dye developer may, for example, be in a coating or layer behind or directly disposed in the respective silver halide stratum and such dye developer structure may be applied by use of a coating solution containing about 0.5 to 8 percent, by weight, of the respective dye developer distributed in a film-forming natural, or synthetic, polymer. for example, gelatin, polyvinyl alcohol, and the like, adapted to be permeated by the chosen diffusion transfer fluid processing composition.
An extensive compilation of specific dye developers particularly adapted for employment in photographic diffusion transfer processes is set forth in U.S. Pat. No. 2,983,606 and in the various copending U.S. applications referred to in that patent, especially in the table of U.S. applications incorporated by reference into the patent as detailed in column 27. As examples of additional U.S. patents detailing specific dye developers for photographic transfer process use, mention may be made of U.S. Pat. Nos. 2,983,605; 2,992,106; 3,047,386; 3,076,808; 3,076,820; 3,077,402; 3,126,280; 3,131,061; 3,134,762; 3,134,765; 3,135,604; 3,135,605; 3,135,606; 3,153,734;
3,141,722; 3,142,565; and the like.
The silver halide strata comprising the multicolor photosensitive laminate preferably possess predominant spectral sensitivity to separate regions of the spectrum and each has associated therewith a dye developer which is, most preferably, substantially soluble in the reduced form only at a first pH possessing, subsequent to processing, a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion.
In a preferred embodiment of the present invention, the film unit is specifically adapted to provide for the production of a multicolor dye transfer image and the photosensitive laminate comprises, in order, at least two selectively sensitized silver halide emulsion strata each having dye image-providing material of predetermined image color subsequent to processing associated therewith which is soluble and diffusible substantially only at a first pH, as a function of the photoexposure of its associated silver halide emulsion stratum.
The silver halide emulsions comprising the multicolor photosensitive laminate preferably possess predominant spectral sensitivity to separate regions of the spectrum and each has associated therewith a dye, which is a silver halide developing agent and is, most preferably, substantially soluble in the reduced form only at a first pH, possessing subsequent to photoexposure or processing a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion. Specifically preferred dyes comprise dyes which exhibit major spectral absorption outside of the primary regions of the spectrum to which the associated silver halide emulsion is sensitive and a spectral transmission substantially complementary to that absorption, during exposure of the emulsion, and major spectral absorption within the spectral range to which the associated silver halide emulsion is sensitive and a spectral transmission substantially complementary to that absorption, subsequent to exposure or processing of said emulsion, for example, of the type disclosed in U.S. Pat. No. 3,307,947.
In one embodiment each of the emulsion strata, and its associated dye, may be spaced from the remaining emulsion strata, and their associated dye, by separate alkaline solution permeable polymeric interlayers and the dyeable polymeric layer next adjacent the polymeric acid layer may be separated from that layer by an alkaline solution permeable polymeric spacer layer, most preferably a polymeric spacer layer having decreasing permeability to alkaline solution with increasing temperature.
In such preferred embodiments of the invention, the silver halide emulsion comprises photosensitive silver halide dispersed in gelatin and is about 0.6 to 6 microns in thickness; the dye itself may be dispersed in an aqueous alkaline solution permeable polymeric binder, preferably gelatin, as a separate layer about 1 to 7 microns in thickness; the alkaline solution permeable polymeric interlayers, for example, gelatin, may be about 1 to microns in thickness; the alkaline solution permeable and dyeable polymeric layers are transparent and may be about 0.25 to 0.4 mil in thickness; the alkaline solution polymeric spacer layers are transparent and may be about 0.1 to 0.7 mil in thickness; the alkaline solution permeable polymeric acid layers are transparent and may be about 0.3 to 1.5 mils in thickness; and the dimensionally stable transparent layers are alkaline solution impermeable and may be about 2 to 6 mils in thickness. It will be specifically recognized that the relative dimensions recited above may be appropriately modified, in accordance with the desires of the operator, with respect to the specific product to be ultimately prepared.
In the preferred embodiment of the present inventions film unti for the production of a multicolor transfer image, the respective silver halide/dye developer units of the photosensitive element will be in the form of a tripack configuration which will ordinarily comprise a yellow dye developer/blue-sensitive emulsion unit, a cyan dye developer/red-sensitive emulsion unit and a magenta dye developer/green-sensitive emulsion unit intermediate those units, recognizing that the relative order of such units may be varied in accordance with the desires of the operator.
In those instances, where either or both the respec tive yellow and magenta dye developers, employed in a preferred tripack configuration which positions the yellow dye developer/blue-sensitive emulsion unti distal the opaque layer dimensionally stable transparent layer and the cyan dye developer/red-sensitive emulsion unit proximal the opaque layer to provide the multicolor transfer image, comprise a dye developer which exhibits major spectral absorption outside of the primary region of the spectrum to which its associated silver halide emulsion is sensitive and a spectral transmission substantially complementary to that absorption, during exposure of the emulsion, then, in many circumstances, it may be advantageous to incorporate filter agents adapted to insure the correct selective exposure of the respective emulsions less proximal the exposure surface of the laminate. Specifically, in the instance where the yellow dye developer exhibits major spectral transmission within the primary regions of the spectrum to which its associated silver halide emulsion is sensitive, that is, the blue region of the visible spectrum, during exposure of the emulsions, then a yellow filter agent may advantageously be incorporated intermediate the blue-sensitive emulsion and the remaining greenand red-sensitive emulsions, in order to prevent undesired exposure of the latter emulsions by reason of their inherent sensitivity to actinic radiation within the blue range of the spectrum generally present. In the instance where the magenta dye developer employed exhibits major spectral transmission within the primary region of the spectrum to which its associated silver halide emulsion is sensitive, that is, the green region of the visible spectrum, during exposure of the emulsions, a magenta filter agent may be advantageously incorporated intermediate the greenand red-sensitive emulsions in instances wherein the red-sensitive emulsion possesses sensitivity to actinic radiation within the green region of the spectrum.
Reference is now made to FIGS. 1 through 7 of the drawings wherein there is illustrated a preferred film unit of the present invention and wherein like numbers, appearing in the various figures, refer to like components.
As illustrated in the drawings, FIG. 1 sets forth a perspective view of the film unit, designated 10, and each of FIGS. 2 through 7 illustrate diagrammatic crosssectional views of film unit 10, along the stated section lines 2--2, 3-3, 5 -5 and 7-7, during the various depicted stages in the performance of a photographic diffusion transfer process as detailed hereinafter.
Film unit 10 comprises rupturable container 11, retaining, prior to processing, aqueous alkaline solution 12, and photosensitive element 13 including, in order, dimensionally stable transparent layer 24a; neutralizing layer 23a; spacer layer 23a; processing composition permeable, dye image-forming material barrier layer 25; blue-sensitive silver halide emulsion layer 15 containing yellow dye developer; interlayer 16; greensensitive silver halide emulsion layer 17 containing magenta dye developer; interlayer 18; red-sensitive silver halide emulsion layer 19 containing cyan dye developer; opaque layer 20; image-receiving layer 21; spacer layer 22b; neutralizing layer 23b; and dimensionally stable transparent layer 24b, both layer 24a and layer 2412 comprising an actinic radiation transparent and processing composition impermeable flexible sheet material.
