US2353661A - Process of obtaining photographic images - Google Patents

Process of obtaining photographic images Download PDF

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Publication number
US2353661A
US2353661A US369123A US36912340A US2353661A US 2353661 A US2353661 A US 2353661A US 369123 A US369123 A US 369123A US 36912340 A US36912340 A US 36912340A US 2353661 A US2353661 A US 2353661A
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silver
image
chloride
emulsion
solution
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US369123A
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Gaspar Bela
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Chromogen Inc
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Chromogen Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor

Definitions

  • My invention relates to the production of photographic images and, more particularly, to the production of photographic reversal images.
  • the silver image first produced is removed either by a solution of sulphuric acid and potassium bichromate or a solution of sulphurie acid and potassium permanganate. Both of these solutions strongly aflect the gelatin, or in the case of a paper support, the paper fiber;
  • an object of my invention to provide on improved method of treatment oithe initial silver image contained in a photographic syer in a reversal process whereby the same may be bleached and removed without the use or strong acidic reactions or energetic oxidizing spouts;
  • Another object of my invention is to provide on improved method of forming reversal images in photographic layers containing a developed silver image in a light-sensitive emulsion and a uniformly distributed substance for coloring which is sensitive to and is destroyed by known bleaching baths having acidic properties.
  • Another object of my invention is to provide such a method wherein the initiel silver image in a reversal process is transformed into a silver salt and afterwards dissolved in a bath by the formation off a complex.
  • a further object of my invention is the pro-. vision of such a method in which the dissolution of the silver salt under complex formation does not result in the dissolution of the remaining silver bromide.
  • My invention will be best understood by an illustration of its application to an emulsion suitably adapted for the production of photographic reversal images.
  • Example 1 After the initial image has been produced in the emulsion by suitable exposure of 'a lightsensitive silver bromide gelatin emulsion and the latent image has been developed, but before the image has been fixed, the emulsion is treated with a mild oxidizing agent, such, for example, as a 540% solution of cupric chloride, which acts to .iorm the developed silver image into silver chloride. The emulsion is then washed, and the silver chloride is dissolved by a medium which does not dissolve silver bromide. For this purpose a saturated solution of sodium chloride is used, and it has been found that this treatment results in the dissolution of the silver chloride in 5 to 20 minutes, depending upon the strength of the image. Alter the silver chloride has been dissolved out, the remaining silver bromide is developed in the usual manner to form the reversal silver imae'e.
  • a mild oxidizing agent such, for example, as a 540% solution of cupric chloride, which acts to .iorm the developed silver image
  • cupric chloride as an oxidizing agent
  • a 2-57, solution of potassium 'ferricyanide containing 2-5% of sodium chloride for the purpose of converting the silver image to a silver salt.
  • mild oxidizing agent characterizes a solution such as copper chloride or a dilute solution or potassium Such SOhl'. tions are indiflerent to the extent that they do not afiect the gelatin emulsion, or the support, or destroy dyes or dyeforming substances formhis part of a photographic material which is treated in the solutions. In addition, they-are indifierent in that they do not sheet the sensitivity of the undeveloped silver'bromideto as great an extent as the conventional. acidic potassium permanganate or bi-chrnmate solutions previously used as bleaches in the reversal process.
  • cupric chloride bleach By the use oi the above cupric chloride bleach and treatment with a concentrated solution or reactions and energetic oxidizing agents.
  • My invention is not limited to'the use of a concentrated sodium chloride solution for the purpose of removing the silver chloride resulting from bleaching the initialsilver image. Any other completely neutral solution of a substance can be used which dissolves the silver chloride under complex formation and leaves the unexposedsilver bromide undissolved.
  • any other mild oxidizing agent could beused which operates to convert 'the silver into a silver salt which is dissolved.
  • th developed silver might be transformed into silver rhodanide inthe well known manner.
  • My invention is equally applicable to a single layer, or to multilayer materials such a multilayer multicolor photographic material. More which transforms the silver image in each of the layers into silver chloride. After washing. the material is treated in a saturated solution of sodium chloride for 10 to 20 minutes. During the treatment the silver chloride is dissolved by the formation of a complex. By this treatment the silver images in each of the layers are removed -ment a multi-color image is obtained. The remaining silver may be removed by treating the material as previously set forth or it can be removed in accordance with the process described in my United States Patent No. 2,042,253 dated May 26, 1938.
  • Example II On a paper support is placed a red sensitized I silver bromide emulsion containing 0.3 g. per
  • the multi-layer material is then treated in a bleaching bath consisting of a 5 to 10% soiution of An uppermost layer -of silver bromide emulsion containing 0.5 g. per
  • cupric chloride for a period of 5 toll) minutes" tity of acetone or methyl alcohol.
