US3816133A - Process for the production of photographic images by modifying vesicular images - Google Patents

Process for the production of photographic images by modifying vesicular images Download PDF

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Publication number
US3816133A
US3816133A US00222971A US22297172A US3816133A US 3816133 A US3816133 A US 3816133A US 00222971 A US00222971 A US 00222971A US 22297172 A US22297172 A US 22297172A US 3816133 A US3816133 A US 3816133A
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image
images
silver
layer
light
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US00222971A
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English (en)
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E Weyde
M Scheibitz
R Meyer
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/60—Processes for obtaining vesicular images

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  • ABSTRACT Photographic images are produced by forming in a light-sensitive photographic layer a vesicular image which subsequently is transformed by treatment with a swelling agent for the binder into a stable image consisting of differences in the refractive index; the latter image can be made visible by suitable optical means.
  • vesicular images by using a photographic material having a light-sensitive layer in which are dispersed compounds decomposable by light, such as diazonium salts. Upon imagewise exposure the light-sensitive compound is decomposed at the light-struck areas and a gas is evolved. Subsequent heating of the material causes the evolved gas to expand and an image formed by small bubbles is proluded. The vesicular image thus produced causes dispersion of light at the bright-parts of the image while the unilluminated parts largely transmit light. A bubble image therefore appears dark in transmitted light but bright on viewing by' reflected light.
  • layers can be used in the above proce'ss for the production of photographic images which contain compounds capable of forming upon exposure catalase active or peroxidase active catalysts.
  • compounds capable of forming upon exposure catalase active or peroxidase active catalysts For example, certain complex compounds of heavy metals of groups VI b, Vllb or VIII of The Periodic Table of the elements with a monoor poly-basic carboxylic acid are suitable for this purpose. Compounds that on exposure split off iodine or iodide ions have the same effect.
  • light-sensitive photographic materials can also be used containing uniformly distributed, catalase active enzymes or peroxidase active ferments such as catalase, peroxidase, haemoglobin or haemin, which are deactivated on exposure to actinic light. With the said of such materials direct positive images are obtained.
  • capes at least partly through swelling of the layer caused by moisture so that an undesired decrease in density is observed.
  • the optical inhomogeneities arising on elimination of the bubble image may consist of an internal or external wrinkling of the emulsion in accordance with the im age.
  • external wrinkling is meant the phenomenon well known in photography in which the surface of the photographic emulsion does not stay even but is divided up by microscopically small elevations and depressions.
  • inhomogeneities in the refractive index arise as a result of incomplete elimination of the bubble image so that some cavities remain even after prolonged treatment with swelling agents.
  • FIGS. 1 Two possible arrangements of this type are shown in FIGS. 1 3.
  • FIG. 1 shows schematically the reproduction of a schlieren transparency by the Toepler schlieren method.
  • the optical arrangement consists of a light source 1, a condenser 2, a diaphragm 3, a lens 4 in the present case the so-called schlieren head behind which the object to be exposed 5 (schlieren object) is placed. Behind this is the screen or cut-off and an objective 6.
  • the object reproduced on the dark background is indicated by 7.
  • FIG. 2 is a schematic representation of the so-called oblique illuminations method. Elements 1 6 have the same meaning as in FIG. 1. Here too the image 7 appears on the dark background.
  • FIG. 3 another possibility of making visible the op tical inhomogeneities is schematically described.
  • the so-called shadow projection is applied.
  • Light from a source 1 passes through a condenser 2 and a diaphragm 3 and then through the object 5.
  • a shadow image 8 of the object is reproduced on a bright background, unlike both the above mentioned methods. This is caused by the irregular diversion of the transmitted light at the imagewise distributed inhomogeneities in the layer; the shadow image therefore appears darker than theparts of the layer through which the light has passed regularly. The image thus appears dark on a white background.
  • the vesicular images prepared as described in US. Pat. No. 3,615,491 are particularly suitable for the process of the present invention. These are based on lightsensitive silver salt emulsions, especially silver halide emulsions. Either silver chloride or silver bromide emulsions or mixtures thereof, possibly containing up to about mol percent silver iodide, are suitable.
  • the emulsions may contain the silver halide in either fine or coarse grained form, as in the case of ammonia emulsions for example, gelatin or other natural or synthetic film formers or mixtures thereof can be used as binding agents.
  • the photographic materials containing such emulsion layers are imagewise exposed in the usual way, developed and fixed.
  • the silver images thus produced are treated with a compound that is decomposed at the silver image with the formation of gaseous products.
  • Hydrogen peroxide is expecially suitable for use as decomposable com pound.