Photosensitive element 13 may be provided with a binding member 26 extending around, for example, the specified edges of the element maintaining the element intact except at the interface between spacer layer 22a and barrier layer 25 during distribution of processing composition 12. As illustrated in the figures, the binding member may comprise a pressure-sensitive tape 26 securing the photosensitive elements components together at film unit 10s specified edges. Tape 26 will also act to maintainm processing composition 12 intermediate first spacer layer 22a/barrier layer 25 and upon application of compressive pressure to container 11 and distribution of its contents intermediate stated components 220 and 25. Under such circumstances, binder tape 26 will act to prevent leakage of processing composition from the film unit during and subsequent to photographic processing.
As illustrated, binding sheet 26 overlying and secured to the trailing edge sections of transparent layer 24a and transparent layer 24b cooperates with the trailing edge of each of the transparent layers to provide an enclosed chamber or trap area 2 adapted to secure and retain excess processing composition 12, employed to insure adequate processing composition coverage upon distribution. To further facilitate distribution of processing composition 12 between transparent layer 24a and transparent layer 24b, binding member 26 may be provided with one or more air release vents 1 associated with the trailing edge section of the film unit and preferably in direct communication with trap chamber 2 in order to facilitate release of air from the film unit during distribution of processing composition 12.
Rupturable container 11 may be of the type shown and described in any of U.S. Pat. Nos. 2,543,181; 2,634,886; 2,653,732; 2,723,051; 3,056,491; 3,056,492; 3,152,515; and the like. In general, such containers will comprise a rectangular blank of fluidand air-impervious sheet material folded longitudinally upon itself to form two walls 27 which are sealed to one another along their longitudinal and end margins to form a cavity in which processing solution 12 is retained. The longitudinal marginal seal 28 is made weaker than the end seals 29 so as to become unsealed in response to the hydraulic pressure generated within the fluid contents 12 of the container by the application of compressive pressure to walls 27 of the container.
As illustrated in FIGS. 1, 2 and 4, container 11 is fixedly positioned and extends transverse a leading edge of photosensitive laminate 13 whereby to effect unidirectional discharge of the containers contents 12 intermediate first spacer layer 22a and barrier layer 25, upon application of compressive force to container 11. Thus, container 11, as illustrated in FIG. 2, is fixedly positioned and extends transverse a leading edge of laminate 13 with its longitudinal marginal seal 28 directed toward the leading edge of the stated interface. As shown in FIGS. 1, 2 and 4, container 11 is fixedly secured to laminate 13 by extension 30 of tape 26 extending over a portion of one wall 27 of the container, in combination with a separate retaining member such as illustrated retaining tape 31 extending over a portion of the other wall 27 of the container and a portion of laminate 13s surface generally equal in area to about that covered by tape 26.
As illustrated in FIGS. 1, 2 and 4, extension flap 30 of tape 26 may be of such area and dimensions that upon, for example, manual separation of container 11 and leader 31, subsequent to distribution of the composition, from the remainder of film unit 10, flap 30 may be folded over the edge of laminate 13, previously covered by leader 31, in order to facilitate maintenance of the laminates structural integrity, for example, during the flexations inevitable in storage and use of the processed film unit, and to provide a suitable mask or frame, for viewing of the transfer image through the picture viewing area of transparent layer 24. Preferably, however, the film unit will be maintained intact subsequent to processing including retention of the exhausted container, the processing composition in the spacial position assumed during processing. In such instance, the processing composition employed should possess the requisite adhesive capacity, in both the fluid and dry states, to enhance the integrity and stability of the spacial arrangement assumed.
In general, in a particularly preferred embodiment, the opacity of processing composition 12 when distributed will be sufficient to prevent further exposure of the film units silver halide emulsion or emulsions, by actinic radiation incident on transparent layer 24a during processing of the unit in the presence of radiation actinic to the emulsion or emulsions. Accordingly, the film unit may be processed, subsequent to exposure, in the presence of such radiation, in view of the fact that the silver halide emulsion or emulsions of the laminate are appropriately protected from incident radiation, at
one major surface by the opaque layer or layers 20 and at the remaining major surface by opaque processing composition 12 as further described hereinafter. If the illustrated binder tapes are also opaque, as stated above, edge leakage of actinic radiation incident on the emulsion or emulsions will also be prevented. The selected opaque layer or layers 20, however, should be one providing a background suitable for viewing the respective dye developer transfer image formed in the dyeable polymeric layer. In general, while substantially any opaque processing composition and permeable opaque layer may be employed, it is preferred that a processing composition and layer be selected that will not interfere with the color integrity of the dye transfer image carried by the reception layers, as viewed by the observer, and, most preferably, an opaque processing composition and opaque layer which is aesthetically pleasing to the viewer and does not provide a background noise signal degrading, or detracting from, the information content of the dye image. Particularly desirable opaque compositions will be those providing a white background, for viewing the transfer image, and specifically those adapted to be employed to provide background for reflection photographic prints and, especially, those layers possessing the optical properties desired for reflectance of incident radiation.
The opaque layer may comprise substantially any opacifying agent compatible with the photographic system, such as, for example, barium sulfate, titanium dioxide, barium stearate, silver flake, zirconium oxide, and the like, which may be distributed in a permeable polymeric matrix or binder, such as, for example, gelatin, polyvinyl alcohol, and the like.
A particularly preferred opaque layer comprises titanium dioxide due to its highly effective reflection properties. In general, a coating composition, for example, hydroxyethylcellulose, containing sufficient titanium dioxide to provide a precent reflectance of about to percent, respectively, will be employed. In the most preferred embodiments, the percent reflectance desired thus will be in the order of 09 about 85 percent.
Where it is desired to increase the opacifying capacity of a layer containing, for example, titanium dioxide, beyond that ordinarily obtained, an additional opacifying agent such as carbon black, for example, in a concentration of about one part carbon black to one hundred to five hundred parts titanium dioxide may be provided to the layer. Preferably, however, such additional opacifying capacity will be provided by constituting the opacifying layer as a plurality of more or less discrete layers, the layer next adjacent the transparent support comprising a reflection layer and the succeeding layer or layers comprising one or more opacifying agents possessing greater opacifying capacity than that ordi narily obtained from the reflecting agent or agents employed.
Such additional opacifying agent may be any of the multiplicity of such agents known in the art such as carbon black, iron oxide, titanium (III) oxide, titanium (III) hydroxide, and the like. In preferance, the agent or agents should be selected which possess the maximum opacifying capacity per unit weight, is photographically nondeleterious and is substantially nondiffusible throughout the film unit subsequent to distribution. A particularly preferred agent has been found to comprise carbon black employed in a concentration effective, taken together with the selected reflecting agent, to provide the opacity required to prevent undesired physical fogging of the emulsion formulations selected and employed by radiation transmitted through the spread processing composition.
The fluid contents of the container preferably comprise an aqueous alkaline solution having a pH and solvent concentration at which the dye developers are so]- uble and diffusible and contains inorganic lightreflecting pigment in a quantity sufficient, upon distribution, to provide a layer exhibiting optical transmission density about six to prevent exposure of photosensitive silver halide emulsion layers 15, 17 and 19 by actinic radiation incident or dimensionally stable transparent layer 24a during processing in the presence of such radiation and to afford immediate viewing of dye image formation in image-receiving layer 21 during and subsequent to dye transfer image formation. Accordingly, the film unit may be processed, subsequent to distribution of the composition, in the presence of such radiation, in view of the fact that the silver halide emulsion or emulsions of film unit are appropriately protected by incident radiation, at one major surface of the opaque processing composition and at the remaining major surface by opaque layer 20. If the illustrated binder tapes are also opaque, edge leakage of actinic radiation incident on the emulsion or emulsions will also be prevented.