  • the reversal treatment preceding the transformation of the silverimagetothedye imagedoesnot oxidizethe leuoo compoundstothedye aswouldresultifthe known acid bichromate andrpermanganate silver bleach solutions were employed.
  • a method of producing a reversal dye image in a light-sensitive silver halide emulsion containing a developed silver'image and an easily destroyable coloring substance distributed uniformly therein which comprises the steps of treating said emulsion with a mild oxidizing agent which convert said developed image to a/ silver salt image other than the silver halide comprising said light sensitive emulsion without destroying the uniformly distributed coloring substance and complex without ailecting the undeveloped silver bromide or destroying the coloring substance.
  • a method of producing a reversal dye image in a light-sensitive silver bromide emulsion containing a developed silver image and an easily destroyable coloring substance distributed uniformly therein which comprises the steps of treating said emulsion with a solution of cupric chlosubsequently treating the silver salt image with I ,stroying the uniformly distributed coloring substance and subsequently treating the silver salt image with a completely neutral solution comprisin: a saturated solution of sodium chloride to ride to produce a silver chloride image without destroying the uniformly distributed coloring substance and subsequently treating the silver chloride image with a completely neutral solution comprising a saturated solution of sodium chloride to dissolve the silver chloride image by formation of a complex without affecting the undeveloped silver bromide or destroying the coloring substance.
  • a method of producing a reversal dye image in a light-sensitive silverbromide emulsion containing. a developed silver image and an easily destroyabie coloring substance distributed uniformly therein which comprises the steps of treating aid emulsion with a solution of potassium. ferricyanide and sodium chloride to bleach said image by forming a silver chloride. image without destroying the uniformly distributed coloring substance and subsequently treating the silver chloride image with a completely neutral concentrated solution of alkali chloride to dissolve the silver chloride image by formation of a complex without affecting the undeveloped silver bromide or destroying the coloring substance.
  • a method Of producing a reversal dye image in a light-sensitive silver'bromide emulsion condissolve the silver salt image by formation of a taining a developed silver image and an-easlly destroyable coloring substance distributed uniformly therein which comprises the steps of treating said emulsion with a solution of'potasslum ferricyanide and sodium chloride to bleach said "imag by forming a silver chloride image withoutdestroying the uniformly distributed coloring substance and subsequently treating the silver chloride image with a completely neutral salt solution comprising a concentrated solution of sodium chloride to dissolve the silver salt image by formation of a complex without affecting the undeveloped silver bromide or destroying the coloring substance.

Description

?etented' duly 3% l9 2,353,661 success or on'rsmmo enoroensrmo muons Bla Gaspfir, Hollywood, Calif asslgnor to Chromozen, Incorporated, a corporation of Nevada No Drawini', Application December 1, 1940,
Serial No 369,123
5 Claims.
My invention relates to the production of photographic images and, more particularly, to the production of photographic reversal images.
It is common practice to produce photographic reversal images from a suitable emulsion of lightsensitive silver bromide by exposing a portion of it to produce a latent image therein, developing this image, and then, without firing the image, removing the developed x'netallic silver deposit by an oxidizing agent without removing the unexposed silver bromide. The remaining silver bromide is then blackened by exposing it and developing it, or it may be converted by a chemical agent, such for example as sodium hydrosulphite.
In the known processes for the production of reversal images, the silver image first produced is removed either by a solution of sulphuric acid and potassium bichromate or a solution of sulphurie acid and potassium permanganate. Both of these solutions strongly aflect the gelatin, or in the case of a paper support, the paper fiber;
- furthermore, they affect other substances such as sensitive and easily destroyable substances for colcrine that may be contained in theemulsion. More particularly, they may aiiect dyes serving as filter dyes, sensitizing dyes or dyes serving later on in the process for the production of dye im-' ages. Likewise, in the case where a dye forming substance is used in the'emulsion, they may affect the dye forming substance.
it is, therefore, an object of my invention to provide on improved method of treatment oithe initial silver image contained in a photographic syer in a reversal process whereby the same may be bleached and removed without the use or strong acidic reactions or energetic oxidizing spouts;
Another object of my invention is to provide on improved method of forming reversal images in photographic layers containing a developed silver image in a light-sensitive emulsion and a uniformly distributed substance for coloring which is sensitive to and is destroyed by known bleaching baths having acidic properties.