  • the treatment with the compound especially hydrogen peroxide, whichproduces the small bubbles can be performed in very different ways.
  • the layer of emulsion containing the developed silver image can be coated with a new layer containing hydrogen peroxide, for example with a solution .of polyvinylchloride in butanone-(2) containing hydrogen peroxide. The coating is then dried and the bubbles produced by heating.
  • the developed photographic emulsion can also be treated with a solution of hydrogen peroxide, e.g. an alcoholic solution.
  • the best method is to treat the photographic emulsion with gaseous hydrogen peroxide. After about seconds exposure to asaturated hydrogen peroxide vapour the emulsion has taken up sufficient hydrogen peroxide.
  • the time depends on the temperature and concentration of the hydrogen peroxide vapour. For example, temperature of 50 90C are suitable.
  • the developed layer of silver halide emulsion is exposed, after treatment with hydrogen peroxide vapour for about 1 5 seconds, to a steam atmosphere at about 50 4 90C.
  • the intensifying effect which by treatment with hydrogen peroxide alone can be brought about only relatively slowly, occurs very rapidly.
  • a pH in the range of fromv 8 to 12 is suitable. This can easily be brought about by adding small amounts of ammonia or volatile amines to the steam.
  • concentration of the alkaline additives is not critical; in general amounts of from 0.1 to 5 percent by volume, preferably from 0.3 to 1 vol-%, have proved adequate.
  • the production of the visible small bubbles is brought about by expansion of the gaseous reaction products first formed. This is caused by heating to temperatures between 60 and 100C. Production of the bubbles is reinforced by slight softening of the emulsion, for example by moistening. This effect is achieved by the treatment with steam described above. This also has the effect of producing aparticularly favourable type of bubble.
  • the bubbles are very small and the images produced from them therefore havea very high density.
  • the images obtained by this process consist of a silver imagewith a rather low density and of a bubble image coinciding with the silver image.
  • the bubble image disappears with the onset of swelling of the emulsion.
  • the original silver image again appears. If this film is dried, no difference can be detected, by ordinary observation, as compared with the original silver image.
  • an image such as that described is placed in the path of the rays of a suitable optical reproduction system, then the parts of the image which previously contained the bubbles and at which inhomogeneities of the refractive index are-now present, appear either dark on a white background or vice versa, according to the optical means.
  • the layer containing the lowdensity silver image was coatedby means of a liquid-coating roller with a solution of the following composition:
  • the layer was run through a heating zone which dried the layer and at the same time heated the film sufficiently to yield a vesicle image with a total density of 2.0. Then the emulsion was wetted with water for long enough to make the bubble image disappear and the film was dried.
  • EXAMPLE 2 A light-sensitive photographic material with a layer of silver halide emulsion of the type described in Example l but which contained as a binder a mixture of gelatin and the propylene glycol ester of alginic acid in the ratio 1:1, was treated as described in the previous example. A faint silver image with a maximum density of S 0.32 was obtained. After drying briefly, the only slightly swollen emulsion was further treated as follows:
  • the bubble image was then treated with an aqueous bath and the silver image was bleached in a potassium ferricyanide toning bath, washed and dried.
  • EXAMPLE 3 A photographic material with a silver bromide emulsion on a cellulose acetate support, which emulsion calculated on the silver halide contained 3.5 mol-% silver iodide and the silver content of which was 0.2 g silver in the form of silver halide per qm, was imagewise exposed and developed in a developer of the following composition:
  • a negative of the original was obtained having a maximum silver density of 0.25.
  • binding agent can be used for the process of the invention. Those that swell on treatment with water are particularly useful, since the bubble image can easily be eliminated. Gelatin is especially preferred as binding agent but it can be completely or partially replaced by other binders that can be swollen by water, such as alginic acid or its derivatives such as salts, amides or esters, as well as cellulose derivates, like carboxyalkylcellulose, carraghenate, starch or similar materials.
  • a process for the production of photographic images by imagewise exposure of a supported layer consisting of a water-swellable binding agent and a lightsensitive silver salt, developing the exposed layer to form a metallic silver image, treating the layer containing the silver image with a peroxide compound, heating the said layer to decompose the peroxide and to form vesicles coinciding with the silver image
  • the improvement comprises treating the vesicle containing layer in the presence of a swelling agent selected from the group consisting of water and steam for the binder to eliminate the vesicle image and produce an optical inhomogeneity coinciding with the image at those portions of the layer so that at least one portion of the layer has a refractive index that deflects light passed through the layer, and exposing the layer containing the optical inhomogeneity to light under such conditions that part of the light transmitted through the layer is distributed by the deflecting refractive index and irregularly diverted from its regular direction and forming a visible image on a screen by means of said irregularly diverted light