As examples of pigments adapted for employment in processing composition 12, mention may be made of those specifically identified above.
A particularly preferred processing composition reflecting agent comprises carbon black due to its highly effective light-absorption properties.
In general, the opacifying adjuvants to be employed are those which remain substantially immobile within their respective compositions during and subsequent to photographic processing and particularly those reflecting agents which comprise insoluble and nondiffusible inorganic pigment dispersions within the composition in which they are disposed.
Where desired, opacifying adjuvants constituting layer accordingly may thus be distributed within a processing composition permeable polymeric matrix such as gelatin and/or any other such polymeric matrixes as are specifically denoted throughout the specification as suitable for employment as a matrix binder and may be distributed in one or more of the film unit layers which may be separated or contiguous, intermediate the image-receiving layer and next adjacent silver halide layer, provided that its distribution and concentration is effective to provide the denoted post processing masking function, and the opacifying agent component of the processing composition may be ultimately disposed within the processing composition residuum located intermediate barrier layer 25 and transparent layer 24a.
In the performance of a diffusion transfer multicolor process employing film unit 10, the unit is exposed to radiation, actinic to photosensitive laminate 13, incident on the laminates exposure surface 34, as illustrated by FIG. 2.
Subsequent to exposure as illustrated by FIGS. 2 and 4, film unit 10 is processed by being passed through opposed suitable gapped rolls 33 in order to apply compressive pressure to frangible container 1 1 and to effect rupture of longitudinal seal 28 and distribution of processing composition 12, containing opacifying agent and having a pH at which the cyan, magenta and yellow dye developers are soluble and diffusible, intermediate first spacer layer 22a and barrier layer 25 coextensive their respective surfaces.
Processing composition 12 permeates through barrier layer 25 and into emulsion layers l5, l7 and 19 to initiate development of the latent images contained in the respective emulsions. The cyan, magenta and yellow dye developers, oflayers 15, 17 and 19, are immobilized, as a function of the development of their respective associated silver halide emulsions, preferably substantially as a result of their conversion from the reduced form to their relatively insoluble and nondiffusible oxidized form, thereby providing imagewise distributions of mobile, soluble and diffusible cyan, magenta and yellow dye developer, as a function of the point-t0- point degree of their associated emulsions exposure. At least part of the imagewise distributions of mobile cyan, magenta and yellow dye developer transfer, by diffusion, to processing composition dyeable polymeric layer 21 to provide to such layer a multicolor dye transfer image viewable through dimensionally stable transparent layer 24b. Subsequent to substantial transfer image formation, a sufficient portion of the ions comprising aqueous composition 12 transfer, by diffusion, through permeable spacer layers 22a and 22b and to permeable polymeric acid layers 23a and 23b whereby solution 12 decreases in pH, as a function of neutralization, to a pH at which the cyan, magenta and yellow dye developers, in the reduced form, are substantially insoluble and nondiffusible, to thereby provide increases stability to the multicolor dye transfer image.
Subsequent to distribtuion of processing solution 12, container 11, optionally, may be manually dissociated from the remainder of the film unit, as described above.
As previously stated, the multicolor dye transfer image is viewable through dimensionally stable transparent layer 24b both during and subsequent to transfer image formation, in the preferred embodiment detailed above.
The present invention will be further illustrated and detailed in conjunction with the following illustrative constructions which set out representative embodiments and photographic utilization of the novel photographic film units of this invention, which, however, are not limited to the details therein set forth and are intended to be illustrative only.
Film units similar to that shown in the drawings may be prepared, for example, by providing, in succession, on a first 4 mil. transparent polyester film base, the following layers:
1. the partial butyl ester of polyethylene/maleic anhydride copolymer at a coverage of about 2,500 mgs./ft. to provide a polymeric acid layer;
2. a timing layer containing about a 49:1 ratio of a /30/4/6 copolymer of butyacrylate, diacetone acrylamide, styrene and methacrylic acid and polyacrylamide at a coverage of about 500 mgs/ftF; and
3. a 2:1 mixture, by weight, of polyvinyl alcohol and poly-4-vinylpyridine, at a coverage of about 300 mgs./ft. to provide a polymeric image-receiving layer;
4. a 25:1 mixture of titanium dioxide and a 60/30/4/6 copolymer of butyl acrylate, diacetone acrylamide, styrene and methacrylic acid at a coverage of about 1800 mgs./ft.
5. gelatin at a coverage of about 50 mgs/ft 6. a 1:0.8:0.l mixture of carbon black, Rhoplex E-32 (an acrylic latex sold by Rohm and Haas Co., Philadelphia, Pa., U.S.A.) and polyacrylamide at a coverage of about 240 mgs./ft. measured as carbon;
7. a 1:1 mixture of (a) a solid dispersion of the cyan dye developer and gelatin coated to provide a coverage of about 100 mgs./ft. of dye developer and about 87 -mgs./ft. of gelatin and (b) a green-sensitive gelatino silver iodobromide emulsion coated to provide a coverage of about mgs./ft. silver iodobromide measured as silver and about 22 mgs./ft. gelatin;
HC-NHO S N===C CN a I 3 H0 l SO NH- -(|ZH N-C11N\ OH i T acl:rmo s HO u c C-N CH n I 3 SO NHCH H 1 gelatin and polyvinyl hydrogen phthalate coated to provide a coverage of about 67 mgs./ft. dye developer, about 97 mgs./ft. of gelatin and about 5 mgs./ft. of polyvinyl hydrogen phthalate and (b) a red-sensitive gelatino silver iodobromide emulsion coated to provide a coverage of about 67 mgs/ft. silver iodobromide measured as silver and about 29 mgs./ft. gelatin;
8. a red-sensitive gelatino silver iodobromide emulsion and polyvinyl hydrogen phthalate coated at a coverage of about 62 mgs./ft. silver iodobromide measured as silver, about 60 mgs./ft. gelatin and about 0.8 mgs./ft. polyvinyl hydrogen phthalate;
9. a layer of butyl acrylate/diacetone acrylamide/styrene/methacrylic acid (60/30/4/6) and polyacrylamide coated in a ratio of about 29: 1, respectively, at a coverage of about 162 mgs./ft.
10. a 1:1 mixture of (a) a solid dispersion of the magenta dye developer HO-CH -CH 1 1. a green-sensitive gelatino silver iodobromide emulsion and polyvinyl hydrogen phthalate coated at a coverage of about 40 mgs./ft. silver iodobromide measured as silver, about 87 mgs./ft. gelatin and about 1.3 mgs./ft. polyvinyl hydrogen phthalate;
12. a layer of butyl acrylate/diacetone acrylamide/styrene/methacrylic acid (/30/4/6) and polyacrylamide coated in a ratio of about 29:4, respectively, at a coverage of about mgs./ft. and succindialdehyde coated at a coverage of about 10 mgs./ft.