Another object of my invention is to provide such a method wherein the initiel silver image in a reversal process is transformed into a silver salt and afterwards dissolved in a bath by the formation off a complex.
Another object oi my invention is to provide such a method'oi forming reversal imageswhere-= in'the initial silver image of a layer is treated to form 2. silver salt and the silver salt is later -dis= solved by the formation or a complex without deferricyanide and sodium chloride.
straying or deleteriously affecting the coloring substance employed in the layer.
A further object of my invention is the pro-. vision of such a method in which the dissolution of the silver salt under complex formation does not result in the dissolution of the remaining silver bromide.
These and other objects of my invention will appear as the description proceeds, and its scope will be pointed out in the claims appended hereto.
My invention will be best understood by an illustration of its application to an emulsion suitably adapted for the production of photographic reversal images.
, Example 1 After the initial image has been produced in the emulsion by suitable exposure of 'a lightsensitive silver bromide gelatin emulsion and the latent image has been developed, but before the image has been fixed, the emulsion is treated with a mild oxidizing agent, such, for example, as a 540% solution of cupric chloride, which acts to .iorm the developed silver image into silver chloride. The emulsion is then washed, and the silver chloride is dissolved by a medium which does not dissolve silver bromide. For this purpose a saturated solution of sodium chloride is used, and it has been found that this treatment results in the dissolution of the silver chloride in 5 to 20 minutes, depending upon the strength of the image. Alter the silver chloride has been dissolved out, the remaining silver bromide is developed in the usual manner to form the reversal silver imae'e.
Instead oi using cupric chloride as an oxidizing agent, I might use a 2-57,) solution of potassium 'ferricyanide containing 2-5% of sodium chloride for the purpose of converting the silver image to a silver salt. In this specification the term mild oxidizing agent" characterizes a solution such as copper chloride or a dilute solution or potassium Such SOhl'. tions are indiflerent to the extent that they do not afiect the gelatin emulsion, or the support, or destroy dyes or dyeforming substances formhis part of a photographic material which is treated in the solutions. In addition, they-are indifierent in that they do not sheet the sensitivity of the undeveloped silver'bromideto as great an extent as the conventional. acidic potassium permanganate or bi-chrnmate solutions previously used as bleaches in the reversal process.
By the use oi the above cupric chloride bleach and treatment with a concentrated solution or reactions and energetic oxidizing agents.
My invention is not limited to'the use of a concentrated sodium chloride solution for the purpose of removing the silver chloride resulting from bleaching the initialsilver image. Any other completely neutral solution of a substance can be used which dissolves the silver chloride under complex formation and leaves the unexposedsilver bromide undissolved. In the same manner, instead of using a solution of cupric chloride or potassium ferricyanide and sodium chloride for" the purpose of converting the silver image into a silver chloride image, any other mild oxidizing agent could beused which operates to convert 'the silver into a silver salt which is dissolved.
more readily under complex formation than silver bromide. For example, th developed silver might be transformed into silver rhodanide inthe well known manner.
All of these solutions have the common property that they'do not affect the gelatin. Likewise,- -if the emulsion is coated on a paper support, they do notaifect the paper fiber. Furthermore, the practice of the process comprised in my invention has the added advantage that'the sensitivity of the silver bromide is-influenced to a smaller extent than it would be in the case of treatment with bichromate or permanganate. It is, therefore, especially suitable in those photographic processes where the emulsion is again exposed prior to the second development.
My invention is equally applicable to a single layer, or to multilayer materials such a multilayer multicolor photographic material. More which transforms the silver image in each of the layers into silver chloride. After washing. the material is treated in a saturated solution of sodium chloride for 10 to 20 minutes. During the treatment the silver chloride is dissolved by the formation of a complex. By this treatment the silver images in each of the layers are removed -ment a multi-color image is obtained. The remaining silver may be removed by treating the material as previously set forth or it can be removed in accordance with the process described in my United States Patent No. 2,042,253 dated May 26, 1938.
- Example III A silver bromide layer containing uniformly distributed therein 1 g. per square meter of the particularly, it is applicable to emulsions containing coloring substances distributed uniformly therein which coloring substances are defined for ed claims as dyes..or dye-forming substances such asthose used for color development or for the color-forming substances, the full advantages of my improved method are realized in that the silver image can be converted into a reversal im-' age without affecting these dyes or color-forming substances as is disclosed in the following examples: 7
Example II On a paper support is placed a red sensitized I silver bromide emulsion containing 0.3 g. per
square meter of Diamine Pure Blue F.
