Classifications

• • 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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/492—Photosoluble emulsions
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/153—Multiple image producing on single receiver

Definitions

• ABSTRACT OF THE DISCLOSURE Process for forming images comprising (a) exposing a photosoluble silver halide emulsion layer imagewise so that the layer will have (i) areas of high exposure sufficient to form a photosoluble latent image, (ii) areas of intermediate exposure to form a developable latent image, and (iii) areas of no exposure insuflicient to form a developable or photosoluble latent image, (b) treating the layer, prior to reducing the silver halide, with a silver halide solvent solution to effect solubilization of silver halide in areas (i) at a rate greater than in areas (ii) and (iii) until a positive image is formed, and (c) treating the layer with a developing solution to develop areas (ii) and not areas (iii).
• the process is useful in obtaining unusual and artistic efiects, conversion of silhouette images to colored outlined images, and in two-color duplication of black and white originals.
• This invention relates to a process for forming images from photosoluble silver halide emulsion layers.
• the process of this invention comprises, in the order stated, the sequential steps of (a) exposing a layer containing photosoluble silver halide crystals made relatively less soluble in a silver halide solvent by treatment with an organic compound capable of forming a silver salt of lower solubility in water than silver chloride, to an image producing pattern of actinic radiation so that the layer will have (i) Areas of relatively high exposure, suflicient to form a photosoluble latent image,
• a photosoluble latent image results when a photosoluble layer is imagewise exposed to sufiicient actinic radiation to render it soluble in an aqueous silver halide solvent at a rate substantially greater in exposed than in unexposed areas.
• a developable latent image results when a photosoluble layer is imagewise exposed to suflicient actinic radiation to render it reducible to silver in a conventional aqueous photographic developer at a rate substantially greater in exposed than in unexposed areas.
• Photosoluble silver halide emulsion layers useful in accordance with this invention are disclosed in Blake, U.S.P. 3,155,507.
• a very large number of organic compounds are disclosed as suitable for use in treating silver halide emulsions to give them the desired properties.
• This Blake patent also describes qualitative testing procedures to determine whether or not a particular organic compound was satisfactory and quantitative tests useful in estimating the needed concentration of the organic compound.
• a photosoluble layer is prepared in a manner taught in US. 3,15,507.
• a gelatino-silver halide (especially silver chloride) emulsion is precipitated, ripened, and washed to remove soluble salts, all in a conventional manner.
• the emulsion is digested at a temperature of F. to 200 F. in the presence of a selected organic compound, e.g., one of the aromatic mercaptans listed in said patent.
• an optical sensitizing dye may also be present during this digestion as disclosed in the above Blake application, Ser. No. 390,460 U.S.P.
• the photosoluble element thus prepared is exposed to at least three different levels of acetinic radiation, one of which levels may include zero exposure.
• levels may include zero exposure.
• the element is then treated with an aqueous solution of a silver halide solvent, e.g., a conventional photographic fixing solution containing Na S O
• a silver halide solvent e.g., a conventional photographic fixing solution containing Na S O
• the photosolubilized silver halide of area (i) will be removed by the silver halide solvent. Treatment with the solvent is stopped prior to the removal of any substantial quantity of silver halide in the less exposed areas (ii) and (iii).
• An optional step of Washing the element in water may follow treatment with the silver halide solvent.
• the element is treated with a conventional photographic developing solution of a concentration and for a period sufficient to develop the latent image in the remaining silver halide.
• a conventional photographic developing solution of a concentration and for a period sufficient to develop the latent image in the remaining silver halide.
• the silver halide in the area of intermediate exposure, area (ii) will be reduced to a metallic silver image while the area of low or zero exposure, area (iii), will be essentially unaffected by the photographic developer solution.
• Optional washing and drying steps may follow the treatment with the developer solution.
• the variation in image composition can be made more apparent visually by toning the remaining silver halide with a mordanting dye or by fogging and color-coupler developing it. If the first developer used is also a colorcoupler developer, two colored images result which may be seen more clearly if the developed silver is removed by a bleaching step. In either case image color is exposuredependent.
• One or more color developing steps may be employed and/or one or more color couplers may be used simultaneously.