13. a 1:1 mixture of (a) a solid dispersion of the yellow dye developer NSO =N CH HO.'CH2 CHZ N/ Cr-H O c i1 cn==n Cr--H O C--CH2--CH2 and gelatin coated to provide a coverage of about 120 mgs./ft. dye developer and about 48 mgs./ft. of gelatin; and (b) a blue-sensitive gelatino silver iodobromide emulsion and polyvinyl hydrogen phthalate coated to provide a coverage of about 50 mgs./ft. silver iodobromide measured as silver, about 22 mgs./ft. gelatin and about 0.3 mgs./ft. polyvinyl hydrogen phthalate;
14. a blue-sensitive gelatino silver iodobromide emulsion, polyvinyl hydrogen phthalate and 4'- methylphenyl hydroquinone in N,N-diethyl lauramide coated at a coverage of about 100 mgs./ft. silver iodobromide measured as silver, about 66 mgsjft. gelatin, about 0.6 mgs./ft. polyvinyl hydrogen phthalate and about 25 mgs./ft. 4-methylphenyl hydroquinone;
15. a layer of butyl acrylate/diacetone acrylamide/styrene/methacrylic acid (60/ 30/4/6) coated at a coverage of about 100 mgs./ft.
A second 4 mil. transparent polyester film base may then be taped to the photosensitive element in laminate form, at their respective lateral and trailing edges, by means of a pressure-sensitive binding tape extending around, in contact with, and over the edges of the resultant laminate.
A rupturable container comprising an outer layer of lead foil and an inner liner or layer of polyvinyl chloride retaining an aqueous alkaline processing solution such as, for example, about 0.8 cc. of 0.5 cc. of 1N sodium hydroxide and about 0.8 cc. of water, about 100 cc. of 10.5 grams of potassium hydroxide, about 2.3 grams of carboxymethyl cellulose, about 95.6 grams of titanium dioxide, about 2.9 grams of N-benzyLapicolinium bromide, about 1.7 grams of n-phenethyl-apicolinium bromide, about 1.7 grams of an aqueous silica dispersion comprising about 30 percent SiO one or more antifoggants such as about 1.3 grams of benzotriazole and about 006 gram of 6-methyl-5-br0mo-4- azabenzimidazole, about 0.67 gram of 6-methyl uracil, about 0.47 gram of bis-(B-aminoethyl)-sulfide, about 0.94 gram of 6-benzyl-amino purine, about 1.22 grams of polyethylene glycol, about 1.9 grams of l-hydroxyethyl-ethylene diamine tetra acetic acid, about 0.22 gram of lithium nitrate, and about 0.25 gram of lithium hydroxide may then be fixedly mounted on the leading edge of each of the laminates, by pressure-sensitive tapes interconnecting the respective containers and laminates, such that, upon application of compressive pressure to the container, its contents may be distributed, upon rupture of the containers marginal seal, between the second transparent polyester film base and its next adjacent layer 15.
The photosensitive composite film units may be exposed through radiation incident on the second transparent polyester film base and processed by passage of the exposed film units through appropriate pressureapplying members, such as suitably gapped, e.g., to mils, opposed rolls, to effect rupture of the container and distribution of its contents. Subsequent to processing, multicolor dye transfer image formation may be viewed through the first transparent polyester layer against a titanium dioxide reflection layer.
Film units, fabricated essentially as denoted above, may be processed in the stated manner, subsequent to exposure through a conventional step wedge, to provide graphic illustration of the characteristic curves of the respective dye transfer images forming the multicolor dye positive images. Specifically, the detailed characteristic curves may be determined by plotting the density of the respective images to red, green and blue light, as a function of the log exposure of the photosensitive element, e.g., the characteristic cyan, magenta and yellow transfer image dye curves (read to red, green and blue reflected light) of the test film units.
By addition of an effective concentration of C ontinued' to the processing composition, for example, 6.17 and 1.37 grams, respectively, to the second processing composition component identified above, image formation in the second image-receiving layer may be immediately viewed upon distribution of the processing composition by reason of the protection against incident radiation afforded the photosensitive silver halide emulsion layers by the compositions optical transmission density of about six density units and against the titanium dioxides effective reflective background afforded by reason of the composition possessing an opti* cal reflection density of about one density units.
Processing composition permeable dye impermeable layer 25 of the structure detailed, in accordance with the present invention, allows passage of the fluid processing composition including processing adjuvants of a molecular size less than that of the stated yellow, magenta and cyan dye developers simultaneously preventing passage or extraction of processing composition solubilized dye developer from the photosensitive laminate into the processing composition in accordance with differential dye concentration gradients between the laminate and the compositions initial distribution locus and the dye sink capacity of processing compositions generally employed in dye diffusion transfer photographic systems. By restriction of diffusion of the dye to the photosensitive laminate during processing of the film unit, there is provided the efficiencies and economic advantages resultant from decreased dye required per unit dye transfer density of the resultant transfer image in addition to optimized control of the dye employed by its associated silver halide layer, as a function of the point-topoint degree of the layer exposure to actinic radiation, with the resultant increased acuity of the resultant dye transfer image generated.
As examples of additional polymeric compositions specifically adapted to provide the required processing composition permeable layer of the present invention impermeable to dye developer for the effective duration of the processing of a film unit constructed as detailed immediately above, mention may be made of, for example, butyl acrylate/diacetone acrylamide/styrene/- methacrylic acid (60/30/4/6) +polyacrylamide at 1 to 2 percent by weight of the tetrapolymer coated at a coverage of about 100 mgs./ft. butyl acrylate/diacetone acrylamide/styrene/methacrylic acid (60/30/4/6) polyvinyl alcohol at a :1 ratio coated at a coverage of about 100 mgs./ft. 2-sulfoethyl methacrylate/ethylacrylate/methacrylic acid; Rhoplex E-32, HA12 or HA-l6 (trade designation of Rohm and Haas Co., Philadelphia, Pennsylvania, USA, for certain acrylic latices) less than 1 percent polyacrylamide; and the like.
The pH and solvent concentration of the alkaline H-SO processing solution initially employed will preferably possess a pH above the pKa of the optical filter agents where the latter are employed, that is, the pH at which about fifty percent of the agents are present as the lesser absorbing species and about fifty percent are present as the greater absorbing species, preferably a pKa of about 1 1 and most preferably about 12 and a pH at which the dye developers employed are soluble and diffusible. Although it has been found that the specific pH to be employed may be readily determined empirically for any dye developer and optical filter agent, or group of dye developers and filter agents, most particularly desirable dye developers are soluble at pHs above 9 and relatively insoluble at pHs below 9, in reduced form, and the system can be readily balanced accordingly for such dye developers. In addition, although as previously noted, the processing composition, in the preferred embodiment, will include the stated film-forming viscosity-increasing agent, or agents, to facilitate spreading of the composition and to provide maintenance of the spread composition as a structurally stable layer of the laminate, subsequent to distribution, it is not necessary that such agent be employed as a component of the composition. In the latter instance, however, it will be preferred that the concentration of solvent, that is, water, etc., comprising the composition be the minimum amount necessary to conduct the desired transfer process, in order not to adversely effect the structural integrity of the laminate and that the layers forming the laminate can readily accommodate and dissipate the solvent throughout during processing and drying without effecting undesirable dimensional changes in the layers forming the laminate.'