' the purposes of this specification and the appendsulfate ester salt of the leuco-compound of (A) hexa-brom-indigo or (B) 6.6"di-brom-dimethylbis-thionaphthene indigo is coated on a reflecting or transparent support. The material is exposed by printing through a negative or by direct exposure in a camera. The material is then treated in accordance with Example I except that after the second development the dye image-is formed by the methods disclosed in my United States Reissue Patent No. 21,513 granted July 23, 1940. More particularly, I prefer to transform the silver image into a dye image by the use of a fresh solution consisting of 1/10% potassium bichromate and 1% of hydrobromic acid. After 5'to 10 minutes treatment a reversal blue dye image is formed in the layer if the material contains the compound designated by (A) and a reversal magenta dye' image will be formed in the layer if it contains the compoimd designated by (B). After this treatment th silver and also the unused leucocom'poundisranovedinanalkalinetreat- -ingbathpreferablyonecontainingasmallquan- (Schultz-seventh edition, 170.511) distributed uniformly therein and a green sensitized silverbromide emulsion is placed on top thereof containing 0.4 g. per square meter of Sirius-Rubin B (Ullmann-Enzyklop'idie der Technischen Chemie, vol. 9, page 524).
' posed through color separation negatives and the silver images developed in each of the layers. The multi-layer material is then treated in a bleaching bath consisting of a 5 to 10% soiution of An uppermost layer -of silver bromide emulsion containing 0.5 g. per
cupric chloride for a period of 5 toll) minutes" tity of acetone or methyl alcohol. The reversal treatment preceding the transformation of the silverimagetothedye imagedoesnot oxidizethe leuoo compoundstothedye aswouldresultifthe known acid bichromate andrpermanganate silver bleach solutions were employed.
.Emnrple IV I 'Example 1. The second development is carried on with the following color-forming developing solution:
Diethyl pars-phenylen dlamine -g 1 Sodiumcarbonate (anhydrous g 20 Sodiumsulflte g .0 water or 1,000
By this treatment a reversed magenta dye image and asilver imageis formedrAfter washing, the
silver-imueis removed y treating't c tain methods embraced therein for the purpose of explaining its principle and its application, but it will be obvious to those skilled in the art that many modifications and variations are possible. I aim, therefore, to cover all such modifications and variation as fall within the scope of my invention which is defined in the appended claims.
What I claim is:
l. A method of producing a reversal dye image in a light-sensitive silver halide emulsion containing a developed silver'image and an easily destroyable coloring substance distributed uniformly therein, which comprises the steps of treating said emulsion with a mild oxidizing agent which convert said developed image to a/ silver salt image other than the silver halide comprising said light sensitive emulsion without destroying the uniformly distributed coloring substance and complex without ailecting the undeveloped silver bromide or destroying the coloring substance.
3. A method of producing a reversal dye image in a light-sensitive silver bromide emulsion containing a developed silver image and an easily destroyable coloring substance distributed uniformly therein, which comprises the steps of treating said emulsion with a solution of cupric chlosubsequently treating the silver salt image with I ,stroying the uniformly distributed coloring substance and subsequently treating the silver salt image with a completely neutral solution comprisin: a saturated solution of sodium chloride to ride to produce a silver chloride image without destroying the uniformly distributed coloring substance and subsequently treating the silver chloride image with a completely neutral solution comprising a saturated solution of sodium chloride to dissolve the silver chloride image by formation of a complex without affecting the undeveloped silver bromide or destroying the coloring substance.
4. A method of producing a reversal dye image in a light-sensitive silverbromide emulsion containing. a developed silver image and an easily destroyabie coloring substance distributed uniformly therein, which comprises the steps of treating aid emulsion with a solution of potassium. ferricyanide and sodium chloride to bleach said image by forming a silver chloride. image without destroying the uniformly distributed coloring substance and subsequently treating the silver chloride image with a completely neutral concentrated solution of alkali chloride to dissolve the silver chloride image by formation of a complex without affecting the undeveloped silver bromide or destroying the coloring substance.
5. A method Of producing a reversal dye image in a light-sensitive silver'bromide emulsion condissolve the silver salt image by formation of a taining a developed silver image and an-easlly destroyable coloring substance distributed uniformly therein, which comprises the steps of treating said emulsion with a solution of'potasslum ferricyanide and sodium chloride to bleach said "imag by forming a silver chloride image withoutdestroying the uniformly distributed coloring substance and subsequently treating the silver chloride image with a completely neutral salt solution comprising a concentrated solution of sodium chloride to dissolve the silver salt image by formation of a complex without affecting the undeveloped silver bromide or destroying the coloring substance.
ism-A GAsPAR.
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