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US00222971A 1971-02-05 1972-02-02 Process for the production of photographic images by modifying vesicular images Expired - Lifetime US3816133A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19712105488 DE2105488A1 (de) 1971-02-05 1971-02-05 Verfahren zur Herstellung photographischer Bilder

Publications (1)

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US3816133A true US3816133A (en) 1974-06-11

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US (1) US3816133A (enrdf_load_stackoverflow)
BE (1) BE778772A (enrdf_load_stackoverflow)
DE (1) DE2105488A1 (enrdf_load_stackoverflow)
FR (1) FR2124503B1 (enrdf_load_stackoverflow)
GB (1) GB1373432A (enrdf_load_stackoverflow)
IT (1) IT948421B (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977875A (en) * 1970-03-13 1976-08-31 Ciba-Geigy Ag Method for modifying vesicular images
US4065312A (en) * 1974-04-19 1977-12-27 Agfa-Gevaert, A.G. Process for the production of photographic vesicular images in photographic silver halide material
US4260674A (en) * 1974-04-19 1981-04-07 Agfa-Gevaert Aktiengesellschaft Silver salt photographic material for the production of silver and bubble photographic images with 80% transparency
US4569903A (en) * 1980-02-11 1986-02-11 Fuji Photo Film Co., Ltd. Optical recording medium
US20090272560A1 (en) * 2006-12-21 2009-11-05 Fujifilm Corporation Conductive film and method of producing thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB402737A (en) * 1932-03-04 1933-12-07 Kalle & Co Ag Manufacture of negative copies
GB645825A (en) * 1945-09-26 1950-11-08 Gen Aniline & Film Corp Photographic vesicular images and process of making same
US2911299A (en) * 1952-07-22 1959-11-03 Kalvar Corp System of photographic reproduction
US3298833A (en) * 1960-12-30 1967-01-17 Gen Electric Method for storing information
US3316088A (en) * 1963-02-11 1967-04-25 Ibm Process of electrophotography based on electrophotolytic reactions and element therefor
US3549376A (en) * 1967-11-02 1970-12-22 Du Pont Image-forming compositions containing polymer binding agents and coordination complexes of iron (iii) organic salts
US3594166A (en) * 1965-01-08 1971-07-20 Agfa Gevaert Ag Process for producing copies by image-wise heating
US3615491A (en) * 1967-12-23 1971-10-26 Agfa Gevaert Ag Photographic images
US3615476A (en) * 1965-06-01 1971-10-26 Agfa Gevaert Nv Method for recording and reproducing information by surface deformation of a polymeric composition
US3684511A (en) * 1969-12-05 1972-08-15 Agfa Gevaert Ag Method of forming vesicular images with peroxidase active,iodide ions generating compounds
US3694207A (en) * 1969-11-06 1972-09-26 Agfa Gevaert Ag Treatment of imagewise exposed catalase active or peroxidase active enzyme containing layer with peroxide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL287343A (enrdf_load_stackoverflow) * 1962-01-02

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB402737A (en) * 1932-03-04 1933-12-07 Kalle & Co Ag Manufacture of negative copies
GB645825A (en) * 1945-09-26 1950-11-08 Gen Aniline & Film Corp Photographic vesicular images and process of making same
US2911299A (en) * 1952-07-22 1959-11-03 Kalvar Corp System of photographic reproduction
US3298833A (en) * 1960-12-30 1967-01-17 Gen Electric Method for storing information
US3316088A (en) * 1963-02-11 1967-04-25 Ibm Process of electrophotography based on electrophotolytic reactions and element therefor
US3594166A (en) * 1965-01-08 1971-07-20 Agfa Gevaert Ag Process for producing copies by image-wise heating
US3615476A (en) * 1965-06-01 1971-10-26 Agfa Gevaert Nv Method for recording and reproducing information by surface deformation of a polymeric composition
US3549376A (en) * 1967-11-02 1970-12-22 Du Pont Image-forming compositions containing polymer binding agents and coordination complexes of iron (iii) organic salts
US3615491A (en) * 1967-12-23 1971-10-26 Agfa Gevaert Ag Photographic images
US3694207A (en) * 1969-11-06 1972-09-26 Agfa Gevaert Ag Treatment of imagewise exposed catalase active or peroxidase active enzyme containing layer with peroxide
US3684511A (en) * 1969-12-05 1972-08-15 Agfa Gevaert Ag Method of forming vesicular images with peroxidase active,iodide ions generating compounds

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Nieset, R. T., The Journal of Photographic Science, 1962, pp. 188 195. *
The Focal Encyclopedia , Vol. II, The Focal Press, 1965, pp. 319 320. *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977875A (en) * 1970-03-13 1976-08-31 Ciba-Geigy Ag Method for modifying vesicular images
US4065312A (en) * 1974-04-19 1977-12-27 Agfa-Gevaert, A.G. Process for the production of photographic vesicular images in photographic silver halide material
US4260674A (en) * 1974-04-19 1981-04-07 Agfa-Gevaert Aktiengesellschaft Silver salt photographic material for the production of silver and bubble photographic images with 80% transparency
US4569903A (en) * 1980-02-11 1986-02-11 Fuji Photo Film Co., Ltd. Optical recording medium
US20090272560A1 (en) * 2006-12-21 2009-11-05 Fujifilm Corporation Conductive film and method of producing thereof
US7985527B2 (en) * 2006-12-21 2011-07-26 Fujifilm Corporation Conductive film and method of producing thereof

Also Published As

Publication number Publication date
DE2105488A1 (de) 1972-08-10
GB1373432A (en) 1974-11-13
BE778772A (nl) 1972-08-01
FR2124503A1 (enrdf_load_stackoverflow) 1972-09-22
FR2124503B1 (enrdf_load_stackoverflow) 1977-04-01
IT948421B (it) 1973-05-30

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