As disclosed in the previously cited patents, the liquid processing composition referring to for effecting multicolor diffusion transfer processes comprises at least an aqueous solution of an alkaline material, for example, diethylamine, sodium hydroxide or sodium carbonate and the like, and preferably possessing a pH in excess of 12, and most preferably includes a viscosity-increasing compound constituting a film-forming material of the type which, when the composition is spread and dried, forms a relatively firm and relatively stable film. The preferred film-forming materials disclosed comprise high molecular weight polymers such as polymeric, water-soluble ethers which are insert to an alkaline solution such as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Additionally, film-forming materials or thickening agents whose ability to increase viscosity is substantially unaffected if left in solution for a long period of time arealso disclosed to be capable of utilization. As stated, the film-forming material is preferably contained in the processing composition in such suitable quantities as to impart to the composition a viscosity in excess of 100 cps. at a temperature of approximately 24 C. and preferably in the order of 100,000 cps. to 200,000 cps. at that temperature.
Neutralizing means, for example, a polymeric acid layer of the type discussed above will be incorporated, as stated, in the film unit of the present invention, to provide reduction of the alkalinity of the processing solution from a pH at which the dyes are soluble as a function of film unit photoexposure and above the pKa of selected optical filter agents where desired to a pH below the pKa of the filter agent selected and at which the dyes are substantially nondiffusible, in order to advantageously further stabilize and optimize reflectivity of the respective dye transfer images. In such instance, the neutralizing layer may comprise particulate acid reacting reagent disposed within the film unit or a polymeric acid layer, for example, a polymeric acid layer approximately 0.3 to 1.5 mils in thickness, positioned intermediate the first and/or second transparent support and the next adjacent functional layer and the film unit may also contain a polymeric spacer or barrier layer, for example, approximately 0.1 to 0.7 mil in thickness, next adjacent the respective polymeric acid layer or layers, opposite the respective support layer, as previously described.
Specifically, the film units may employ the presence of a polymeric acid layer such as, for example, of the type set forth in US. Pat. No. 3,362,819 which, most preferably, includes the presence of an inert timing or spacer layer intermediate the polymeric acid layer carried on a support and the image-receiving layer.
As previously noted, the pH of the processing composition preferably is of the order of about least 12 to 14 and the pKa of the selected optical filter agents will accordingly preferably be in the order of 12 or greater. The polymer layer is disclosed to contain at least sufficient acid groups to effect a reduction in the pH of the image layer from a pH of about 12 to 14 to a pH of at least ll or lower at the end of the imbibition period, and preferably to a pH of about to 8 within a short time after imbibition, thus requiring, of course, that the action of the polymeric acid be accurately so controlled as not to interfere with either development of the negative or image transfer of unoxidized dye developers. For this reason, the pH of the image layer must be kept at a functional transfer level, for example, 12 to 14 until the dye image has been formed after which the pH is reduced very rapidly to a pH below that at which dye transfer may be accomplished, for example, at least about 1 l and preferably about pH 9 to 10. Unoxidized dye developers containing hydroquinonyl developing radicals diffuse from the negative to the positive as the sodium or other alkali salt. The diffusion rate of such dye image-forming components thus is at least partly a function of the alkali concentration, and it is necessary that he pH of the image layer remain on the order of, for example, 12 to 14 until transfer of the necessary quantity of dye has been accomplished. The subsequent pH reduction, in addition to its desirable effect upon image light stability, serves a highly valuable photographic function by substantially terminating further dye transfer.
In order to prevent premature pH reduction during transfer processing, as evidenced, for example, by an undesired reduction in positive image density, the acid groups are disclosed to be so distributed in the polymer layer that the rate of their availability to the alkali is controllable, e.g., as a function of the rate of swelling of the polymer layer which rate in turn has a direct relationship to the diffusion rate of the alkali ions. The desired availability of the acid groups in the polymer layer may be effected by mixing acid polymer with a polymer free of acid groups, or lower in concentration of acid groups, and compatible therewith, as a modulated system, or by using only an acid polymer but selecting one having a predetermined acid group availability rate.
The layer containing the polymeric acid may also contain a water-insoluble polymer, preferably a cellulose ester, which acts to control or modulate the rate at which the alkali salt of the polymer acid is formed. As examples of cellulose esters contemplated for use, mention is made of cellulose acetate, cellulose acetate butyrate, etc. The particular polymers and combinations of polymers employed in any given embodiment are, of course, selected so as to have adequate wet and dry strength and when necessary or desirable, suitable subcoats are employed to help the various polymeric layers adhere to each other during storage and use.
The inert spacer layer of the last-mentioned patent, for example, an inert spacer layer comprising polyvinyl alcohol or gelatin, acts to time control the pH reduction by the polymeric acid layer. This timing is disclosed to be a function of the rate at which the alkali diffuses through the inert spacer layer. It is there stated to have been found that the pH does not drop until the alkali has passed through the spacer layer, i.e., the pH is not reduced to any significant extent by the mere diffusion into the interlayer, but the pH drops quite rapidly once the alkali diffuses through the spacer layer.
As disclosed in aforementioned US. Pat. No. 3,362,819, the presence of an inert spacer layer was found to be effective in evening out the various reaction rates over a wide range of temperatures, for example, by preventing premature pH reduction when imbibition is effected at temperatures above room temperature, for example, at to F. By providing an inert spacer layer, that application discloses that the rate at which alkali is available for capture in the polymeric acid layer becomes a function of the alkali diffusion rates.
However, as disclosed in US. Pat. No. 3,455,686, preferably the aforementioned rate at which the cations of the alkaline processing composition, i.e., alkali ions, are available for capture in the polymeric acid layer should be decreased with increasing transfer processing temperatures in order to provide diffusion transfer color processes relatively independent of positive transfer image variations over an extended range of ambient temperatures.
Specifically, it is there stated to have been found that the diffusion rate of alkali through a permeable inert polymeric spacer layer increases with increased processing temperature to the extent, for example, that at relatively high transfer processing temperature, that is, transfer processing temperatures above approximately 80 F., a premature decrease in the pH of the transfer processing composition occurs due, at least in part, to the rapid diffusion of alkali from the dye transfer environment and its subsequent neutralization upon contact with the polymeric acid layer. This was stated to be especially true of alkali traversing an inert spacer layer possessing permeability to alkali optimized to be effective with the temperature range of optimum transfer processing. Conversely, at temperatures below the optimum transfer processing range, for example, temperatures below approximately 40 F the lastmentioned inert spacer layer was disclosed to providel an effective diffusion barrier timewise preventing effective traverse of the inert spacer layer by alkali having temperature depressed diffusion rates and to result in maintenance of the transfer processing environments high pH for such an extended time interval as to facilitate formation of transfer image stain and its resultant degradation of the positive transfer images color definition.
It is further stated in the last-mentioned U.S. Pat. No. 3,455,686 to have been found, however, that if the inert spacer layer of the print-receiving element is replaced by a spacer layer which comprises a permeable polymeric layer exhibiting permeability inversely dependent on temperature, that is, a polymeric filmforming material which exhibits decreasing permeability to solubilized alkali derived cations such as alkali metal and quaternary ammonium ions under conditions of increasing temperature, that the positive transfer image defects resultant from the aforementioned overextended pH maintenance and/or premature pl-l reduction are obviated.