• a silhouette By exposing the photosoluble film to a silhouette image, a silhouette also results corresponding in color to the toner or second color coupler but it is bordered by a fine outline of black silver in the first case, or a colored outline corresponding to the first color coupler in the second case. This outline results from light scattered by the exposed region. If the remaining silver halide is fixed instead of toned or color coupling developed, only the silhouette outline remains.
• the photosoluble film is exposed through two different black and white transparencies in register, the first exposed with intensity sufiicient for solubilization, the second exposed with intensity sufiicient to form 2.
• developable latent image but not to be solubilized then the processing sequence of fixing and developing gives silver halide where the two transparencies are both black, and gives black silver where the first transparency is black and the second is not (two distinctive colors could also be produced using a toner or color-coupler developers).
• Final fixing of the silver-silver halide image leaves the silver image corresponding to where the first transparency is black and the second is clear.
• the invention is the process of producing an image whose composition is exposure dependent, starting with unfogged photosoluble layers.
• the process comprises image exposure, fixing, developing, and optionally, other steps to make the composition variation more apparent visually, physically, or chemically.
• the gelatin-silver-silver halide image is treated with a peroxide oxidizing bleach, the gelatin in silver areas is degraded giving a resist which could be etched in open areas to give a relief.
• the silver halide-gelatin image remaining could be differentiated by development.
• a second peroxide etching treatment could then be carried out as disclosed in E. J. Wall, History of Three-Color Photography (American Publishing Company, Boston, Mass. (1925), page 357.
• the invention also includes elements resulting from the above defined basic process or any embodiment of the process subgeneric thereto.
• the invention will be further illustrated but is not to be limited to the following examples wherein, unless otherwise specified, all operations were carried out in darkness or under appropriate safe lights.
• EXAMPLE I A light sensitive gelatino-silver chloride coagulate, made by precipitation and coagulation Washing in the manner taught in Moede, US. 2,772,165, was redispersed in an aqueous gelatin solution so as to achieve a gelatin to silver chloride weight ratio of 0.79 to 1.0. The resulting emulsion was digested in th? presence of 0.8 g. of 2- mercapto-4-phenylthiazole and 0.025 g. of a merocyanine spectral sensitizing dye 1 per mole of silver chloride at F. for 20 minutes.
• a sheet of the dried photosoluble film was exposed through a black and white, continuous tone, positive transparency for 5 seconds at 23 inches distance from a high intensity tungsten filament incandescent lamp (General Electric Reflector Photofiood Lamp, No. PH/RFL 2).
• the exposed film was then processed under appropriate safe lights, with all solutions at 70 F.
• the film was then washed in water for 3 minutes and dried in air.
• This latent image by the treatment with the photographic developer solution, was converted to a black, silver, negative-positive image which was superimposed over the earlier formed white, silver chloride, positive image.
• the white silver chloride photolyzed to a brownish color (somewhat pinkish by reflected light).
• the black silver image was actually a negative only at lower exposure levels. As exposure level increased, more and more sllver halide was removed by the treatment with silver halide solvent. Wlth less silver halide available, less metallic silver could be formed and thus the black silver image ap: peared as a positive Image at higher exposure levelsv ditional processing steps which will be described in subsequent examples are capable of yielding many interesting results.
• Example II was repeated through the processing steps of treatment with silver halide solvent (fixing), washing, treatment with photographic developer, and washing, but omitting the final drying. At this point, the film was given a 15 second overall exposure using the same light as in the original, imaging exposure. The film was then treated for 2 minutes in the silver halide solvent solution used earlier but to which had been added 0.1 g. of KI per liter of solution. This was followed by a 3 minute water wash and drying in air.
• Example I The superimposed silver chloride positive image of Example I was thus removed by the extra fixing step and there remained only a black silver image. Highest optical densities of this silver image were found in areas of intermediate exposure while in the highest and'lowest exposure areas there remained only clear gelatin.
• EXAMPLE III A sheet of the photosoluble film prepared in Example I was exposed as in that example except that the exposure time was increased to seconds. The film was then processed at 70 F. starting with a one minute treatment in the silver halide solvent (fixing) solution of Example I and a 3 minute water wash. Then the film containing a positive silver halide image, was developed for one and a half minutes in a color developer solution having pH 11 at 80 F., and of the following formulation:
• the film was given a 15-second flash exposure using the same light source as in the original, imaging exposure. With the remaining silver halide image thus fogged, the film was again developed for one and a half minute in the color developer solution described above to which, this time, there was added 2 g. per liter of a magenta color coupler, 2,4,6- trichlorophenyl-3-p-nitroanilino-Z-pyrazoline 5 one.
• the positive silver halide image was converted to both a black positive metallic silver image and a magenta positive dye image in the areas receiving the lowest image exposure.
• the fixing solution was the same solution of silver halide solvent used in the first processing step following the imaging exposure except for the addition of 0.1 g. KI per liter of solution.
• the bleaching solution had the following formulation:
• Example IV Using another sheet of the photosoluble film of Example I, the processing sequence of Example III was varied by inserting an additional color development step with a yellow coupler. All other processing steps were identical to those described above but following the development with cyan coupler and the related washing step, the film was developed for one and a half minute in the above described color developer solution to which there was added 2 g. per liter of a yellow color coupler, 4 (p-toluenesulfonyl-amino)-w-benzoylacetanilide.
• the processing sequence of this example was repeated except that the transparency through which the original exposure was made was a radiograph of a human head.
• the resultant copy of the radiograph exhibited potential utility for diagnostic purposes because the soft tissue area (corresponding to the high intensity region of the radiograph) was reproduced as magenta and bluish tones while bone areas gave green and clear areas. These color variations were much more apparent than the density variations in the original radiograph,
• Example II was repeated in. all details except for the transparency through which the photosoluble film was given the original, imaging exposure.
• the transparency in this case, was prepared from a lithographic negative and consisted of an image of large, block letters where there was no silver (transparent areas) against a background of black metallic silverof very high optical density.
• the exposure of the photosoluble film through this transparency resulted in highly exposed areas corresponding to the letters and areas of essentially zero exposure corresponding to the background of the transparency. Due to light scattering, there was a very thin line of intermediate exposure surrounding the highly exposed letter areas.
• Treatment with the silver halide solvent caused removal of the silver halide in the highly exposed letter areas. If the film had been examined in white light one would have observed a positive copy of the originaltransparency except that thebackground are-as would have been a white silver chloride image corresponding to the original black silver image. However, the film was kept in the dark while it was treated with the developer solution.
• the silver halide area contained a latent image (thin lines surrounding the transparent letter areas) where light scat- 4 See Footnote 1, Example I.
• Example V was repeated through the steps of exposing, treating with a silver halide solvent to remove silver chloride in the heavily exposed areas, washing, treating with a silver halide reducing agent to develop the latent image (thin black line surrounding the transparent letter areas), and the washing step which followed.
• the process of the present invention is applicable to any unfogged photosoluble element, e.g., as described in Blake, US. 3,155,507.
• Various types of silver halide crystals are disclosed in that patent as being suitable for use in preparing photosoluble elements, although silver chloride and silver chlorobromide are preferred.
• the suitable photosoluble elements may be coated on any of the supports disclosed in US. 3,155,507, and may employ any of the binders, adjuvants, etc. as disclosed in that patent.
• a process which comprises, in the order stated, the sequential steps of (a) exposing a layer containing photosoluble silver halide crystals made relatively less soluble in a silver halide solvent by treatment with an organic compound capable of forming a silver salt of lower solubility in water than silver chloride, to an image producing pattern of actinic radiation so that the layer will have at least:
• a process according to claim 1 wherein the silver halide is silver chloride.
• step (c) is completed the remaining silver halide is toned with a solution containing a mordanting dye.
• step (c) the silver halide is fogged and then treated in a color coupling developer solution.
• step (c) is completed the remaining silver halide is toned with a solution containing a mordanting dye.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Citations (2)

• 1966
  • 1966-04-29 US US546202A patent/US3486895A/en not_active Expired - Lifetime
• 1967
  • 1967-04-28 BE BE697795D patent/BE697795A/xx unknown

Patent Citations (2)

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