As examples of materials, for use as the imagereceiving layer, mention may be made of solution dyeable polymers such as nylon as, for example, N- methoxymethyl polyhexamethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate with filler as, for example, one-half cellulose acetate and one-half oleic acid; gelatin; and other materials of a similar nature. Preferred materials comprise polyvinyl alcohol or gelatin containing a dye mordant such as poly-4- vinylpyridine, as disclosed in U.S. Pat. No. 3,148,061, issued Sept. 8, 1964.
It will be noted that the liquid processing composition employed may contain an auxiliary or accelerating developing agent, such as p-methylaminophenol, 2,4- diaminophenol, p-benzylaminophenyl, hydroquinone, toluhydroquinone, phenylhydroquinone, 4'-methylphenylhydroquinone, etc. It is also contemplated to employ a plurality of auxiliary or accelerating developing agents, such as a 3-pyrazolidone developing agent and a benzenoid developing agent, as disclosed in U.S. Pat. No. 3,039,869, issued June 19, 1962. As examples of suitable combinations of auxiliary developing agents, mention may be made of l-phenyl-3-pyrazolidone in combination with p-benzylaminophenol and l-phenyl- 3-pyrazolidone in combination with 2,5-bisethylenimino-hydroquinone. Such auxiliary developing agents may be employed in the liquid processing composition or they may be initially incorporated, at least in part, in any one or more of the silver halide emulsion strata, the strata containing the dye developers, the interlayers, the image-receiving layer, or in any other auxiliary layer, or layers, of the film unit.
It may be noted that at least a portion of the dye developer oxidized during development may be oxidized and immobilized as a result of a reaction, e.g., an energy-transfer reaction, with the oxidation product of an oxidized auxiliary developing agent, the latter developing agent being oxidized by the development of exposed silver halide. Such a reaction of oxidized developing agent with unoxidized dye developer would regenerate the auxiliary developing agent for further reaction with the exposed silver halide.
In addition, development may be effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed in U.S. Pat. No. 3,173,786, issued Mar. 16, 1965.
lt will be apparent that the relative proportions of the agents of the diffusion transfer processing composition may be altered to suit the requirements of the operator. Thus, it is within the scope of thisinvention to modify the herein described developing compositions by the substitution of preservatives, alkalies, etc., other than those specifically mentioned, provided that the pH of the composition is initially at the first pH required. When desirable, it is also contemplated to include, in the developing composition, components such as restrainers, accelerators, etc. Similarly, the concentration of various components may be varied over a wide range and when desirable adaptable components may be disposed in the photosensitive element, prior to exposure, in a separate permeable layer of the photosensitive element and/or in the photosensitive emulsion.
The dimensionally stable layers or sheets referred to may comprise any of various types of conventional transparent rigid or flexible materials, for example, papers and polymeric films of both synthetic types and those derived from naturally occurring products. Suitable materials include alkaline solution impermeable materials such as polymethacrylic acid methyl and ethyl esters; vinyl chloride polymers, polyvinyl acetal; polyamides such as nylon; polyesters such as polymeric films derived from ethylene glycol and terephthalic acid; and cellulose derivatives such as cellulose acetate; triacetate, nitrate, propionate, butyrate, acetatepropionate or acetate-butyrate. It will be recognized that one or more or the designated layers may not be required where the remaining layers of the laminate are such as to provide the functions of these layers in the absence of same, for example, where the remaining layers of the laminate provide the prerequisite dimensional stability and radiation filtering properties.
In all examples of this specification, percentages of components are given by weight unless otherwise indicated.
Although the invention has been discussed in detail throughout employing dye developers, the preferred image-providing materials, it will be readily recognized that other, less preferred, diffusion transfer process dye image-providing materials may be substituted in replacement of the preferred dye developers in the practice of the invention. For example, there may be employed dye image-forming materials such as those disclosed in U.S. Pat. Nos. 2,647,049; 2,661,293; 2,698,244; 2,698,798; 2,802,735; 3,148,062; 3,227,550; 3,227,551; 3,227,552; 3,227,554; 3,243,294; 3,330,655; 3,347,671; 3,352,672; 3,364,022; 3,443,939; 3,443,940; 3,443,941; 3,443,943; etc., wherein color diffusion transfer processes are described which employ color coupling techniques comprising, at least in part, reacting one or more dye image-providing color developing agents and one or more dye image-providing color formers or couplers to provide a dye transfer image to a superposed image-receiving layer and those disclosed in U.S. Pat. Nos. 2,774,668 and 3,087,817, wherein color diffusion transfer processes are described which employ the imagewise differential transfer of complete dyes by the mechanisms therein described to provide a transfer dye image to acontiguous image-receiving layer, and thus including the employment of dye image-providing materials in whole or in part initially insoluble or nondiffusible as disposed in the film unit which diffuse during processing as a direct or indirect function of exposure.
Where desired, the film unit may also contain ultraviolet absorbing materials to protect the mordanted dye transfer image from fading due to ultraviolet light such as those selected from the general class of benzotriazoles and benzophenones as, for example, the substituted Z-phenyl-benzotriazole agents disclosed in US. Pats. Nos. 3,004,896; 3,189,615; etc.; the 2- hydroxybenzophenones such as 2-hydroxy-4- methoxybenzophenone; 2,2 '-dihydroxy-4- methoxybenzophenone; 2-hydroxy-4- octyloxybenzophenone; etc., both water and organic solvent soluble agents being contemplated, and/or brightening agents such as those selected from the general class of triazinestilbenes, coumarins, anthracenes, terphenyls, tetraphenylbutadienes, quinoxalines, conventional for use as fluorescent agents and as optical brightening agents. Suitable triazinestilbene optical brightening agents are disclosed in US. Pat. No. 2,933,390; coumarines are disclosed in British Pat. No. 786,234; and various agents are disclosed in US. Pat. Nos. 2,171,427; 2,473,475; 2,595,030; 3,660,578; and British Pat. Nos. 595,065; 623,849; 624,051; 624,052; 678,291; 681,642; 705,406; etc. Commercially available brightening agents are distributed under the trade designation Tinopal (SP, WR, SFG, BV277, 28, GS, NG) Leucophor B, Calcoflour White MR, Blaneofor SC, l-litamine (BSP, N, SOL., 6T6), and the like, and commercially available ultraviolet absorbing agents are distributed under the trade designation Tinuvin and the like.
In general, ultraviolet absorbing and optical brightening agents may be employed in concentrations varying over an extended range. Suitable concentrations include those within the range of about 0.2 to mgs./ft. of receptor layer surface area and, preferably, between about 1 to 5 mgs./ft.
The agents may be incorporated in any one or more of the layers of the film unit preferably intermediate an opaque layer forming the background against which an image is viewed and the viewing surface in any suitable manner as, for example, a constituent component of the casting and/or coating solution or formulation employed to provide such layer or layers employing an organic solvent or water carrier or as a latex dispersion.
1n the circumstances wherein the receptor layer or layers possess the dimensional stability to provide a self-sustaining layer conformation, the layer may optionally be coated on or carried by an appropriate dimensionally stable support layer of the various types and classes specifically designated hereinbefore or not at the election of the operator.
Ordinarily, when the image receptor stratum comprises a layer carried on a separate dimensionally stable support layer, the receptor stratum will comprise in the order of about 0.1 to 0.4 mil in thickness whereas such stratum employed as a self-sustaining layer will comprise in the order of about 3 to 6 mils in thickness.
In addition to conventional techniques for the direct dispersion of a particulate solid material in a polymeric, or colloidal, matrix such as ball-milling and the like techniques, the preparation of the dye developer and color coupler dispersions may also be obtained by dissolving the dye and/or coupler in an appropriate solvent, or mixture of solvents, and the resultant solution distributed in the polymeric binder, with optional subsequent removal of the solvent, or solvents, employed, as, for example, by vaporization where the selected solvent, or solvents, possesses a sufficiently low boiling point or washing where the selected solvent, or solvents, possesses a sufficiently high differential solubility in the wash medium, for example, water, when measured against the solubility of the remaining composition components, and/or obtained by dissolving both the polymeric binder and dye in a common solvent.
For further detailed treatment of solvent distribution systems of the types referred to above, and for an extensive compilation of the conventional solvents traditionally employed in the art to effect distribution of photographic color-providing materials in polymeric binders, specifically for the formation of component layers of photographic film units, reference may be made to US Pats. Nos. 2,269,158; 2,322,027; 2,304,939; 2,304,940; 2,801,171; and the like.
For the production of the photosensitive gelatino silver halide emulsions employed to provide the film unit, the silver halide crystals may be prepared by reacting a water-soluble silver salt, such as silver nitrate, with at least one water-soluble halide, such as ammonium, potassium or sodium bromide, preferably togehter with a corresponding iodide, in an aqueous solution of a peptizing agent such as a colloidal gelatin solution; digesting the dispersion at an elevated temperature, to provide increased crystal growth; washing the resultant water-soluble salts by chilling the dispersion, noodling the set dispersion, and washing the noodles with cold water, or alternatively, employing any of the various flocc systems, or procedures, adapted to effect removal of undesired components, for example, the procedures described in US. Pats. Nos. 2,614,928; 2,614,929; 2,728,662; and the like; after-ripening the dispersion at an elevated temperature in combination with the addition of gelatin and various adjuncts, for example, chemical sensitizing agents of US. Pats. Nos. 1,574,944; 1,623,499; 2,410,689; 2,597,856; 2,597,915; 2,487,850; 2,518,698; 2,521,926; and the like; all according to the traditional procedures of the art, as described in Neblette, C. B., Photography Its Materials and Processes, 6th Ed., 1962.
Optical sensitization of the emulsionss silver halide crystals may be accomplished by contact of the emulsion composition with an effective concentration of the selected optical sensitizing dyes dissolved in an appropriate dispersing solvent such as methanol, ethanol, acetone, water, and the like; all according to the traditional procedures of the art, as described in Hammer, F. M., The Cyanine Dyes and Related Compounds.
Additional optional additives, such as coating aids, hardeners, viscosity-increasing agents, stabilizers, preservatives, and the like, for example, those set forth hereinafter, also may be incorporated in the emulsion formulation, according to the conventional procedures known in the photographic emulsion manufacturing art.
The photoresponsive material of the photographic emulsion will, as previously described, preferably comprise a crystal of silver, for example, one or more of the silver halides such as silver chloride, silver iodide, silver bromide, or mixed silver halides such as silver chlorobromide, silver chloroiodobromide or silver iodobromide, of varying halide ratios and varying silver concentrations.
As the binder for the respective emulsion strata, the aforementioned gelatin may be, in whole or in part, replaced with some other colloidal material such as albumin; casein; or zein; or resins such as a cellulose deriva tive, as described in US. Pat. Nos. 2,322,085 and 2,327,808; polyacrylamides, as described in US. Pat. No. 2,541,474; and vinyl polymers such as described in an extensive multiplicity of readily available US. and
Although the preceding description of the invention has been couched in terms of the preferred photosensitive component construction wherein at least two selectively sensitized photosensitive strata are in contiguous coplanar relationship and, specifically, in terms of the preferred tripack type structure comprising a redsensitive silver halide emulsion stratum, a greensensitive silver halide emulsion stratum and a bluesensitive silver halide emulsion stratum having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer, the photosensitive component of the film unit may comprise at least two sets of selectively sensitized minute photosensitive elements arranged in the form of a photosensitive screen wherein each of the minute photosensitive elements has associated therewith, for example, an appropriate dye image-forming material in or behind its respective silver halide emulsion portion. In general, a suitable photosensitive screen may comprise minute red-sensitized emulsion elements, minute green-sensitized emulsion elements and minute bluesensitized emulsion elements arranged in side-by-side relationship in a screen pattern and having associated therewith, respectively, for example, a cyan, a magenta and a yellow dye developer.
The present invention also includes the employment of a black dye image-providing material and the use of a mixture of, for example, dye developers adapted to provide a black-and-white transfer image, for example, the employment of dye developers of the three subtractive colors in an appropriate mixture in which the quantities of the dye developers are proportioned such that the colors combine to provide black.
Where in the specification, the expression positive image has been used, this expression should not be interpreted in a restrictive sense since it is used primarily for purposes of illustration, in that it defines the image produced on the image-carrying layers as being reversed, in the positive-negative sense, with respect to the image in the photosensitive emulsion layers. As an example of an alternative meaning for positive image, assume that the photosensitive element is exposed to actinic light through a negative transparency. In this case, the latent image in the photosensitive emulsion layers will be a positive and the dye image produced on the image-carrying layers will be negative. The expression positive image is intended to cover such an image produced on the image-carrying layer.
In addition to the described essential layers, it will be recognized that the film unit may also contain one or more subcoats or layers, which in turn, may contain one or more additives such as plasticizers, intermediate essential layers for the purpose, for example, of improving adhesion, and that any one or more of the described layers may comprise a composite of two or more strata of the same, or different, components and which may be contiguous, or separatedfrom, each other, for example, two or more neutralizing layers or the like.
Where desired sheet 24a, illustrated in the figures as transparent and superposed coextensive the exposure surface of the photosensitive laminate in the preferred embodiment, may be adapted to be superposed on the laminate subsequent to photoexposure of the film unit as, for example, by fixedly positioning a leading edge of the sheet extending transverse a leading edge of the photosensitive laminate and adapted to be superposed, subsequent to photoexposure, on and coextensive the exposure surface of the laminate, at least during processing, to facilitate distribution of processing composition upon, for example, rupture of the container and unidirectional discharge of its processing composition contents contiguous the exposure surface of the laminate. In such embodiment the displaceable sheet may be transparent or opaque and the processing composition may or may not retain opacifying agent, at the election of the operator. Subsequent to distribution of the processing composition, the sheet may be manually dissociated from the remainder of the film unit individually and/or in combination with the processing composition employed and/or the expended processing composition rupturable container.
In accordance with the present invention, the preferred form of the film assemblage for the production of a dye reflection print comprises a photosensitive film unit constructed as described above and specifically adapted to be processed in the presence of ambient radiation and the dye reflection print image to be viewed during and subsequent to processing without separation of film unit components and includes leader means for coupling film units and selectively withdrawing the units sequentially from a film pack or magazine and opacifying agent, preferably disposed in whole or in part in the processing composition, taken together with the opaque layer, adapted to prevent exposure of the first sheet elementss photoresponsive material by radiation actinic thereto incident on the film unit in the processing mode.
A preferred form of film pack or magazine embodying the designated film units comprises a plurality of the film assemblies, each adapted to be individually exposed to a camera, enclosed in an initially light-proof container which allows the film units to be sequentially exposed. The container includes a forward wall having a light-transmitting section, e.g., an exposure aperture, therein and an opening in one wall through which film assemblies can be individually withdrawn. The photosensitive film units are positioned together in stacked relationship within the container underlying the exposure aperture with the exposure surface of each film unit uppermost and the rupturable container positioned adjacent the opening through which the film units are withdrawn so that following the exposure of each film unit, the unit is moved, by drawing on the leader of the film unit, and withdrawn from the container through the opening. The film pack is initially provided with a cover element or sheet mounted within the container and extending across the exposure aperture for closing the aperture against the admission of light. The cover element also includes a leader extending from the container through the opening and being removable therethrough.
The film pack is employed by being positioned in a camera, including a pair of juxtaposed pressureapplying members, with the opening located adjacent the pressure-applying members and the exposure aperture disposed approximately in the exposure plane of the camera. A leader for the cover element extends from the pack and from the camera where the lastmentioned leader may be grasped for withdrawing the I cover element from the pack through the pressureapplying members and camera to allow'the film units of the pack to be selectively exposed. After each successive film unit is exposed, that film unit is then individually withdrawn from the container and camera between the pressure-applying members by withdrawing the leader of the first film unit and of successive film 27 units from the container and camera.
Reference is now made to FIGS. 1, 8 and 9 of the drawings wherein there are illustrated film units and an assemblage of film units in the form of a film pack. Each film unit 10 includes a leader sheet 31 having a leading end section designated 38 and a trailing end section 40 at which the leader sheet 31 is coupled with the film unit near the leading end thereof. Leader sheet 31 including leading and trailing end sections 38 and 40 is approximately equal in width to the film unit 10 and leading end section 38 of each leader sheet 31 is secured to the trailing end of the next preceding film unit or, in the case of the first film unit, to the cover sheet, preferably near the trailing end section of the preceding element (cover sheet or film unit). The length of leader sheet 31 between its leading edge attachment to one film unit and the trailing edge to the next succeeding film unit is substantially equal to the length of the film units between their leading and trailing edges; and the connected film units and leaders are arranged in zig-zag folded relation.
A film pack or assemblage of film units 10 embodying the invention is shown in FIGS. 8 and 9 of the drawings. This film pack, designated 44, comprises all of the components and structure including pressure-applying means required to produce a plurality of diffusion transfer process color prints. Film pack 44 comprises a generally parallelepipedshaped container or box 46 for holding and enclosing a plurality of film units 10 arranged in stacked relation. Container 46 is shown as comprising a forward wall 48, side walls 50, a trailing end wall 52, a leading end wall 54, and a rear wall 56 and is preferably formed of plastic material that is at least semi-rigid and adapted to conventional molding techniques. Forward wall 48 is provided with a generally rectangular exposure aperture 58 for transmitting light for exposing the forwardmost of the film units carried in stacked relation within the container. Leading end wall 54 is provided with a generally rectangular withdrawal slot or exit opening 60 the forward edge of which is defined by forward wall 48 and through which film units 10 carried by the container are adapted to be withdrawn one at a time following exposure. In order to help insure that only one film unit at a time passes through opening 60, restraining means in the form of one or more projections or extensions 62 of end wall 54 may be provided. Projections 62, which as illustrated are integral parts of end wall 54, project forwardly part way across opening 60 to positions whereat they suffuciently obstruct the opening to the extent that they must be deformed in order to permit the passage of the forwardmost film unit in the stack, that is, the film unit positioned for exposure across aperture 58 against forward wall 48. Projections 62 comprise a resilient construction such that as the leading film unit is withdrawn through opening 60, the leading edge of the film unit will engage and deflect projections 62 outward sufficiently to permit the forward film unit only to move through slot 60, while preventing the next succeeding film unit from moving through the slot.
The film pack of the invention is initially provided with a dark slide or cover sheet 64 formed of an actinic light-impermeable sheet material for preventing admission of light through exposure aperture 58 prior to loading of the film pack into a camera or attachment of the film pack to the rear of the camera. Cover sheet 64 includes a section at least coextensive in area with forward wall 48 for preventing the admission of light and a leading end section 66 which may be tapered, as
shown, extending from the film pack and providing a leader which may be grasped for manually withdrawing the cover sheet from the film pack to permit exposure of film units arranged in stacked relation underlying the exposure opening and cover sheet. A lip 68 is provided on forward wall 48 surrounding opening 58 for cooperating with the camera to properly locate the film pack and exposure opening therein with respect to the exposure systems of the camera and in instances where the film pack is coupled to the rear of the camera rather than being completely enclosed therein, lip 68 also cooperates to form a light-tight seal between the interior of the camera and the interior of the film pack container.
As previously noted, the film units 10 are arranged in stacked relation between the forward and rear walls of the film pack with sheets 24a facing forwardly and the exposure areas of the film units aligned with exposure opening 58. Means are provided for resiliently biasing the film units 10 and cover sheet 64 forwardly against the rear surface of forward wall 48 to light-seal the exposure aperture when the cover'sheet is in place and following cover sheet removal, locate the forwardmost film unit in proper position for exposure in the image plane of the camera, i.e., against the rear surface of forward wall 48. These means include a spring and pressure plate assembly designated 70, preferably formed of resilient sheet metal and including a generally rectangular frame 72 for engaging and supporting the rearwardmost film unit and a transverse portion 74 from which extend rearwardly biased spring sections 76 engaged with the rear wall 56 of the film pack for biasing frame 72 and the film units supported thereby, forwardly toward forward wall 48.
As previously noted, each film unit 10 includes a leader 31 attached at its trailing end 40 to the forward surface of the film unit near the leading end thereof. The film units and leaders are arranged in the film pack container with the trailing end of each leader 31 folded back upon itself so that the leader extends toward the trailing end of the film unit and pack container between the forward surface of the film unit of which it is a component and the rear surface of the cover sheet 64 (in the case of the forwardmost film unit) or the rear surface of the preceding film unit next adjacent forward wall 48 and exposure aperture 58. The leading end 38 of each leader is folded forwardly upon itself and attached to the rear surface of the component, i.e., cover sheet 64 or film unit 10, located next adjacent the forward wall and is secured to said component near the trailing end thereof. Thus the cover sheet 64 and succession of film units 10 are joined by leaders 31, each of which extends from the trailing end of the component to the leading end of the next component (film unit) to be withdrawn from the pack. The leaders 3] are folded in zig-zag fashion to provide a stack comprising cover sheet 64, a leader 31, a film unit 10, another leader 31, and so forth. Each leader 31 may be weakened by perforations, precutting, or the like so that the portion of a leader attached to a film unit within the pack and extending from the pack to provide a leader for withdrawing the last-mentioned film unit may be severed from the portion of the leader attached to the preceding component, i.e., cover sheet 64 or film unit 10.
In accordance with the invention, film pack 44 includes means for compressively engaging each film unit as it is withdrawn therefrom following exposure, to rupture container 11 causing the discharge of its liquid
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|US6203970 *||Dec 16, 1999||Mar 20, 2001||Eastman Kodak Company||Photographic element with porous membrane overcoat|
|U.S. Classification||430/214, 430/236, 430/215|
|International Classification||G03C8/44, G03C8/00|